JPH01180923A - Recovering method for noble metal - Google Patents
Recovering method for noble metalInfo
- Publication number
- JPH01180923A JPH01180923A JP63004091A JP409188A JPH01180923A JP H01180923 A JPH01180923 A JP H01180923A JP 63004091 A JP63004091 A JP 63004091A JP 409188 A JP409188 A JP 409188A JP H01180923 A JPH01180923 A JP H01180923A
- Authority
- JP
- Japan
- Prior art keywords
- gold
- waste liquid
- precious
- iodine
- precious metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 10
- 229910000510 noble metal Inorganic materials 0.000 title abstract description 14
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000010931 gold Substances 0.000 claims abstract description 86
- 229910052737 gold Inorganic materials 0.000 claims abstract description 85
- 239000002699 waste material Substances 0.000 claims abstract description 46
- 239000011630 iodine Substances 0.000 claims abstract description 40
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 40
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 9
- 239000010970 precious metal Substances 0.000 claims description 97
- 239000007788 liquid Substances 0.000 claims description 46
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 25
- 229910052709 silver Inorganic materials 0.000 claims description 25
- 239000004332 silver Substances 0.000 claims description 25
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 238000000151 deposition Methods 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 3
- 239000012530 fluid Substances 0.000 abstract 5
- 238000006722 reduction reaction Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000005530 etching Methods 0.000 description 10
- 238000000926 separation method Methods 0.000 description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 3
- 229940005633 iodate ion Drugs 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- -1 iodate ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QOGLYAWBNATGQE-UHFFFAOYSA-N copper;gold;silver Chemical compound [Cu].[Au][Ag] QOGLYAWBNATGQE-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
Abstract
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は貴金属の回収方法に関するものである。[Detailed description of the invention] (Industrial application field) The present invention relates to a method for recovering precious metals.
（従来の技術とその問題点）
ヨウ素を含む貴金属含有廃液は、貴金属をヨウ素を含む
エツチング液でエツチングしたりヨウ素溶解液で溶解す
る工程より排出され、半導体産業や貴金属に関連する事
業所など多岐にわたっている。貴金属は高価で稀少な材
料であるので、こうしたヨウ素を含む貴金属含有廃液か
ら貴金属を回収することは非常に重要なことである。(Conventional technology and its problems) Waste liquid containing precious metals containing iodine is discharged from the process of etching precious metals with an etching solution containing iodine or dissolving them with an iodine solution, and is used in a wide variety of industries, including the semiconductor industry and businesses related to precious metals. spans over. Since precious metals are expensive and rare materials, it is very important to recover precious metals from such iodine-containing precious metal-containing waste liquids.
従来のヨウ素を含む貴金属含有廃液は、金が含まれるこ
とが多（１，主な回収すべき貴金属は金であったが、近
年では使用材料の多様化に伴い、銀やパラジウム、白金
など、金の他に金以外の貴金属が含まれるようになって
きている。Conventional precious metal-containing waste liquids containing iodine often contain gold (1) The main precious metal to be recovered was gold, but in recent years, with the diversification of materials used, silver, palladium, platinum, etc. In addition to gold, precious metals other than gold are increasingly included.
こうしたヨウ素を含む貴金属含有廃液より金と金以外の
貴金属を回収するには、ヒドラジンや水素化ホウ素ナト
リウムなどの還元剤により貴金属を還元析出させるのが
一般的であるが、還元剤により貴金属が同時に析出して
しまうので、貴金属は金と他の貴金属が混じった形状で
得られ、その後の貴金属の分離精製操作に手間がかかる
といった問題点があった。またヨウ素を含む貴金属含有
廃液にふくまれている遊離ヨウ素成分（Ｉ２及び■３−
）をすべて分解した後でないと貴金属が析出してこない
ので多量の還元剤を使用しないと貴金属を回収すること
ができないといった問題点があった。In order to recover gold and precious metals other than gold from such precious metal-containing waste liquid containing iodine, it is common to reduce and precipitate the precious metals using a reducing agent such as hydrazine or sodium borohydride. Because of the precipitation, the precious metal is obtained in the form of a mixture of gold and other precious metals, and the subsequent separation and purification of the precious metal is time-consuming. In addition, free iodine components (I2 and ■3-
), the precious metals do not precipitate out until all of them have been decomposed, so there was a problem that the precious metals could not be recovered unless a large amount of reducing agent was used.
