JP4399633B2 - Processing method of workpiece - Google Patents
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- JP4399633B2 JP4399633B2 JP2004080829A JP2004080829A JP4399633B2 JP 4399633 B2 JP4399633 B2 JP 4399633B2 JP 2004080829 A JP2004080829 A JP 2004080829A JP 2004080829 A JP2004080829 A JP 2004080829A JP 4399633 B2 JP4399633 B2 JP 4399633B2
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- 238000003672 processing method Methods 0.000 title description 7
- 229910052709 silver Inorganic materials 0.000 claims description 128
- 239000004332 silver Substances 0.000 claims description 128
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 123
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 111
- 238000002386 leaching Methods 0.000 claims description 102
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 93
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 78
- 229910017604 nitric acid Inorganic materials 0.000 claims description 78
- 229910052737 gold Inorganic materials 0.000 claims description 59
- 239000010931 gold Substances 0.000 claims description 59
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 57
- 238000000034 method Methods 0.000 claims description 37
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 229910052802 copper Inorganic materials 0.000 claims description 25
- 239000010949 copper Substances 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 17
- 238000005868 electrolysis reaction Methods 0.000 description 33
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 28
- 229910052697 platinum Inorganic materials 0.000 description 16
- 229910052763 palladium Inorganic materials 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 7
- 241000557876 Centaurea cineraria Species 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 150000002343 gold Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000010946 fine silver Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003378 silver Chemical class 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)
Description
本発明は、金、銀及び白金族元素を含有する銀電解スライム等の被処理物から、銀及び白金族元素を回収する被処理物の処理方法に関する。 The present invention relates to a processing method for a processing object for recovering silver and platinum group elements from a processing object such as silver electrolytic slime containing gold, silver and platinum group elements.
以下、被処理物として銀スライムを用いた場合を例として背景技術について説明する。
銀の精製工程において生じた銀電解スライムには、金、銀、及び白金族元素(白金やパラジウム等)が濃縮されている。そこで、この銀電解スライムを硝酸浸出(パーチング;分金)処理して、銀電解スライム中の銀及び白金族元素を硝酸に浸出させ、一方、浸出残渣から製造された金電解用アノードを用いて金電解により金を精製している。
Hereinafter, the background art will be described by taking as an example the case where silver slime is used as an object to be processed.
Gold, silver, and platinum group elements (platinum, palladium, etc.) are concentrated in the silver electrolysis slime generated in the silver refining process. Therefore, this silver electrolysis slime was subjected to nitric acid leaching (parting), and silver and platinum group elements in the silver electrolysis slime were leached into nitric acid, while using an anode for gold electrolysis produced from the leaching residue. Gold is refined by gold electrolysis.
ところが、銀電解スライム中の銀や白金族元素の含有量が多くなると、従来の硝酸浸出処理において銀及び白金族元素が硝酸に十分に浸出されず、浸出残渣中に相当量残ってしまう。このため、金電解工程において、上記浸出残渣から製造される金電解用アノードから、銀はスライムとなり、白金族元素は金電解液中に溶出してしまう。その結果、金電解液中から金以外の不純物金属元素、この場合には銀及び白金族元素を除去する浄液の負荷が増大すると共に、金電解液中に白金族元素が滞留することによって、滞留金利が上昇してしまう。 However, when the content of silver and platinum group elements in the silver electrolytic slime increases, silver and platinum group elements are not sufficiently leached in nitric acid in the conventional nitric acid leaching treatment, and a considerable amount remains in the leaching residue. For this reason, in the gold electrolysis process, silver becomes slime from the anode for gold electrolysis produced from the leaching residue, and the platinum group element is eluted in the gold electrolyte. As a result, the load of the cleaning solution for removing impurity metal elements other than gold from the gold electrolyte, in this case, silver and platinum group elements increases, and the platinum group elements stay in the gold electrolyte, The staying interest rate will rise.
ここで、銀電解スライムから金、銀及び白金族元素を回収する方法として、銀電解スライムの硝酸浸出後、浸出残渣を塩酸浸出するものが特許文献1に記載されている。また、銀電解スライム中の白金族元素を、塩酸及び過酸化水素を用いて金と共に溶解し、金のみを後に還元して析出させるものが特許文献2に記載されている。 Here, as a method for recovering gold, silver, and platinum group elements from silver electrolytic slime, Patent Document 1 discloses that a leaching residue is leached after hydrochloric acid leaching of silver electrolytic slime. Further, Patent Document 2 discloses that a platinum group element in silver electrolysis slime is dissolved together with gold using hydrochloric acid and hydrogen peroxide, and only gold is reduced and precipitated later.
