JPH021895B2 - - Google Patents
Info
- Publication number
- JPH021895B2 JPH021895B2 JP9645683A JP9645683A JPH021895B2 JP H021895 B2 JPH021895 B2 JP H021895B2 JP 9645683 A JP9645683 A JP 9645683A JP 9645683 A JP9645683 A JP 9645683A JP H021895 B2 JPH021895 B2 JP H021895B2
- Authority
- JP
- Japan
- Prior art keywords
- palladium
- hydrochloric acid
- extraction
- aqueous solution
- platinum
- 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.)
- Expired - Lifetime
Links
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 85
- 229910052763 palladium Inorganic materials 0.000 claims description 43
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 41
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 40
- 238000000605 extraction Methods 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 229910052697 platinum Inorganic materials 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 229910052703 rhodium Inorganic materials 0.000 claims description 17
- 239000010948 rhodium Substances 0.000 claims description 17
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 230000002378 acidificating effect Effects 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000010953 base metal Substances 0.000 claims description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 24
- 229910052737 gold Inorganic materials 0.000 description 22
- 239000010931 gold Substances 0.000 description 22
- 239000012074 organic phase Substances 0.000 description 13
- 229910052797 bismuth Inorganic materials 0.000 description 11
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 11
- LHNRHYOMDUJLLM-UHFFFAOYSA-N 1-hexylsulfanylhexane Chemical compound CCCCCCSCCCCCC LHNRHYOMDUJLLM-UHFFFAOYSA-N 0.000 description 10
- 238000000926 separation method Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 8
- 239000004332 silver Substances 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 238000000638 solvent extraction Methods 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 6
- 238000005191 phase separation Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229910052714 tellurium Inorganic materials 0.000 description 4
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- -1 platinum group metals Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- KZVBBTZJMSWGTK-UHFFFAOYSA-N 1-[2-(2-butoxyethoxy)ethoxy]butane Chemical compound CCCCOCCOCCOCCCC KZVBBTZJMSWGTK-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Description
本発明は、白金、ロジウム、パラジウム、卑金
属を主として含有する塩酸酸性水溶液からパラジ
ウムを溶媒抽出法によつて分離する方法の改良に
関する。
金、パラジウム、白金、ロジウム等の金及び白
金族金属を含有する塩酸酸性水溶液は、例えば銅
精錬における銅電解スライムの処理工程におい
て、銀電解スライム処理工程で生成する。
銀電解スライムを硝酸で分解すると、銀抽出液
と残渣が得られるが、この銀抽出液を中和して一
旦沈殿物を得てこれを塩酸溶解すると、金、白
金、ロジウム、パラジウム、卑金属を含有する塩
酸酸性水溶液が得られる。一方、この残渣に塩酸
と過酸化水素とを使用した酸処理を施すことによ
つても、前記塩酸酸性水溶液が得られる。このよ
うにして得られた塩酸酸性水溶液は大体次のよう
な組成を有している。即ち、金：５ｇ／以下、
銀：0.1ｇ／以下、パラジウム：５〜80ｇ／、
白金：２〜30ｇ／、ロジウム：0.2〜10ｇ／、
ビスマス：５〜80ｇ／、テルル：５〜40ｇ／
、銅：10ｇ／以下、鉛：５ｇ／以下、塩酸
約１モルである。
上記のような塩酸酸性水溶液からその中に含有
される金、パラジウム、白金、ロジウムを分離す
る方法としては、従来から化学的沈澱分離法が採
用されているが、この方法では、実際にはこれら
金属の分離効率が低いため、複雑で熟練を要する
工程が必要であるばかりでなく、直接実収率が低