（発明が解決しようとする問題点）
本発明はこうした問題点に鑑みてなされたもので、ヨウ
素を含む貴金属含有廃液より金と金以外の貴金属を回収
するに際し、遊離ヨウ素成分の分解に多量の還元剤を必
要とせず、析出した貴金属の分離精製操作に手間のかか
らない貴金属の回収方法を提供せんとするものである。(Problems to be Solved by the Invention) The present invention has been made in view of these problems, and when recovering gold and precious metals other than gold from a waste liquid containing precious metals containing iodine, a large amount of free iodine is required to decompose the free iodine component. It is an object of the present invention to provide a method for recovering precious metals that does not require a reducing agent and does not require much time and effort for separation and purification of precipitated precious metals.
（問題点を解決するための手段）
上述のごとく本発明による貴金属の回収方法は、ヨウ素
を含む貴金属含有廃液より金と金以外の貴金属を分離回
収するに際し、
ａ）、該ヨウ素を含む貴金属含有廃液のｐＨを１２以上
の強アルカリ性として該貴金属含有廃液中の金を選択的
に析出させ、
ｂ）、析出した金と全析出後の前記貴金属含有廃液とを
分離し、
ｃ）１分離した該全析出後の貴金属含有廃液をさらに化
学還元剤及び／または電解により残る貴金属を析出させ
金と他の貴金属を分離回収することを特徴とするもので
ある。(Means for Solving the Problems) As described above, the method for recovering precious metals according to the present invention, when separating and recovering gold and precious metals other than gold from a waste liquid containing precious metals containing iodine, a) selectively precipitating gold in the precious metal-containing waste liquid by making the pH of the waste liquid strongly alkaline at 12 or higher; b) separating the precipitated gold from the precious metal-containing waste liquid after total precipitation; and c) separating the separated gold. The method is characterized in that the remaining precious metals are further precipitated from the precious metal-containing waste liquid after the total precipitation using a chemical reducing agent and/or electrolysis, and the gold and other precious metals are separated and recovered.
（作用） 以下本発明の作用についてのべる。(effect) The effects of the present invention will be described below.
ヨウ素を含む貴金属含有廃液としては、半導体産業など
で貴金属のエツチングに使用されるヨウ素エツチング廃
液や、貴金属化合物や貴金属の回収、精製に伴う廃液な
どがある。含まれる貴金属としては、金、銀、白金、パ
ラジウムなどかあり、稀には他の貴金属がふくまれてい
る。Examples of precious metal-containing waste liquids containing iodine include iodine etching waste liquids used for etching precious metals in the semiconductor industry, etc., and waste liquids associated with the recovery and purification of precious metal compounds and precious metals. The precious metals included include gold, silver, platinum, and palladium, and in rare cases, other precious metals are also included.
該ヨウ素を含む貴金属含有廃液のｐＨを１２以上の強ア
ルカリ性とすると、貴金属含有廃液中の貴金属のうち金
か選択的に析出しく１式）２ＡｕＩａ−＋６０８−−２
Ａｕ ＋ １０３− ＋ ７１− １式ヨウ素を含む
貴金属含有廃液に含まれている貴金属を溶かす能力を有
する遊離ヨウ素成分（Ｉ２及びＩ３−）は、ヨウ素の不
均化反応によりヨウ素酸イオンとヨウ素イオンとになり
（２式）、強アルカリ性であることも関与して貴金属を
溶かす能力を失う。When the pH of the precious metal-containing waste liquid containing iodine is made strong alkaline to 12 or more, gold selectively precipitates among the precious metals in the precious metal-containing waste liquid.
Au + 103- + 71- The free iodine components (I2 and I3-) that have the ability to dissolve precious metals contained in the precious metal-containing waste liquid containing Formula 1 iodine are converted into iodate ions and iodine ions by the disproportionation reaction of iodine. (Formula 2), and the fact that it is strongly alkaline also plays a role, causing it to lose its ability to melt precious metals.