しかしながら、特許文献1に記載の方法は浸出処理の際、硝酸のほかに塩酸も使用するため、薬剤の使用量が増し、しかも、2つの浸出処理を実施するため処理に長時間を要し、コストが上昇してしまう。 However, since the method described in Patent Document 1 uses hydrochloric acid in addition to nitric acid during the leaching process, the amount of the drug used increases, and the two leaching processes require a long time for the treatment, Cost will rise.
また、特許文献2に記載の方法は、塩酸及び過酸化水素を使用するため、薬剤の使用量が増し、しかも、後に金を析出させるなどの処理が煩雑で処理に長時間を要するため、コストが上昇してしまう。 In addition, since the method described in Patent Document 2 uses hydrochloric acid and hydrogen peroxide, the amount of chemicals used increases, and the treatment such as the subsequent deposition of gold is complicated and requires a long time for the treatment. Will rise.
本発明の目的は、上述の事情を考慮してなされたものであり、金、銀及び白金族元素を含有する銀スライム等の被処理物から、銀及び白金族元素を低コストで回収できる被処理物の処理方法を提供することにある。 The object of the present invention has been made in view of the above circumstances, and is capable of recovering silver and platinum group elements at a low cost from an object to be treated such as silver slime containing gold, silver and platinum group elements. The object is to provide a method for processing a processed product.
課題を解決するための第1の手段は、金、銀及び白金族元素を含有する被処理物と硝酸とを槽内で反応させて、被処理物中の銀及び白金族元素を硝酸に浸出して回収する被処理物の処理方法であって、
被処理物と硝酸との反応により発生する窒素酸化物を槽内に充満させた状態で、被処理物中の銀及び白金族元素を硝酸に浸出させることを特徴とする被処理物の処理方法である。
The first means to solve the problem is to react the object to be processed containing gold, silver and platinum group elements with nitric acid in the tank, and leaching the silver and platinum group elements in the object to be processed into nitric acid. A processing method of a workpiece to be collected,
A method for treating an object to be treated, which comprises leaching silver and platinum group elements in an object to be treated into nitric acid in a state where nitrogen oxides generated by the reaction between the object to be treated and nitric acid are filled in the tank. It is.
第2の手段は、金、銀及び白金族元素を含有する被処理物と硝酸とを反応させて、被処理物中の銀及び白金族元素を硝酸に浸出して回収する被処理物の処理方法であって、
被処理物と硝酸との反応中に、窒素酸化物の発生を促進する金属を添加することを特徴とする被処理物の処理方法である。
The second means is a treatment of an object to be processed which reacts an object to be processed containing gold, silver and a platinum group element with nitric acid, and leaches and recovers silver and platinum group element in the object to be processed in nitric acid. A method,
A method for treating an object to be treated is characterized by adding a metal that promotes the generation of nitrogen oxides during the reaction between the object to be treated and nitric acid.
第3の手段は、金、銀及び白金族元素を含有する被処理物と硝酸とを槽内で反応させて、被処理物中の銀及び白金族元素を硝酸に浸出して回収する被処理物の処理方法であって、
被処理物と硝酸との反応中に、窒素酸化物の発生を促進する金属を添加し、被処理物と硝酸との反応により発生する窒素酸化物を槽内に充満させた状態で、被処理物中の銀及び白金族元素を硝酸に浸出させることを特徴とする被処理物の処理方法である。
The third means is to treat the object to be treated containing gold, silver and platinum group elements and nitric acid in the tank, and leaching and recovering silver and platinum group elements in the object to be treated by nitric acid. A processing method of an object,
During the reaction between the object to be treated and nitric acid, a metal that promotes the generation of nitrogen oxide is added, and the tank is filled with nitrogen oxide generated by the reaction between the object to be treated and nitric acid. A processing method for an object to be processed, characterized in that silver and platinum group elements in the object are leached into nitric acid.
第4の手段は、第2または第3の手段に記載の発明において、上記窒素酸化物の発生を促進する金属が、銅および/または銀であることを特徴とする被処理物の処理方法である。 A fourth means is a method for treating an object to be treated according to the invention described in the second or third means, wherein the metal that promotes the generation of nitrogen oxides is copper and / or silver. is there.