いこと及び仕掛り中に要する時間や金額の損失が
大きいことなどの問題があつた。そこで、最近
は、処理工程の簡略化、短縮化が可能であるこ
と、金属の選択分離が鋭敏であり、分離金属の精
製回収が容易であることなどの利点を有する溶媒
抽出法に関心が寄せられ、その具体的方法も種々
提案されている。
塩酸酸性水溶液からその中に含有される金、パ
ラジウム、白金、ロジウムを溶媒抽出法を利用し
て分離する方法として、硫酸第一鉄を添加して金
を沈殿させ、該沈殿を分離して得られた濾液を硫
化ジ−ｎ−ヘキシルを抽出溶剤とする有機溶媒と
接触させパラジウムを抽出した有機相と水相とを
分離する方法は、特開昭51−84702号公報、特開
昭57−79135号公報によつて公知である。
また、上記のように硫化ジ−ｎ−ヘキシルを抽
出溶剤としてパラジウムを溶媒抽出する前に、パ
ラジウムを含有する水溶液中の白金をそのイオン
状態を２価から４価に酸化しておいた方が、パラ
ジウムの抽出分離がより選択的になることは、
CIM Special Volume 21 ｐ 24〜31「Selective
Solvent Extractants for the Refining of Pla
−tinum Metals」において開示されている。
しかしながら、白金、ロジウム、パラジウムの
他にビスマスやテルルを含有する塩酸酸性水溶液
に硫化ジ−ｎ−ヘキシルを含有する有機溶媒を用
いてパラジウムを有機相中に抽出する際には、ビ
スマスも該有機相中に抽出され易く、そのビスマ
スがその後有機相中のパラジウムをアンモニア水
で逆抽出するときに相分離を困難にしていた。
本発明は、上記従来法の問題点を解消して、白
金、ロジウム、ビスマス、パラジウム、テルルを
主として含有する塩酸酸性水溶液からパラジウム
を選択性、効率共に分離することができる方法を
提供することを目的するものであり、高級アルコ
ールを外割容量で３〜12％含有させた硫化ジ−ｎ
−ヘキシルを抽出溶剤とすることによつてこの目
的を達成することができた。
以下、本発明を詳細に説明する。
本発明方法によつて金、白金、ロジウム、ビス
マス、パラジウム、テルルを含有する塩酸酸性水
溶液からパラジウムを分離するには、まず金を分
離し、次いでその残液から、その中に含有される
白金及びロジウムを高酸化状態にした後、パラジ
ウムを分離する。
まず金を分離するのは、金を分離しないと次工
程で硫化ジ−ｎ−ヘキシルによつてパラジウムを
溶媒抽出する際、金も全量抽出され抽出された金
は、その後のアンモニア水によるパラジウム逆抽
出において沈殿物となりクラツド生成の一因とな
る他、回収したパラジウムを汚染するからであ
る。金を分離するには、公知の抽出剤としてジブ
チルカルビトールを用いる溶媒抽出法やヒドラジ
ン、第一鉄塩、過酸化水素、シユウ酸、亜硫酸ガ
ス等の還元剤を添加する沈殿分離法が適用でき
る。金を分離した残液から次に硫化ジ−ｎ−ヘキ
シルによつてパラジウムを溶媒抽出するが、該残
液中に２価及び３価イオンとして夫々含有されて
いる白金及びロジウムはその一部が同時に抽出さ
れ、パラジウムの分離効率が低下するので、該溶
媒抽出の前に上記２価の白金及び３価のロジウム
を夫々４価、６価に酸化しておく必要がある。こ
の酸化処理は、２価の白金及び３価のロジウムが
微量であれば省略できる。また、使用する酸化剤
としては塩素ガス、アルカリ金属の次亜塩素酸
塩、塩素酸塩、過塩素酸塩などが好適なものとし
て挙げられる。抽出溶剤として硫化ジ−ｎ−ヘキ
シルを使用してパラジウムを抽出する際には、水
と混和しない、シエルゾールAB（シエル化学の
商品名）などの芳香族溶剤やドスブ、シエルゾー
ルＴ（いずれもシエル化学の商品名）などの脂肪
族溶剤によつて硫化ジ−ｎ−ヘキシルを希釈して
使用するが、本発明はこのような抽出溶剤と希釈
剤からなる抽出溶媒に対して高級アルコールを外
割容量で３〜12％添加することにより、ビスマス
の有機相への抽出を極力抑えてパラジウムを抽出
することができるようにしたものである。
高級アルコールの添加が３％未満ではビスマス
の有機相への抽出が無視できず、有機相中のパラ
ジウムを逆抽出するときに相分離が困難になる。
また、該添加が12％を超えると水溶液中に共存す
る白金が２価に還元され易くなるためか、白金の
有機相への抽出が起り易くなり、パラジウム抽出
の選択分離性が低下する。なお、このパラジウム
抽出において使用する硫化ジ−ｎ−ヘキシルの純
度を99重量％程度の高純度のものとした方が純度
96重量％程度のものとするよりビスマス及び白金
の有機相への抽出を抑える意味で好ましいが、純
度96重量％程度のものでもパラジウムを充分な選
択分離性をもつて抽出することができる。
以下、本発明を実施例について更に詳細に説明
する。
実施例 １
供試水溶液として、銀電解スライムを硝酸で分
解して得た銀抽出液を中和して生成した沈殿物を
塩酸溶解して得られた、第１表の成分、組成を有
する塩酸酸性水溶液を使用した。
The present invention relates to an improvement in a method for separating palladium from an acidic hydrochloric acid aqueous solution containing mainly platinum, rhodium, palladium, and base metals by a solvent extraction method. A hydrochloric acid acidic aqueous solution containing gold and platinum group metals such as gold, palladium, platinum, and rhodium is produced, for example, in a silver electrolytic slime treatment process in a copper electrolytic slime treatment process in copper refining. When silver electrolytic slime is decomposed with nitric acid, a silver extract and a residue are obtained. When this silver extract is neutralized and a precipitate is obtained, which is dissolved in hydrochloric acid, gold, platinum, rhodium, palladium, and base metals are recovered. An acidic aqueous solution containing hydrochloric acid is obtained. On the other hand, the above-mentioned hydrochloric acid acidic aqueous solution can also be obtained by subjecting this residue to acid treatment using hydrochloric acid and hydrogen peroxide. The hydrochloric acid acidic aqueous solution thus obtained has approximately the following composition. That is, gold: 5g/or less,