３Ｉ２＋６０Ｈ−→ＩＯ３−＋５Ｉ−２式析出した金は
貴金属含有廃液より分離することにより金を回収するこ
とかできる。3I2+60H-→IO3-+5I-2 The precipitated gold can be recovered by separating it from the precious metal-containing waste liquid.
貴金属含有廃液のｐＨか１２以下であると１弐の反応が
起こらず、金を析出させることができない。If the pH of the precious metal-containing waste liquid is below 12, the first reaction will not occur and gold will not be deposited.
また２弐の反応も起こらないので該貴金属を酸化し溶か
す能力のある遊離ヨウ素成分が貴金属含有廃液中に存在
してしまう。金を析出する条件としては、ｐＨ＝１２以
上であればよいが好ましくは１２．５〜１４．５の範囲
である。Furthermore, since the second reaction does not occur, free iodine components capable of oxidizing and dissolving the precious metals are present in the precious metal-containing waste liquid. The conditions for depositing gold may be pH=12 or higher, preferably in the range of 12.5 to 14.5.
この操作により比較的品位の高い金を得ることができ、
元のヨウ素を含む貴金属含有廃液の各貴金属の濃度割合
や種類にもよるが、その品位はおおむね９５％以上であ
る。This operation allows you to obtain relatively high-grade gold,
Although it depends on the concentration ratio and type of each precious metal in the original precious metal-containing waste liquid containing iodine, its quality is generally 95% or higher.
従来の操作により貴金属を回収した場合は、元のヨウ素
を含む貴金属含有廃液の各貴金属の濃度割合が、得られ
る金の品位を決めてしまうので、金とともに他の貴金属
が多く含まれる場合には精製操作を数回繰り返し行う必
要が生じるが、本発明では他の貴金属成分の割合が多く
ても金を選択的に析出させることができ、金の品位の高
いものが得られるので、次工程での金の精製操作の手間
が少なくなる。When precious metals are recovered using conventional operations, the concentration ratio of each precious metal in the original precious metal-containing waste liquid containing iodine determines the quality of the gold obtained. Although it is necessary to repeat the refining operation several times, in the present invention, gold can be selectively deposited even if the proportion of other precious metal components is high, and high-quality gold can be obtained. The labor involved in gold refining operations will be reduced.
該分離後の貴金属含有廃液中の貴金属は、化学還元剤及
び／または電解により析出させ回収する。After the separation, the precious metals in the precious metal-containing waste liquid are precipitated and recovered using a chemical reducing agent and/or electrolysis.
化学還元剤としては、前述のヒドラジンや水素化ホウ素
ナトリウムなどのほかに、マグネシウムやアルミニウム
、亜鉛末などの金属還元剤など多くのものがあるが、当
該貴金属含有廃液のｐＨを１２以下としであるので、そ
の条件で貴金属を還元する能力のあるものならば特に問
題はない。また電解により陰極に貴金属を析出させても
よく、以上の操作により残る貴金属を回収することがで
きる。In addition to the aforementioned hydrazine and sodium borohydride, there are many chemical reducing agents, such as metal reducing agents such as magnesium, aluminum, and zinc powder. Therefore, there is no particular problem as long as it has the ability to reduce precious metals under those conditions. Further, the noble metal may be deposited on the cathode by electrolysis, and the remaining noble metal can be recovered by the above operation.