第5の手段は、第1から第4のいずれかに記載の手段において、上記被処理物と硝酸との反応終了後に酸素を投入して、窒素酸化物を分解することを特徴とするものである。 A fifth means is characterized in that, in the means according to any one of the first to fourth aspects, oxygen is introduced after the reaction between the object to be treated and nitric acid is completed to decompose nitrogen oxides. is there.
第1の手段によれば、被処理物と硝酸との反応により発生する窒素酸化物を槽内に充満させた状態で、被処理物中の銀及び白金族元素を硝酸に浸出させることから、上記窒素酸化物の作用により、被処理物からの銀及び白金族元素の浸出率を向上させることができる。このため、被処理物中の銀及び白金族元素を、他の薬剤を用いることなく、しかも短時間に回収でき、回収コストを低減できる。 According to the first means, the silver and platinum group elements in the object to be treated are leached into nitric acid in a state in which the tank is filled with nitrogen oxide generated by the reaction between the object to be treated and nitric acid. The leaching rate of silver and platinum group elements from the object to be processed can be improved by the action of the nitrogen oxide. For this reason, silver and platinum group elements in the object to be processed can be recovered in a short time without using other chemicals, and the recovery cost can be reduced.
第2の手段によれば、被処理物と硝酸との反応中に、窒素酸化物の発生を促進する金属を添加することから、この反応中に窒素酸化物の発生量が増加することから、上記窒素酸化物の作用により、被処理物からの銀及び白金族元素の浸出率を向上させることができる。このため、被処理物中の銀及び白金族元素を、他の薬剤を用いることなく、しかも短時間に回収でき、回収コストを低減できる。 According to the second means, since the metal that promotes the generation of nitrogen oxides is added during the reaction between the object to be treated and nitric acid, the amount of nitrogen oxides generated during this reaction increases. The leaching rate of silver and platinum group elements from the object to be processed can be improved by the action of the nitrogen oxide. For this reason, silver and platinum group elements in the object to be processed can be recovered in a short time without using other chemicals, and the recovery cost can be reduced.
第3の手段によれば、被処理物と硝酸との反応中に、窒素酸化物の発生を促進する金属を添加し、発生する窒素酸化物を槽内に充満させた状態で、被処理物中の銀及び白金族元素を硝酸に浸出させることから、槽内に窒素酸化物がより一層充満し、被処理物から硝酸に浸出する銀及び白金族元素の浸出率を一層向上させることができる。 According to the third means, during the reaction between the object to be treated and nitric acid, a metal that promotes the generation of nitrogen oxides is added, and the object to be treated is filled with the generated nitrogen oxides in the tank. Since the silver and platinum group elements are leached into nitric acid, the tank is further filled with nitrogen oxides, and the leaching rate of silver and platinum group elements leached from the object to be treated into nitric acid can be further improved. .
第4の手段によれば、被処理物と硝酸との反応中に、窒素酸化物の発生を促進する金属として銅および/または銀を添加することから、この反応中に窒素酸化物の発生量が増加して、被処理物から硝酸に浸出する銀及び白金族元素の浸出率を向上させることができると伴に、当該反応系内に余分な元素を持ち込むことにならず、使用薬剤の寿命を延ばすと共に生産性の向上に寄与する。 According to the fourth means, during the reaction of the object to be treated and nitric acid, copper and / or silver is added as a metal that promotes the generation of nitrogen oxides. Increase the leaching rate of silver and platinum group elements leached from the object to be treated into nitric acid, and without introducing extra elements into the reaction system. Will contribute to improving productivity.
第5の手段によれば、被処理物と硝酸との反応終了後に酸素を投入して、窒素酸化物を分解することから、有害な窒素酸化物を迅速に除去して次工程へ進めることができる。 According to the fifth means, oxygen is introduced after the reaction between the object to be treated and nitric acid to decompose nitrogen oxides, so that harmful nitrogen oxides can be quickly removed and proceeded to the next step. it can.
以下、本発明を実施するための最良の形態を、被処理物として銀スライムを用いた場合を例として、図面に基づき説明する。
図1は、本発明に係る被処理物の処理方法の一実施の形態が適用された硝酸浸出工程などを示すフローチャートである。
Hereinafter, the best mode for carrying out the present invention will be described with reference to the drawings, taking as an example the case where silver slime is used as an object to be processed.