Silver: 0.1g/or less, Palladium: 5-80g/,
Platinum: 2-30g/, Rhodium: 0.2-10g/,
Bismuth: 5-80g/, Tellurium: 5-40g/
, copper: 10 g/or less, lead: 5 g/or less, and about 1 mole of hydrochloric acid. The chemical precipitation separation method has traditionally been used to separate the gold, palladium, platinum, and rhodium contained therein from the above-mentioned hydrochloric acid acidic aqueous solution. Since the metal separation efficiency is low, not only is a complicated process requiring skill, but there are also problems such as a low direct yield rate and a large loss of time and money during the work in progress. Therefore, recently there has been interest in the solvent extraction method, which has advantages such as simplification and shortening of the treatment process, sensitive selective separation of metals, and easy purification and recovery of separated metals. Various specific methods have been proposed. As a method for separating gold, palladium, platinum, and rhodium contained therein from an acidic hydrochloric acid aqueous solution using a solvent extraction method, ferrous sulfate is added to precipitate gold, and the precipitate is separated. A method of contacting the obtained filtrate with an organic solvent containing di-n-hexyl sulfide as an extraction solvent to separate an organic phase from which palladium has been extracted and an aqueous phase is disclosed in JP-A-51-84702 and JP-A-57- It is known from the publication No. 79135. Furthermore, before solvent extraction of palladium using di-n-hexyl sulfide as an extraction solvent as described above, it is better to oxidize the platinum in the palladium-containing aqueous solution from divalent to tetravalent. , the extraction separation of palladium becomes more selective.
CIM Special Volume 21 p. 24-31 “Selective
Solvent Extractants for the Refining of Plas
-tinum Metals”. However, when palladium is extracted into the organic phase using an organic solvent containing di-n-hexyl sulfide in an acidic hydrochloric acid aqueous solution containing bismuth and tellurium in addition to platinum, rhodium, and palladium, bismuth is also extracted from the organic phase. The bismuth easily extracted into the phase, making phase separation difficult when palladium in the organic phase was subsequently back-extracted with ammonia water. The present invention aims to solve the problems of the conventional methods described above and to provide a method capable of separating palladium with both selectivity and efficiency from an acidic hydrochloric acid aqueous solution mainly containing platinum, rhodium, bismuth, palladium, and tellurium. It is a sulfurized di-n containing 3 to 12% of higher alcohol by volume.