ｐＨ１２以下の条件では、ヨウ素を含む貴金属含有廃液
に含まれている遊離ヨウ素成分（Ｉ２及び■３−）を、
全て分解した後でないと貴金属が析出してこないか、本
発明では、金を析出させる際の操作で予めｐＨ１２以上
の強アルカリ性に調整しであるので、遊離ヨウ素成分は
、２式に従いヨウ素酸イオンとなり貴金属を酸化する能
力を失う。また酸化還元電位か変化し、貴金属が析出し
てこないとヨウ素酸が分解されなくなるので、還元剤を
加えた際は、貴金属の析出の後、ヨウ素酸の分解も一部
おこる。実際の反応では、貴金属の析出と共にヨウ素酸
の分解も一部おこるか、従来のように全ての遊離ヨウ素
成分を分解させる必要がなく、本発明では全てのヨウ素
酸塩が分解されなくても貴金属を析出、回収することが
できるので、薬品効率や電気効率が向上する。Under conditions of pH 12 or lower, the free iodine components (I2 and ■3-) contained in the waste liquid containing iodine,
Precious metals do not precipitate until after all of them have been decomposed.In the present invention, the pH is adjusted to a strong alkalinity of 12 or more in advance in the operation when depositing gold, so the free iodine component is converted to iodate ion according to equation 2. and loses its ability to oxidize precious metals. In addition, the oxidation-reduction potential changes and iodic acid will not be decomposed unless the noble metal is precipitated, so when a reducing agent is added, some of the iodic acid will be decomposed after the noble metal is precipitated. In an actual reaction, some of the iodic acid decomposes along with the precipitation of the precious metal, or it is not necessary to decompose all the free iodine components as in the past, and in the present invention, the precious metal can be precipitated and recovered, improving chemical efficiency and electrical efficiency.
還元剤の使用に伴いｐＨが下がったりすることがあり、
１２以下になると薬品の使用量が増加する。The pH may drop due to the use of reducing agents,
When the number is below 12, the amount of chemicals used increases.
従って貴金属の還元、析出は１２を下回らないｐＨか良
く、好ましくは１２．５〜１４．５の範囲の条件下で行
い、その条件はアルカリ規定度に換算すると０．０３〜
３Ｎである。Therefore, the reduction and precipitation of noble metals should be carried out at a pH not lower than 12, preferably in the range of 12.5 to 14.5, and the conditions are 0.03 to 14.5 when converted to alkaline normality.
It is 3N.
（実施例１）
貴金属を含有するヨウ素エツチング廃液（金：８．７ｇ
／ｎ、銀： ２．２ｇ＃２、遊離ヨウ素としての酸化
還元規定度： ０．２４Ｎ、総ヨウ素濃度：２２５ｇ／
Ｉ！、、１） Ｈ＝８．５） １５５ｆｉに水酸化ナト
リウムのフレークを攪拌しながら５ｋｇ加えてｐ ＨＩ
３．４として金を析出させた。３０分間の攪拌後、析出
した金と全析出後のヨウ素エツチング廃液とを分離した
。(Example 1) Iodine etching waste liquid containing precious metals (gold: 8.7 g
/n, silver: 2.2g #2, redox normality as free iodine: 0.24N, total iodine concentration: 225g/n
I! ,,1) H=8.5) Add 5kg of sodium hydroxide flakes to 155fi with stirring and adjust to p HI
Gold was deposited as 3.4. After stirring for 30 minutes, the precipitated gold and the iodine etching waste liquid after all the precipitation were separated.
析出した金は洗浄乾燥し分析したところ、金として１２
７４．０ ｇが回収され、品位は９９．６％と純金に近
い物であった。また残る０、４％はほとんどが銀であっ
た。When the precipitated gold was washed, dried and analyzed, it was found to be 12% gold.
74.0 g was recovered, and the quality was 99.6%, close to pure gold. The remaining 0.4% was mostly silver.
全析出後のヨウ素エツチング廃液は、固液分離操作の結
果液量が１５５！から１６２！に増加したので、分析を
したところ金： ０．４６ ｇ ／ Ｅ、銀：２．１ｇ
／／２になり、ヨウ素酸イオンとしての酸化還元規定度
は、以前より有していた遊離ヨウ素としての酸化還元規
定度のほかに、金を析出した際に精製するヨウ素酸イオ
ン分が加わり、０．３５Ｎに増加した。The iodine etching waste liquid after total precipitation has a liquid volume of 155% as a result of the solid-liquid separation operation! From 162! When analyzed, gold: 0.46 g/E, silver: 2.1 g
//2, and the redox normality as iodate ion is not only the redox normality as free iodine that it already had, but also the iodate ion that is purified when gold is deposited. It increased to 0.35N.
