JP2010229446A - Method of recovering platinum group element - Google Patents
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- JP2010229446A JP2010229446A JP2009076079A JP2009076079A JP2010229446A JP 2010229446 A JP2010229446 A JP 2010229446A JP 2009076079 A JP2009076079 A JP 2009076079A JP 2009076079 A JP2009076079 A JP 2009076079A JP 2010229446 A JP2010229446 A JP 2010229446A
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 44
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- -1 ammonium ions Chemical class 0.000 claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 238000005805 hydroxylation reaction Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 230000033444 hydroxylation Effects 0.000 claims description 9
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000006864 oxidative decomposition reaction Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 25
- 239000003513 alkali Substances 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 12
- 229910052741 iridium Inorganic materials 0.000 description 11
- 238000011084 recovery Methods 0.000 description 11
- 229910052763 palladium Inorganic materials 0.000 description 7
- 229910052703 rhodium Inorganic materials 0.000 description 7
- 239000010948 rhodium Substances 0.000 description 7
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- 150000002500 ions Chemical group 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000007670 refining Methods 0.000 description 4
- 239000005708 Sodium hypochlorite Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- IUJMNDNTFMJNEL-UHFFFAOYSA-K iridium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ir+3] IUJMNDNTFMJNEL-UHFFFAOYSA-K 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005406 washing Methods 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
本発明は、白金族元素を含有するアンモニウム溶液から白金族元素を回収する方法に関する。 The present invention relates to a method for recovering a platinum group element from an ammonium solution containing the platinum group element.
白金族元素は存在量が非常に少ないことが良く知られているが、非鉄製錬における電解精製工程で発生する陽極泥には白金族元素が濃縮されており、白金族元素回収原料とされている。陽極泥からの白金族元素の回収に関しては種々のプロセスが開発されているが、近年、溶媒抽出剤を利用した湿式精錬が主流となっている。 It is well known that platinum group elements are present in very small amounts, but the anode mud generated in the electrolytic refining process in non-ferrous smelting is enriched with platinum group elements and is used as a platinum group element recovery raw material. Yes. Various processes have been developed for the recovery of platinum group elements from anode mud, but in recent years, wet refining using a solvent extractant has become the mainstream.
このような用途におけるもっとも一般的な溶媒抽出剤としてトリブチル燐酸（ＴＢＰ）が利用されている。例えば特許文献１に開示されているように、ロジウム精製プロセスにおいてロジウム以外の白金族元素の抽出、除去を行う目的で使用されている。 Tributyl phosphoric acid (TBP) is used as the most common solvent extractant for such applications. For example, as disclosed in Patent Document 1, it is used for the purpose of extracting and removing platinum group elements other than rhodium in a rhodium purification process.
ＴＢＰをはじめとする溶媒抽出剤は高価であるのでその再利用のために、また同時に、抽出された白金族元素の回収のためにＴＢＰからの白金族元素の逆抽出反応が行われる。特許文献２に開示されているように、この逆抽出反応では塩化アンモニウム溶液が用いられる。 Since solvent extractants such as TBP are expensive, the platinum group element is back-extracted from TBP for reuse and at the same time for recovery of the extracted platinum group element. As disclosed in Patent Document 2, an ammonium chloride solution is used in this back extraction reaction.
該方法により逆抽出された溶液中には、数グラム／リットル程度の白金族元素が含有されており、この溶液を銅精錬の上流工程、例えば、自熔炉または転炉に戻すことで再度陽極泥として白金族元素回収原料とすることが可能である。しかし、該溶液に含有される白金族元素のうちイリジウムに関しては該溶液をその回収精製プロセスの出発原料とするのが最も適しており、よってこの観点から該溶液からの白金族元素の回収が望ましい。 The solution back-extracted by this method contains about several grams / liter of a platinum group element, and this solution is returned to an upstream process of copper refining, for example, a flash smelting furnace or a converter, so that anode mud is again obtained. As a platinum group element recovery raw material. However, regarding iridium among platinum group elements contained in the solution, it is most suitable to use the solution as a starting material for the recovery and purification process. Therefore, recovery of the platinum group element from the solution is desirable from this viewpoint. .