- This objective could be achieved by using hexyl as the extraction solvent. The present invention will be explained in detail below. In order to separate palladium from a hydrochloric acid aqueous solution containing gold, platinum, rhodium, bismuth, palladium, and tellurium by the method of the present invention, the gold is first separated, and then the platinum contained therein is separated from the residual liquid. After bringing rhodium to a highly oxidized state, palladium is separated. First, the gold is separated. If the gold is not separated, in the next step, when palladium is solvent extracted with di-n-hexyl sulfide, all of the gold will be extracted and the extracted gold will be removed from the palladium in the subsequent aqueous ammonia solution. This is because it becomes a precipitate during extraction, contributing to the formation of cladding, and also contaminates the recovered palladium. To separate gold, a known solvent extraction method using dibutyl carbitol as an extractant or a precipitation separation method using a reducing agent such as hydrazine, ferrous salt, hydrogen peroxide, oxalic acid, or sulfurous acid gas can be applied. . Palladium is then solvent-extracted from the residual liquid from which gold has been separated using di-n-hexyl sulfide, but some of the platinum and rhodium contained in the residual liquid as divalent and trivalent ions, respectively. Since they are extracted at the same time and the separation efficiency of palladium decreases, it is necessary to oxidize the divalent platinum and trivalent rhodium to tetravalent and hexavalent, respectively, before the solvent extraction. This oxidation treatment can be omitted if divalent platinum and trivalent rhodium are present in trace amounts. Suitable oxidizing agents to be used include chlorine gas, alkali metal hypochlorites, chlorates, perchlorates, and the like. When extracting palladium using di-n-hexyl sulfide as an extraction solvent, aromatic solvents such as Schielzol AB (trade name of Schiel Chemical Co., Ltd.), which are immiscible with water, or Dosubu, Schielzol T (both trade names of Schiel Chemical Co., Ltd.) are recommended. Di-n-hexyl sulfide is used after being diluted with an aliphatic solvent such as (trade name), but in the present invention, the higher alcohol is added by volume to an extraction solvent consisting of such an extraction solvent and a diluent. By adding 3 to 12% of bismuth to the organic phase, palladium can be extracted while minimizing the extraction of bismuth into the organic phase. If the amount of higher alcohol added is less than 3%, extraction of bismuth into the organic phase cannot be ignored, and phase separation becomes difficult when back-extracting palladium from the organic phase.
Furthermore, if the addition exceeds 12%, the platinum coexisting in the aqueous solution is likely to be reduced to a divalent state, so platinum is more likely to be extracted into the organic phase, and the selective separation of palladium extraction is reduced. In addition, it is better to use di-n-hexyl sulfide with a purity of about 99% by weight for this palladium extraction.
A purity of about 96% by weight is preferable in terms of suppressing the extraction of bismuth and platinum into the organic phase, but palladium can be extracted with sufficient selective separation even with a purity of about 96% by weight. Hereinafter, the present invention will be described in more detail with reference to Examples. Example 1 As a test aqueous solution, hydrochloric acid having the components and composition shown in Table 1 was obtained by dissolving in hydrochloric acid the precipitate produced by neutralizing the silver extract obtained by decomposing silver electrolytic slime with nitric acid. An acidic aqueous solution was used.
【表】
この溶液７を60℃に加温した後、これに100
ｇ／の塩酸ヒドラジンを、この酸化還元電位が
780ｍＶ（飽和甘汞電極基準、以下省略する）から
680ｍＶになるまで添加した金を還元した。沈降
した金粉末を濾別、洗浄、乾燥後、分析すると金
の純度は98.0重量％あつた。また、第２表の成
分、組成を有する脱金液7.3を得た。[Table] After heating this solution 7 to 60℃, add 100%
g/g of hydrazine hydrochloride, this redox potential is
From 780mV (saturated Amane electrode standard, omitted below)
The added gold was reduced to 680 mV. The precipitated gold powder was filtered, washed, dried, and analyzed, and the purity of the gold was 98.0% by weight. In addition, gold removal liquid 7.3 having the components and composition shown in Table 2 was obtained.