FIG. 1 is a flowchart showing a nitric acid leaching process to which an embodiment of a processing method of an object to be processed according to the present invention is applied.
非鉄製錬工程では、一般に、銅、銀、金、白金などを順次精製する。このうちの銅については、鉱石及びリサイクル原料から銅溶錬工程を経て銅電解用アノードを得、この銅電解用アノードを用いて銅電解工程を実施し、カソードに銅を析出して銅を精製する。 In the non-ferrous smelting process, copper, silver, gold, platinum and the like are generally purified sequentially. For copper, copper anode is obtained from ore and recycled raw materials through copper smelting process, copper electrolysis process is carried out using this copper electrolysis anode, and copper is deposited on the cathode to refine copper. To do.
銅電解工程により生じた銅電解スライムには金、銀などの貴金属元素や、白金、パラジウムなどの白金族元素が濃縮されているため、次に銀を精製する。つまり、銅電解スライムを、精銀工程を経て銀電解アノードとし、図1に示す銀電解工程(ステップS1)を実施して、カソードに銀を析出し銀を精製する。 Since the copper electrolysis slime produced by the copper electrolysis process is concentrated with noble metal elements such as gold and silver and platinum group elements such as platinum and palladium, silver is then purified. That is, the copper electrolysis slime is converted into a silver electrolytic anode through a fine silver process, and the silver electrolysis process (step S1) shown in FIG. 1 is performed to deposit silver on the cathode and purify the silver.
銀電解により生じた銀電解スライムには金が約60%、銀が約25%、白金及びパラジウムなどの白金族元素が約5%濃縮して含有されている。そこで、金を精製するために、銀電解スライムから銀及び白金族元素を分離すべく、銀電解スライムを浸出槽内で硝酸と反応させる硝酸浸出(パーチング;分金)処理を実施して(ステップS2)、銀電解スライム中の銀及び白金族元素を硝酸に浸出して回収する。この硝酸浸出処理については後に詳説する。 Silver electrolysis slime produced by silver electrolysis contains about 60% gold, about 25% silver, and about 5% platinum group elements such as platinum and palladium. Therefore, in order to purify gold, in order to separate silver and platinum group elements from the silver electrolysis slime, a nitric acid leaching (parting) process is performed in which the silver electrolysis slime reacts with nitric acid in the leaching tank (step). S2) The silver and platinum group elements in the silver electrolytic slime are leached into nitric acid and recovered. This nitric acid leaching process will be described in detail later.
上記硝酸浸出で得られた浸出残渣を濾過・洗浄処理し(ステップS3)、乾燥処理した後鋳造して金電解用アノードとする。この金電解用アノードを用い所謂「Wholwill」法により金電解工程を実施して(ステップS4)、カソードに金を析出し金を精製する。尚、上記硝酸浸出処理において浸出液に回収された銀及び白金族元素に対し別途処理を実施し、白金などの白金族元素を精製する。 The leaching residue obtained by the nitric acid leaching is filtered and washed (step S3), dried and cast to obtain an anode for gold electrolysis. Using this gold electrolysis anode, a gold electrolysis process is performed by the so-called “Wholwill” method (step S4), and gold is deposited on the cathode to purify the gold. The silver and platinum group elements recovered in the leaching solution in the nitric acid leaching process are separately treated to purify platinum group elements such as platinum.
さて、以下に本発明に係る硝酸浸出処理を詳説する。この硝酸浸出処理には、第1の態様、第2の態様、第3の態様があるが、工程の設備状況等により適宜な態様を選択すれば良い。
[第1の態様]
例えば、槽として浸出槽を用いた場合、この浸出槽を密閉構造とすることで、銀電解スライムと硝酸との反応により発生する窒素酸化物を浸出槽内に充満させた状態で、銀電解スライム中の銀及び白金族元素を硝酸に浸出させる。銀電解スライム中の銀及び白金族元素は、浸出槽内に充満した窒素酸化物の作用で硝酸への浸出率が高められる。
Now, the nitric acid leaching process according to the present invention will be described in detail below. The nitric acid leaching treatment includes a first aspect, a second aspect, and a third aspect, and an appropriate aspect may be selected depending on the facility status of the process.