当該全析出後のヨウ素エツチング廃液中（０，３５ＮＸ
１６２℃−５６．７当量：ヨウ素酸の酸化還元当量）の
銀と未反応の金（計４．３当量分）を回収するために、
亜鉛末を５００ｇ （１５，３当量分）加えてよく攪拌
した。水素ガスの発生と共に金と銀が析出し、約１時間
後に攪拌を止めて、金と銀を濾過により分離して回収し
たが、ヨウ素酸の分解に必要な還元剤の当量以下で貴金
属を回収することができた。In the iodine etching waste liquid after the total precipitation (0.35NX
In order to recover silver and unreacted gold (4.3 equivalents in total) at 162°C - 56.7 equivalents (oxidation-reduction equivalent of iodic acid),
500g (15.3 equivalents) of zinc powder was added and stirred thoroughly. Gold and silver precipitated with the generation of hydrogen gas, and after about an hour, stirring was stopped and the gold and silver were separated and recovered by filtration, but the precious metals were recovered with less than the equivalent amount of reducing agent required to decompose iodic acid. We were able to.
析出した金と銀は洗浄乾燥し、分析したところ、総重量
４１６．９ ｇに対して、金か１８．０％、銀が８０．
５％、亜鉛後の不純物が１．５％含まれており、金とし
て７５．１ｇ、銀として３３５．５ｇが回収された。The precipitated gold and silver were washed and dried, and when analyzed, the total weight of 416.9 g was found to be 18.0% gold and 80% silver.
5% and 1.5% impurities after zinc, and 75.1 g of gold and 335.5 g of silver were recovered.
回収した金銀は金の割合が低いので、うち４００ｇに硝
酸１．２！を加えて、そのまま硝酸分金法により金と銀
に分離したところ、純金と硝酸銀の溶液とに容易に分離
することができた。The recovered gold and silver has a low gold content, so 400g of it contains 1.2 nitric acid! When the gold and silver were separated using the nitric acid separation method, it was possible to easily separate pure gold and a solution of silver nitrate.
（従来例１）
貴金属を含有するヨウ素エツチング廃液（金：８．７
ｇ ／ ｆｆ、銀： ２．２ｇ／１．、遊離ヨウ素と
しての酸化還元規定度： ０．２４Ｎ、総ヨウ素濃度＝
２５５ｇ／ｆｆｉ、ｐ Ｈ＝８．５）１０ｆｆｉに水加
ヒドラジンを加えて貴金属を還元した。遊離ヨウ素を分
解するに必要な酸化還元当量の２．４当量（０，２４Ｎ
Ｘ１０℃−２，４当量）と金と銀を回収するために必要
な１．５当量とを合計した３１ｇ当量の１．２倍に相当
する４、６８当量の水加ヒドラジンを加えたにもかかわ
らす貴金属を全て還元することができなかったので、さ
らに２．３４当量を加えて当該貴金属を含有するヨウ素
エツチング廃液中の金銀を還元、析出させた。析出した
金と銀は濾過、洗浄、乾燥の後、分析したところ、総重
量１０９．１ｇに対して、金が７９．８％、銀が１９．
８％、その他の不純物が０．４％含まれており、金とし
て８７．１ｇ、銀として２１．６ｇが回収された。(Conventional example 1) Iodine etching waste liquid containing precious metals (gold: 8.7
g/ff, silver: 2.2g/1. , redox normality as free iodine: 0.24N, total iodine concentration =
255g/ffi, pH=8.5) Hydrazine hydrate was added to 10ffi to reduce the noble metal. 2.4 equivalents (0.24N) of the redox equivalents required to decompose free iodine
Even if 4.68 equivalents of hydrazine were added, which is equivalent to 1.2 times the 31 g equivalent of the sum of 1.5 equivalents required to recover gold and silver ( Since all of the noble metals could not be reduced, 2.34 equivalents were further added to reduce and precipitate the gold and silver in the iodine etching waste liquid containing the noble metals. The precipitated gold and silver were filtered, washed, dried, and then analyzed. The total weight was 109.1g, and the gold content was 79.8% and the silver content was 19.9%.