【表】
この脱金液を6.8と0.5とに２分し、前者の
液には酸化処理即ち有効塩素５重量％の次亜塩素
酸ナトリウム水溶液を添加してその酸化還元電位
を800ｍＶとした後、また後者の液は前記のよう
な酸化処理を行なわずそのまゝでパラジウムの溶
媒抽出供試液とした。この供試液を試験毎に100
ml採取し、これからのパラジウムの抽出は、相率
（水相：有機相、以下これを省略する）２：１で
シエルゾールABに硫化ジ−ｎ−ヘキシルを溶解
した20容量％溶液を用いて行なつた。脱金液と有
機溶液の混合物を25℃で60分撹拌して沈降させ
た。上記有機溶液は、更に第３表のような純度
（重量％）のものを使用し、高級アルコールとし
てのｎ−ヘキシル−アルコールの添加（外割容量
％）を行なつた。この抽出による有機溶液への抽
出率を第３表各欄の上段に示した。[Table] This degold solution was divided into two parts, 6.8 and 0.5, and the former solution was oxidized, that is, by adding a sodium hypochlorite aqueous solution containing 5% by weight of available chlorine to bring the redox potential to 800 mV. The latter solution was used as a palladium solvent extraction test solution without being subjected to the oxidation treatment as described above. 100% of this sample solution is used for each test.
ml was collected, and palladium was extracted from this using a 20% by volume solution of di-n-hexyl sulfide dissolved in Schierzol AB at a phase ratio (aqueous phase: organic phase, hereinafter omitted) of 2:1. Summer. The mixture of gold removal solution and organic solution was stirred at 25° C. for 60 minutes to allow precipitation. The above organic solution had a purity (% by weight) as shown in Table 3, and n-hexyl alcohol was added as a higher alcohol (% by volume). The extraction rate of this extraction into the organic solution is shown in the upper row of each column in Table 3.
【表】
次に得られた抽出有機相からのパラジウムの逆
抽出は、相率２：３で６容量％アンモニア水溶液
を用いて行なつた。両溶液の混合物を25℃で10分
撹拌して沈降させた。この逆抽出による水相への
抽出率を第３表各欄の下段に示した。この逆抽出
は、全比較例においてクラツドの生成が見られ、
試験No.３において明瞭な相分離が困難になり、ま
た試験No.５及び６においては明瞭な相分離が不可
能であつた。
第３表から、酸化処理を行なわないと、抽出時
にパラジウムと同時に白金及びロジウムの一部も
抽出され、パラジウムの分離効率が低下すること
並びにｎ−ヘキシル−アルコールを添加しない
と、抽出時にパラジウムと同時にビスマスの抽出
もかなりみられることが判る。
実施例 ２
供試水溶液として、銀電解スライムを硝酸で分
解して得た残渣に塩酸と過酸化水素とを使用した
酸処理を施して得られた、第４表の成分、組成を
有する塩酸酸性水溶液を使用した。[Table] Palladium was then back-extracted from the extracted organic phase obtained using a 6% by volume ammonia aqueous solution at a phase ratio of 2:3. The mixture of both solutions was stirred at 25° C. for 10 minutes to allow sedimentation. The extraction rate into the aqueous phase by this back extraction is shown at the bottom of each column in Table 3. In this back extraction, formation of crud was observed in all comparative examples,
Clear phase separation became difficult in Test No. 3, and clear phase separation was impossible in Test Nos. 5 and 6. Table 3 shows that if oxidation treatment is not performed, some platinum and rhodium will be extracted at the same time as palladium, reducing the separation efficiency of palladium, and if n-hexyl alcohol is not added, palladium and rhodium will be extracted during extraction. At the same time, it can be seen that a considerable amount of bismuth is extracted. Example 2 As a test aqueous solution, a hydrochloric acid acidic solution having the components and composition shown in Table 4 was obtained by subjecting the residue obtained by decomposing silver electrolytic slime with nitric acid to acid treatment using hydrochloric acid and hydrogen peroxide. An aqueous solution was used.
【表】
この溶液７を60℃に加温した後、これに100
ｇ／の塩酸ヒドラジンを添加しこの酸化還元電
位を900ｍＶから630ｍＶとして金を還元した。沈
降した金粉末を濾別、洗浄、乾燥後、分析すると
金の純度は98.0重量％であつた。また、第５表の
成分、組成を有する脱金液7.7を得た。[Table] After heating this solution 7 to 60℃, add 100%
The gold was reduced by adding 1 g/g of hydrazine hydrochloride to increase the redox potential from 900 mV to 630 mV. The precipitated gold powder was filtered, washed, dried, and analyzed, and the purity of the gold was 98.0% by weight. In addition, gold removal liquid 7.7 having the components and composition shown in Table 5 was obtained.