[First embodiment]
For example, when a leaching tank is used as a tank, the leaching tank has a sealed structure, so that nitrogen oxide generated by the reaction of silver electrolytic slime and nitric acid is filled in the leaching tank. Leaching silver and platinum group elements in nitric acid. Silver and platinum group elements in the silver electrolysis slime are enhanced in the leaching rate into nitric acid by the action of nitrogen oxides filled in the leaching tank.
つまり、浸出槽内で30〜40%の硝酸を撹拌しながら、銀電解スライムを、銀電解液が付着した状態で浸出槽内に投入し、浸出槽内における銀電解スライムのスラリー濃度を10〜30%とする。その後、浸出槽内の液温が80℃以上となるように加温しつつ浸出槽を密閉状態とし、12時間以上この状態を保持する。この間に、銀電解スライムと硝酸との反応により発生する窒素酸化物が浸出槽内に充満し、この窒素酸化物の作用で、銀電解スライムからの銀及び白金族元素の浸出率が向上する。 That is, while stirring 30 to 40% nitric acid in the leaching tank, the silver electrolytic slime is charged into the leaching tank with the silver electrolyte attached thereto, and the slurry concentration of the silver electrolytic slime in the leaching tank is 10 to 10. 30%. Thereafter, the leaching tank is sealed while heating so that the liquid temperature in the leaching tank is 80 ° C. or higher, and this state is maintained for 12 hours or more. During this time, nitrogen oxide generated by the reaction between silver electrolytic slime and nitric acid fills the leaching tank, and the action of this nitrogen oxide improves the leaching rate of silver and platinum group elements from the silver electrolytic slime.
図2に示すように、硝酸浸出後の浸出残渣中の銀と白金族元素は、浸出槽を開放している場合、浸出残渣中の金は975000ppm、銀は10000ppm、パラジウムは1100ppm、白金は2700ppmあるのに対し、浸出槽を密閉している場合は、金は987000、銀は6000ppm、パラジウムは650ppm、白金は1100ppmとなり、金以外の、銀、パラジウム、白金のいずれの金属も、浸出槽を密閉した場合の方が硝酸により多く浸出していることがわかる(但し、銀電解スライムとして、金を610000ppm、銀を280000ppm、パラジウムを15000ppm、白金を6700ppm含有するものを用いた。)。 As shown in FIG. 2, the silver and platinum group elements in the leaching residue after leaching with nitric acid are 975,000 ppm for gold in the leaching residue, 10,000 ppm for silver, 1100 ppm for palladium, and 2700 ppm for platinum when the leaching tank is opened. On the other hand, when the leaching tank is sealed, gold is 987000, silver is 6000 ppm, palladium is 650 ppm, platinum is 1100 ppm, and any metal other than gold, silver, palladium, and platinum, It can be seen that more nitric acid leached when sealed (however, a silver electrolytic slime containing 610000 ppm of gold, 280000 ppm of silver, 15000 ppm of palladium, and 6700 ppm of platinum was used).
このように、銀電解スライムの硝酸浸出時に発生する窒素酸化物を浸出槽内に充満させ、この窒素酸化物を利用して銀電解スライムからの銀及び白金族元素の浸出率を向上させ、これらの銀及び白金族元素を回収することから、従来例のごとく、硝酸浸出後に塩酸浸出を実施したり、塩酸及び過酸化水素を用いて浸出する場合のように、多種類の薬剤を用いたり、煩雑な操作を実施することがないので、銀電解スライムからの銀及び白金族元素の回収を短時間に低コストで実施できる。 In this way, the nitrogen oxide generated during the leaching of nitric acid from the silver electrolysis slime is filled in the leaching tank, and the leaching rate of silver and platinum group elements from the silver electrolysis slime is improved by using this nitrogen oxide. Since the silver and platinum group elements are recovered, as in the conventional example, hydrochloric acid leaching is carried out after nitric acid leaching, and various types of chemicals are used, such as leaching with hydrochloric acid and hydrogen peroxide, Since complicated operations are not performed, recovery of silver and platinum group elements from the silver electrolytic slime can be performed in a short time and at low cost.