8% and other impurities 0.4%, and 87.1 g of gold and 21.6 g of silver were recovered.
回収した金銀は金の割合が高く、実施例１のようにその
まま硝酸分金法をおこなうと銀を溶かすことが出来ず金
と銀を分離することが出来なくなるので、うち１００ｇ
をとり銅を２２０ｇ加えてるっぼ中で一旦融解させ、金
銀銅の合金とすることにより金の品位を２５％まで下げ
たのち、硝酸１．Ｏｒ！。The recovered gold and silver have a high proportion of gold, and if the nitric acid fractionation method was directly applied as in Example 1, the silver would not be dissolved and the gold and silver could not be separated.
220g of copper was added and melted in a pot to form a gold-silver-copper alloy, reducing the quality of gold to 25%, and then adding 1. Or! .
を加えて、硝酸公金法により金と銀に分離したところ、
純金と多量の銅が溶けた硝酸銀の溶液とに分離すること
ができた。was added and separated into gold and silver using the nitric acid public metal method.
It was possible to separate pure gold and a solution of silver nitrate in which a large amount of copper was dissolved.
実施例１では、アルカリを使用してほとんどの金を析出
させており、また金の品位も高いものが得られるので、
容易に精製することができる。その後に得られる貴金属
の混合物も、前の操作によりほとんどの金を除いた後で
あるので処理量が少な（てすみ、その後の分離、精製操
作が容易になる。In Example 1, most of the gold was precipitated using an alkali, and high quality gold was obtained.
Can be easily purified. Since most of the gold has been removed from the precious metal mixture obtained after that, the amount of processing required is small, and subsequent separation and purification operations are easier.
一方従来例１では、貴金属の濃度割合によって回収され
た貴金属の割合が決まってしまい、金と他の貴金属の分
離に手間がかかり、実施例１での処理量に換算するとそ
の手間は膨大なものとなる。On the other hand, in Conventional Example 1, the proportion of recovered precious metals is determined by the concentration ratio of precious metals, and it takes time and effort to separate gold from other precious metals, and when converted to the amount of processing in Example 1, the time and effort is enormous. becomes.
また還元剤の使用量も遊離ヨウ素成分を分解した後でな
いと貴金属か還元、析出してこないので、約７倍も必要
であった。Moreover, the amount of reducing agent used was about 7 times as large as the precious metal cannot be reduced and precipitated until after the free iodine component has been decomposed.
（実施例２）
ヨウ素を含む貴金属含有廃液（金：１２．５ｇ／、ｅ、
恨１．２ｇ／尼、パラジウム２．６ｇ／、ｅ、白金０．
４ｇ／Ｉ！、、ｐ Ｈ＝ ５．５） １０ｊ２に水酸化
カリウムを加えてｐＨ１２，９として金を析出させた。(Example 2) Precious metal-containing waste liquid containing iodine (gold: 12.5 g/, e,
1.2g/N, palladium 2.6g/e, platinum 0.
4g/I! ,, pH=5.5) Potassium hydroxide was added to 10j2 to adjust the pH to 12.9, and gold was precipitated.
３０分間攪拌した後、析出した金と全析出後の上記ヨウ
素を含む貴金属廃液とを分離した。After stirring for 30 minutes, the precipitated gold and the noble metal waste liquid containing iodine after total precipitation were separated.
析出した金は、洗浄乾燥し、分析したところ、金として
１１３．５ｇが回収され、品位は９７．５％と純金に近
いものであった。また残る２、５％はほとんどが銀とパ
ラジウムであった。The precipitated gold was washed, dried, and analyzed. As a result, 113.5 g of gold was recovered, and the quality was 97.5%, which was close to pure gold. The remaining 2.5% was mostly silver and palladium.