【表】
この脱金液を7.0と0.7とに２分し、前者の
液には酸化処理即ち有効塩素５重量％の次亜鉛素
酸ナトリウム水溶液を添加してその酸化還元電位
を800ｍＶとした後、また後者の液は前記のよう
な酸化処理を行なわずそのまゝで、夫々パラジウ
ムの溶媒抽出供試液とした。この供試液を試験毎
に100ml採取し、これからのパラジウムの抽出は、
相率１：１でシエルゾールABに硫化ジ−ｎ−ヘ
キシルを溶解した20容量％溶液を用いて行なつ
た。両溶液の混合物を25℃で90分間撹拌して沈降
させた。上記有機溶液は、顕に第６表のような純
度（重量％）のものを使用し、高級アルコールと
してのｎ−ヘキシル−アルコールの添加（外割容
量％）を行なつた。この抽出による有機溶液中へ
の抽出率を第６表各欄の上段に示した。
次に得られた抽出有機相からのパラジウムの逆
抽出は、実施例１と全く同様にして行なつた。
この逆抽出による水相への抽出率の結果を第６
表各欄の下段に示した。この逆抽出は、全比較例
においてクラツドの生成が見られ、試験No.９にお
いて明瞭な相分離が困難になり、また試験No.12〜
14においては明瞭な相分離が不可能であつた。
第６表からも第３表について前述したと同様な
ことが判る。[Table] This degold solution was divided into 7.0 and 0.7, and the former solution was oxidized, that is, an aqueous sodium hypozinc oxide solution containing 5% by weight of available chlorine was added to bring the redox potential to 800 mV. The latter solutions were used as sample solutions for palladium extraction with a solvent without being subjected to the oxidation treatment as described above. Collect 100ml of this sample solution for each test, and extract palladium from this.
The experiment was carried out using a 20% by volume solution of di-n-hexyl sulfide dissolved in Schierzol AB at a phase ratio of 1:1. The mixture of both solutions was stirred at 25° C. for 90 minutes to allow sedimentation. The organic solution used had a purity (% by weight) as shown in Table 6, and n-hexyl alcohol was added as a higher alcohol (% by volume). The extraction rate into the organic solution by this extraction is shown in the upper row of each column in Table 6. Palladium was then back-extracted from the extracted organic phase obtained in exactly the same manner as in Example 1. The results of the extraction rate into the aqueous phase by this back extraction are shown in the sixth column.
Shown at the bottom of each column in the table. In this back extraction, formation of cladding was observed in all comparative examples, making clear phase separation difficult in Test No. 9, and in Test No. 12 to
No clear phase separation was possible in No. 14. It can be seen from Table 6 that the same thing as mentioned above regarding Table 3 can be seen.
【表】【table】
Claims (1)
して含有する塩酸酸性水溶液を、高級アルコール
を外割容量で３〜12％含有させた、硫化ジ−ｎ−
ヘキシルを抽出溶剤とする有機溶媒と接触させ、
パラジウムを有機溶媒中に水溶液から分離するこ
とを特徴とする塩酸酸性水溶液からのパラジウム
の分離方法。 ２ 有機溶媒と接触せしめる塩酸酸性水溶液が、
その中に含有される白金及びロジウムを夫々４価
及び６価のイオンの状態に酸化処理されたもので
ある特許請求の範囲１項記載の塩酸酸性水溶液か
らのパラジウムの分離方法。[Scope of Claims] 1. A sulfurized di-n-hydrochloric acid aqueous solution containing mainly platinum, rhodium, palladium, and base metals containing 3 to 12% of higher alcohol by volume.