また、後工程の金電解工程において、上記浸出残渣から製造される金電解アノード中の銀及び白金族元素の含有量が低減されることになるので、この金電解用アノードから生成する銀のスライム量と、金電解液中に溶出される白金族元素の溶出量とが減少する。このため、金電解液中から金以外の不純物である銀及び白金族元素を除去する金電解液の浄液負荷を低減できる。と同時に、金電解液中に銀、白金族元素が多量に滞留することによる滞留金利の上昇を抑制できる。これらの観点からも、低コスト化を実現できる。 In addition, since the content of silver and platinum group elements in the gold electrolytic anode produced from the leaching residue is reduced in the gold electrolysis step in the subsequent step, the silver slime produced from this gold electrolysis anode The amount and the amount of platinum group element eluted in the gold electrolyte solution are reduced. For this reason, the liquid purification load of the gold electrolyte which removes silver and platinum group elements which are impurities other than gold from gold electrolyte can be reduced. At the same time, an increase in the retention rate due to a large amount of silver and platinum group elements remaining in the gold electrolyte can be suppressed. Also from these viewpoints, cost reduction can be realized.
更に、上述の硝酸浸出処理によって銀電解スライムからの銀及び白金族元素の浸出率が高まり、浸出残渣中における銀及び白金族元素の含有量を低減できるので、次工程の金電解工程に代えて、例えば、所謂「Jプロセス」の工程を実施して金を安価に精製できる。この「Jプロセス」は、硝酸浸出後の浸出残渣中の金をヨウ化物とし、このヨウ化物を水酸化カリウムを用いて還元処理して金を析出し、金を精製するものである。 Furthermore, the above-described nitric acid leaching treatment increases the leaching rate of silver and platinum group elements from the silver electrolytic slime, and the content of silver and platinum group elements in the leaching residue can be reduced. For example, gold can be purified at low cost by carrying out a so-called “J process” step. In the “J process”, gold in the leaching residue after leaching with nitric acid is used as an iodide, and this iodide is reduced using potassium hydroxide to precipitate gold, thereby purifying the gold.
ところで、図1に示すように、硝酸浸出による銀電解スライムと硝酸との反応終了後に、浸出槽を密閉状態に保持したまま、この浸出槽内に酸素を投入して(ステップS5)、浸出槽内に充満した窒素酸化物を分解する。これにより、浸出槽内から有害な窒素酸化物を迅速に除去でき、浸出残渣の濾過・洗浄等を早期に実施できる。 By the way, as shown in FIG. 1, after completion of the reaction between silver electrolytic slime and nitric acid by nitric acid leaching, oxygen is introduced into the leaching tank while keeping the leaching tank sealed (step S5), and the leaching tank Decomposes nitrogen oxides filled inside. Thereby, harmful nitrogen oxides can be quickly removed from the inside of the leaching tank, and leaching residue can be filtered and washed at an early stage.
[第2の形態]
第2の形態の硝酸浸出処理は、銀電解スライムと硝酸とを、槽として浸出槽を用いた場合この浸出槽内で反応させる際に、浸出槽は開放状態のままで窒素酸化物の発生を促進する金属、例えば、銅および/または銀の屑粉を上記反応液中に添加し、増加した窒素酸化物の作用で、銀電解スライムから銀及び白金族元素を高浸出率で硝酸中に浸出させるものである。
[Second form]
In the second form of nitric acid leaching treatment, when silver electrolytic slime and nitric acid are used in a leaching tank as a tank, when reacting in this leaching tank, the leaching tank remains open and nitrogen oxides are generated. Accelerating metals, such as copper and / or silver dust, are added to the reaction solution, and silver and platinum group elements are leached into nitric acid at a high leaching rate from silver electrolytic slime by the action of increased nitrogen oxides. It is something to be made.
つまり、浸出槽内で30〜40%の硝酸を撹拌しながら、銀電解スライムを、銀電解液が付着した状態で浸出槽内に投入し、浸出槽内における銀電解スライムのスラリー濃度を10〜30%とする。その後、浸出槽内の液温が80℃以上となるように加温しつつ、浸出槽は開放状態のまま浸出槽内の銀電解スライムと硝酸との反応液中に銅、銀の屑粉を添加し、12時間保持する。上記銅および/または銀の屑粉の添加量は、銀電解スライムの1kgに対し20〜200gの範囲が好ましい。ここで、添加された銅および/または銀の屑粉は、反応液中にあった銅および銀と同元素なので、添加により反応液内に余分な元素を添加することにならず、使用薬剤の寿命を延ばすと共に生産性の向上に寄与することができ好ましい。 That is, while stirring 30 to 40% nitric acid in the leaching tank, the silver electrolytic slime is charged into the leaching tank with the silver electrolyte attached thereto, and the slurry concentration of the silver electrolytic slime in the leaching tank is 10 to 10. 30%. Then, while heating so that the liquid temperature in the leaching tank becomes 80 ° C. or higher, the leaching tank is left open, and copper and silver dust powder is put into the reaction liquid of the silver electrolytic slime and nitric acid in the leaching tank. Add and hold for 12 hours. The added amount of the copper and / or silver dust is preferably in the range of 20 to 200 g with respect to 1 kg of the silver electrolytic slime. Here, the added copper and / or silver dust powder is the same element as the copper and silver in the reaction solution. Therefore, the addition does not add an extra element into the reaction solution. This is preferable because it can extend the life and contribute to the improvement of productivity.