全析出後の貴金属廃液は、陽極にｌ０ＣＴＩＩ Ｘ ２
０ｃ＋ｎの白金メツキしたチタン板、陰極に１０ｃｍＸ
２０ｃｍのステンレス板（ＳＵＳ３１６）を使用して、
１０Ａで４時間電解して、陰極に貴金属を析出させた。After the total precipitation, the precious metal waste liquid is transferred to the anode using 10CTII
0c+n platinized titanium plate, 10cmX on cathode
Using a 20cm stainless steel plate (SUS316),
Electrolysis was carried out at 10 A for 4 hours to deposit a noble metal on the cathode.
電解中に液のｐＨが下がったので水酸化カリウムでｐＨ
を１３．２に言周整した。The pH of the solution decreased during electrolysis, so the pH was adjusted with potassium hydroxide.
The wording has been adjusted to 13.2.
陰極に析出した貴金属を分析したところ、金が１１．７
ｇ、 Ｓ艮が９．６ｇ、パラジウムが２５．１ｇ、白金
が３．９ｇ含まれていたが他の重金属はほとんど含まれ
ていなかった。Analysis of the precious metal deposited on the cathode revealed that gold was 11.7
It contained 9.6 g of g, S, 25.1 g of palladium, and 3.9 g of platinum, but almost no other heavy metals.
（従来例２）
ヨウ素を含む貴金属廃液（金： １２．５ ｇ ／ Ｅ
、１艮： １．２ｇ／ｆｆ、パラジウム：２．６ｇ／
ｊ２、白金：０．４ｇ／４２、ｐＨ＝ ５．５） ５
ｆｆｉを、陽極と陰極に１０ｃｍ Ｘ ２０ｃｍ＋の白
金メツキしたチタン板を使用して、１０Ａで４時間電解
したところ、貴金属が析出するものの、−旦析出した貴
金属が電極より剥離して再ひ液中に溶解してしまうので
、貴金属を回収することはできなかった。(Conventional example 2) Precious metal waste liquid containing iodine (gold: 12.5 g/E
, 1 barb: 1.2g/ff, palladium: 2.6g/ff
j2, platinum: 0.4g/42, pH = 5.5) 5
When ffi was electrolyzed at 10A for 4 hours using platinum-plated titanium plates measuring 10cm x 20cm+ as the anode and cathode, the precious metal was precipitated, but the precipitated precious metal peeled off from the electrode and was re-soaked in the solution. It was not possible to recover the precious metals because they would dissolve into the metals.
（発明の効果）
本発明はヨウ素を含む貴金属含有廃液より金と全以外の
貴金属を分離回収するに際し、まずヨウ素を含む貴金属
含有廃液のｐＨを１２以上の強アルカリ性として該貴金
属含有廃液中の金を選択的に析出させ、ついで析出した
金と全析出後の貴金属含有廃液とを分離し、分離した全
析出後の貴金属含有廃液をさらに化学還元剤及び／また
は電解により残る貴金属を析出させることにより金と他
の貴金属を回収できるようにしている。あらかじめ金を
分離しておくことにより、その後の貴金属の分離、精製
操作が非常に容易になるとともに、強アルカリ性にて反
応させることにより貴金属の回収に多量の還元剤を必要
としなくなるなどの効果がある。この結果、回収、精製
にかかるコストが大幅に改善されるなどの別の効果もあ
り、貴金属のように稀少な金属を回収するうえで、産業
への貢献大なるものと言える。(Effects of the Invention) When the present invention separates and recovers precious metals other than gold and total from a precious metal-containing waste liquid containing iodine, the pH of the precious metal-containing waste liquid containing iodine is first made strong alkaline to 12 or more, and the gold in the precious metal-containing waste liquid is By selectively precipitating gold, then separating the precipitated gold from the precious metal-containing waste liquid after total precipitation, and further precipitating the remaining precious metals from the separated precious metal-containing waste liquid after total precipitation using a chemical reducing agent and/or electrolysis. It allows gold and other precious metals to be recovered. By separating the gold in advance, the subsequent separation and purification of the precious metal becomes very easy, and by reacting in strong alkalinity, there is no need for a large amount of reducing agent to recover the precious metal. be. As a result, there are other effects such as a significant reduction in the cost of recovery and refining, and it can be said to be a great contribution to industry in recovering rare metals such as precious metals.