Contact with an organic solvent using hexyl as an extraction solvent,
A method for separating palladium from an aqueous hydrochloric acid solution, which comprises separating palladium from an aqueous solution in an organic solvent. 2 An acidic aqueous solution of hydrochloric acid brought into contact with an organic solvent,
The method for separating palladium from an acidic aqueous solution of hydrochloric acid according to claim 1, wherein the platinum and rhodium contained therein are oxidized to the state of tetravalent and hexavalent ions, respectively.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58096456A JPS6086220A (en) | 1983-05-31 | 1983-05-31 | Method for separating palladium from aqueous hydrochloric acid solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58096456A JPS6086220A (en) | 1983-05-31 | 1983-05-31 | Method for separating palladium from aqueous hydrochloric acid solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6086220A JPS6086220A (en) | 1985-05-15 |
| JPH021895B2 true JPH021895B2 (en) | 1990-01-16 |
Family
ID=14165524
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58096456A Granted JPS6086220A (en) | 1983-05-31 | 1983-05-31 | Method for separating palladium from aqueous hydrochloric acid solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6086220A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2649225B2 (en) * | 1987-04-27 | 1997-09-03 | 田中貴金属工業 株式会社 | Recovery of rhodium from nitric acid solution containing rhodium |
| JPS63286529A (en) * | 1987-05-18 | 1988-11-24 | Tanaka Kikinzoku Kogyo Kk | Recovering method for pd from pd-containing aqueous solution |
| JPS63286528A (en) * | 1987-05-18 | 1988-11-24 | Tanaka Kikinzoku Kogyo Kk | Recovering method for pd from pd-containing aqueous solution |
| JPH0791597B2 (en) * | 1987-05-18 | 1995-10-04 | 田中貴金属工業株式会社 | Palladium extraction separation method |
| JPH02153028A (en) * | 1988-12-06 | 1990-06-12 | Tanaka Kikinzoku Kogyo Kk | Method for recovering pd from aqueous solution containing pd |
| JP2771218B2 (en) * | 1989-02-15 | 1998-07-02 | 大八化学工業株式会社 | Recovery of palladium from aqueous solution |
| JPH02310326A (en) * | 1989-05-23 | 1990-12-26 | Tanaka Kikinzoku Kogyo Kk | Method for separating and recovering gold from noble metal solution |
| JP2887036B2 (en) * | 1993-01-19 | 1999-04-26 | 住友金属鉱山株式会社 | Separation and purification method of fission-generated noble metal |
-
1983
- 1983-05-31 JP JP58096456A patent/JPS6086220A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6086220A (en) | 1985-05-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0049567B1 (en) | Process for the extraction of precious metals from solutions thereof | |
| JP3741117B2 (en) | Mutual separation of platinum group elements | |
| US6126720A (en) | Method for smelting noble metal | |
| RU2494159C1 (en) | Method of noble metal extraction | |
| JPWO1998058089A1 (en) | Precious metal refining method | |
| US4012481A (en) | Process for the separation of platinum group metals | |
| JP5825484B2 (en) | Method for recovering platinum group metals | |
| JPS5928614B2 (en) | Method for separating and purifying platinum and/or palladium | |
| KR100230826B1 (en) | Method of recovering gold | |
| JP2012246198A (en) | Method for purifying selenium by wet process | |
| JP7198079B2 (en) | Method for treating acidic liquids containing precious metals, selenium and tellurium | |
| JPH021895B2 (en) | ||
| JPH08209259A (en) | A method for separating and recovering a platinum group element from a platinum group-containing iron alloy. | |
| US5284633A (en) | Solvent extraction of precious metals with hydroxyquinoline and stripping with acidified thiourea | |
| JP7337209B2 (en) | Iridium recovery method | |
| EP1577408B2 (en) | Method for separating platinum group elements from selenum/tellurium bearing materials | |
| JP2000239753A (en) | Tellurium separation and purification method | |
| JPH09279264A (en) | Continuous extraction and recovery method for precious metals | |
| JPH10265863A (en) | Precious metal recovery method from smelting residue | |
| JP7400443B2 (en) | Mutual separation method of platinum group elements | |
| US3996046A (en) | Extraction and purification of silver from sulfates | |
| JP4470749B2 (en) | Rhodium recovery method and metal rhodium production method | |
| JP3407600B2 (en) | Silver extraction and recovery method | |
| JP3309801B2 (en) | How to collect gold | |
| RU2200132C1 (en) | Method of recovering and separating platinum-group metals |