この銅および/または銀の屑粉の添加により、銀電解スライムと硝酸との反応中に窒素酸化物の発生量が増加して、銀電解スライムから硝酸中に浸出する銀及び白金族元素の浸出率を向上させることができる。例えば、図3に示すように、銅の屑粉を添加しない場合、硝酸浸出後の浸出残渣中の金は984000ppm、銀は6500ppm、パラジウムは800ppm、白金は4200ppmあるのに対し、銅の屑粉を添加した場合は、金は985000ppm、銀は5500ppm、パラジウムは670ppm、白金は1800ppmとなり、銅の屑粉を添加した場合の方がより多く浸出がおこなわれていることがわかる。(但し、銀電解スライムとして、金を650000ppm、銀を230000ppm、パラジウムを30000ppm、白金を5300ppm含有するものを用いた。) The addition of copper and / or silver dust increases the amount of nitrogen oxides generated during the reaction between silver electrolysis slime and nitric acid, and leaching of silver and platinum group elements leached from the silver electrolysis slime into nitric acid. The rate can be improved. For example, as shown in FIG. 3, when no copper dust is added, gold in the leaching residue after leaching with nitric acid is 984,000 ppm, silver is 6500 ppm, palladium is 800 ppm, and platinum is 4200 ppm. When gold is added, gold is 985000 ppm, silver is 5500 ppm, palladium is 670 ppm, platinum is 1800 ppm, and it can be seen that more leaching is performed when copper dust is added. (However, a silver electrolytic slime containing 650000 ppm of gold, 230000 ppm of silver, 30000 ppm of palladium, and 5300 ppm of platinum was used.)
従って、この第2の形態における硝酸浸出処理を実施した場合にも、第1の形態の場合と同様に、銀電解スライムからの銀及び白金族元素の回収を短時間且つ低コストに実施でき、次工程の金電解工程における金電解液の浄液負荷を低減でき、金電解液中に銀及び白金族元素が多量に滞留することによる滞留金利を抑制できる。 Therefore, even when the nitric acid leaching process in the second embodiment is performed, the silver and platinum group elements can be recovered from the silver electrolysis slime in a short time and at a low cost, as in the first embodiment. The purification load of the gold electrolyte in the gold electrolysis step of the next step can be reduced, and the retention rate due to a large amount of silver and platinum group elements remaining in the gold electrolyte can be suppressed.
尚、この第2の形態においても、浸出槽内に充満した窒素酸化物は、酸素の投入により迅速に分解されて除去される。 In the second embodiment, the nitrogen oxide filled in the leaching tank is quickly decomposed and removed by introducing oxygen.
[第3の形態]
硝酸浸出処理の第3の形態は、上記第1の形態と第2の形態とを併用した形態である。即ち、硝酸浸出実施中(つまり銀電解スライムと硝酸との反応中)に、窒素酸化物の発生を促進する金属、例えば銅および/または銀の屑粉を上記反応液中に添加し、且つ槽として浸出槽を用いた場合、この浸出槽を例えば密閉状態に保持するものである。その添加量は、銀電解スライムの1kg対し10〜100gの範囲が好ましい。
[Third embodiment]
A third form of the nitric acid leaching treatment is a form in which the first form and the second form are used in combination. That is, during nitric acid leaching (that is, during the reaction between silver electrolytic slime and nitric acid), a metal that promotes the generation of nitrogen oxides, such as copper and / or silver dust, is added to the reaction solution, and the tank When a leaching tank is used, the leaching tank is kept in a sealed state, for example. The amount added is preferably in the range of 10 to 100 g per 1 kg of silver electrolytic slime.