出願人 田中貴金属工業株式会社Applicant: Tanaka Kikinzoku Kogyo Co., Ltd.
Claims (2)
金属を分離回収するに際し、 ａ）、該ヨウ素を含む貴金属含有廃液のｐＨを１２以上
の強アルカリ性として該貴金属含有廃液中の金を選択的
に析出させ、 ｂ）、析出した金と金析出後の前記貴金属含有廃液とを
分離し、 ｃ）、分離した該金析出後の貴金属含有廃液をさらに化
学還元剤及び／または電解により残る貴金属を析出させ
金と他の貴金属を分離回収することを特徴とする貴金属
の回収方法。(1) When separating and recovering gold and precious metals other than gold from a precious metal-containing waste liquid containing iodine, a) The pH of the precious metal-containing waste liquid containing iodine is made strongly alkaline to 12 or more to select gold in the precious metal-containing waste liquid. b) separating the precipitated gold from the precious metal-containing waste liquid after gold precipitation; c) further treating the separated precious metal-containing waste liquid after gold precipitation with a chemical reducing agent and/or electrolysis to remove remaining precious metals; A method for recovering precious metals, which is characterized by separating and recovering gold and other precious metals by precipitating them.
、白金、パラジウムからなる群より選択されることを特
徴とする特許請求の範囲第１項に記載の貴金属の回収方
法。(2) The method for recovering precious metals according to claim 1, wherein the precious metal other than gold contained in the precious metal-containing waste liquid is selected from the group consisting of silver, platinum, and palladium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP409188A JP2619893B2 (en) | 1988-01-12 | 1988-01-12 | Precious metal recovery method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP409188A JP2619893B2 (en) | 1988-01-12 | 1988-01-12 | Precious metal recovery method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01180923A true JPH01180923A (en) | 1989-07-18 |
| JP2619893B2 JP2619893B2 (en) | 1997-06-11 |
Family
ID=11575124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP409188A Expired - Lifetime JP2619893B2 (en) | 1988-01-12 | 1988-01-12 | Precious metal recovery method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2619893B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007177289A (en) * | 2005-12-28 | 2007-07-12 | Nikko Kinzoku Kk | Method for collecting gold from etching waste |
| CN110983065A (en) * | 2019-12-23 | 2020-04-10 | 昆山全亚冠环保科技有限公司 | Method for reducing gold in iodine-containing waste liquid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5141625A (en) * | 1974-08-05 | 1976-04-08 | Beisaido Rifuainingu Ando Chem | |
| JPS52144162A (en) * | 1976-05-25 | 1977-12-01 | Automated Med Syst | Method of precipitating metal ion from solution containing metal salts at low concentration |
| JPS58174532A (en) * | 1982-04-05 | 1983-10-13 | Tanaka Kikinzoku Kogyo Kk | Recovery of palladium or noble metal mixed in palladium |
| JPS6417827A (en) * | 1987-07-14 | 1989-01-20 | Tanaka Precious Metal Ind | Refining device for gold and refining method for gold using said device |
-
1988
- 1988-01-12 JP JP409188A patent/JP2619893B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5141625A (en) * | 1974-08-05 | 1976-04-08 | Beisaido Rifuainingu Ando Chem | |
| JPS52144162A (en) * | 1976-05-25 | 1977-12-01 | Automated Med Syst | Method of precipitating metal ion from solution containing metal salts at low concentration |
| JPS58174532A (en) * | 1982-04-05 | 1983-10-13 | Tanaka Kikinzoku Kogyo Kk | Recovery of palladium or noble metal mixed in palladium |
| JPS6417827A (en) * | 1987-07-14 | 1989-01-20 | Tanaka Precious Metal Ind | Refining device for gold and refining method for gold using said device |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007177289A (en) * | 2005-12-28 | 2007-07-12 | Nikko Kinzoku Kk | Method for collecting gold from etching waste |
| CN110983065A (en) * | 2019-12-23 | 2020-04-10 | 昆山全亚冠环保科技有限公司 | Method for reducing gold in iodine-containing waste liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2619893B2 (en) | 1997-06-11 |
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