このように、銀電解スライムと硝酸との反応中に、窒素酸化物の発生を促進する金属(銅および/または銀)を当該反応液中に添加することから、この反応中に窒素酸化物の発生量が増加して、浸出槽内に窒素酸化物がより一層充満し、銀電解スライムから硝酸に浸出する銀及び白金族元素の浸出率を一層向上させることができる。 Thus, during the reaction of the silver electrolytic slime and nitric acid, a metal (copper and / or silver) that promotes the generation of nitrogen oxides is added to the reaction solution. The amount of generation increases, the leaching tank is further filled with nitrogen oxide, and the leaching rate of silver and platinum group elements leached from the silver electrolytic slime into nitric acid can be further improved.
例えば、図4に示すように、硝酸浸出後の浸出残渣中の銀と白金族元素は、浸出槽を開放し、銅の屑粉を添加しない場合は、金が975000ppm、銀が10000ppm、パラジウムが1100ppm、白金が2700ppmであるのに対し、浸出槽を密閉し、且つ銅の屑粉を添加した場合は、金が989000ppm、銀が3500ppm、パラジウムが800ppm、白金が900ppmとなり、銀とパラジウムと白金のいずれの金属も、浸出槽を密閉し、且つ銅の屑粉を添加した場合の方が硝酸により多く浸出していることがわかる。(但し、銀電解スライムとして、金を610000ppm、銀を280000ppm、パラジウムを15000ppm、白金を6700ppm含有するものを用いた。) For example, as shown in FIG. 4, silver and platinum group elements in the leaching residue after leaching with nitric acid, when the leaching tank is opened and no copper dust is added, 975,000 ppm of gold, 10000 ppm of silver, and palladium are added. When 1100ppm and platinum are 2700ppm, but the leaching tank is sealed and copper dust is added, gold is 989000ppm, silver is 3500ppm, palladium is 800ppm, platinum is 900ppm, silver, palladium and platinum It can be seen that any of these metals is more leached with nitric acid when the leaching tank is sealed and copper scraps are added. (However, a silver electrolytic slime containing 610000 ppm of gold, 280000 ppm of silver, 15000 ppm of palladium, and 6700 ppm of platinum was used.)
以上のことから、この第3の実施の形態における硝酸浸出処理を実施した場合にも、第1の形態の場合と同様に、銀電解スライムからの銀及び白金族元素の回収を短時間且つ低コストに実施でき、次工程の金電解工程における金電解液の浄液負荷を低減でき、金電解液中に銀及び白金族元素が多量に滞留することによる滞留金利を抑制できる。 From the above, even when the nitric acid leaching process in the third embodiment is performed, the recovery of silver and platinum group elements from the silver electrolysis slime can be performed in a short time and in the same manner as in the first embodiment. It can be carried out at a low cost, can reduce the load of the gold electrolyte solution in the gold electrolysis step in the next step, and can suppress the retention interest rate due to a large amount of silver and platinum group elements remaining in the gold electrolyte solution.
尚、この第3の実施の形態においても、浸出槽内に充満した窒素酸化物は、酸素の投入により迅速に分解して除去される。 In the third embodiment, the nitrogen oxide filled in the leaching tank is quickly decomposed and removed by introducing oxygen.
Claims (3)
被処理物と硝酸との反応中に、窒素酸化物の発生を促進する金属を添加することを特徴とする被処理物の処理方法。 A treatment method for a treatment object, in which a treatment object containing gold, silver and a platinum group element is reacted with nitric acid, and silver and platinum group elements in the treatment object are leached into nitric acid and recovered.
A method for treating an object to be treated, comprising adding a metal that promotes the generation of nitrogen oxides during the reaction between the object to be treated and nitric acid.
被処理物と硝酸との反応中に、窒素酸化物の発生を促進する金属を添加し、被処理物と硝酸との反応により発生する窒素酸化物を槽内に充満させた状態で、被処理物中の銀及び白金族元素を硝酸に浸出させることを特徴とする被処理物の処理方法。 This is a method for treating an object to be processed, in which an object to be processed containing gold, silver and platinum group elements is reacted with nitric acid in a tank, and silver and platinum group elements in the object to be processed are leached into nitric acid and recovered. And
During the reaction between the object to be treated and nitric acid, a metal that promotes the generation of nitrogen oxide is added, and the tank is filled with nitrogen oxide generated by the reaction between the object to be treated and nitric acid. A method for treating an object to be treated, which comprises leaching silver and platinum group elements in an object into nitric acid.
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