溶液から金属イオンを回収する方法として、一般的に水酸化物形成による沈殿法および硫化法が利用されている。しかし、アンモニウムイオンが多量に含有されている液に対してアルカリ剤を添加して水酸化処理した場合、白金族元素イオンがアンミン錯体を形成するので、液中でより安定な溶質イオンとなり、水酸化物形成は全く起こらない。硫化法では、白金族元素によっては硫化が困難なものがあることと、硫化物を種々の精錬手法にとって最適な形態である塩化物、または、塩化物溶液に転換することは容易ではない。 As a method for recovering metal ions from a solution, a precipitation method by hydroxide formation and a sulfidation method are generally used. However, when an alkaline agent is added to a liquid containing a large amount of ammonium ions and subjected to a hydroxylation treatment, the platinum group element ions form ammine complexes, so that they become more stable solute ions in the liquid. No oxide formation occurs. In the sulfidation method, some platinum group elements are difficult to sulfidize, and it is not easy to convert the sulfide into a chloride or chloride solution which is an optimum form for various refining techniques.
その他に、白金族元素の液中からの回収法として、古くから晶析法と呼ばれるアルカリイオンおよびアンモニウムイオンと塩化物イオンからなる結晶を加えることにより白金族元素のクロロ錯体とアルカリ金属イオンおよびアンモニウムイオンからなる難溶性の結晶を作製することで白金族元素を回収する方法が知られている。しかし、晶析法では、低濃度の白金族元素イオンの液に対しては晶析率が５０〜８０％程度であり、少なからぬ白金族元素の損失が生じる。しかも、得られる晶析物は難溶性のため再溶解が困難であり、特にアンモニウムイオンからなる晶析物の場合、アンモニウムイオンと白金族元素との分離は困難である。 In addition, as a method for recovering platinum group elements from liquids, platinum group chloro complexes, alkali metal ions and ammonium have been added by adding crystals of alkali ions, ammonium ions and chloride ions, which have been called crystallization methods for a long time. A method for recovering a platinum group element by producing a hardly soluble crystal composed of ions is known. However, in the crystallization method, the crystallization rate is about 50 to 80% with respect to a liquid of a low concentration of platinum group element ions, and a considerable loss of platinum group element occurs. In addition, since the obtained crystallized product is hardly soluble, it is difficult to re-dissolve, and particularly in the case of a crystallized product composed of ammonium ions, it is difficult to separate ammonium ions from platinum group elements.
本発明の目的は、白金族元素を含むアンモニウム溶液から白金族元素を回収する方法を提供するものである。 An object of the present invention is to provide a method for recovering a platinum group element from an ammonium solution containing the platinum group element.
本発明は、上記課題を解決するものであって、
（１）白金族元素を含有するアンモニウム溶液から白金族元素を回収する方法において、
該溶液にアルカリ剤を添加し、加熱処理を行うことにより液中のアンモニウムイオンの大部分をアンモニアとして揮発除去を行うアンモニア除去工程
該アンモニア除去処理液を加熱し、酸化剤を添加し、残余のアンモニアを窒素として酸化分解を行い、
さらに塩酸を加え、液ｐＨを７から９に調整を行い、酸化剤を添加することで白金族元素を水酸化物として沈殿処理すること
からなる白金族元素の回収方法。
（２）上記（１）に記載のアンモニア除去工程において、原料溶液に加える塩基は水酸化ナトリウム、水酸化カリウムの何れか一つを含む白金族元素の回収方法。
The present invention solves the above problems,
(1) In a method for recovering a platinum group element from an ammonium solution containing the platinum group element,
An ammonia removing step of adding an alkaline agent to the solution and performing a heat treatment to volatilize and remove most of the ammonium ions in the solution as ammonia. The ammonia removing treatment solution is heated, an oxidizing agent is added, and the remaining amount is removed. Oxidative decomposition using ammonia as nitrogen,
A method for recovering a platinum group element comprising adding hydrochloric acid, adjusting the liquid pH to 7 to 9, and adding an oxidizing agent to precipitate the platinum group element as a hydroxide.
(2) In the ammonia removal step according to the above (1), the base added to the raw material solution is a method for recovering a platinum group element containing one of sodium hydroxide and potassium hydroxide.
（３）上記（１）に記載のアンモニア除去工程において、原料溶液に塩基を加え、液ｐＨを９から１３とする白金族元素の回収方法。
（４）上記（１）に記載のアンモニア除去工程において、
塩基を加えた原料溶液の加熱処理が７０℃から１００℃であり、処理時間が４時間以上である白金族元素の回収方法。
（５）上記（２）に記載のＰＧＭ水酸化処理工程において、加える酸化剤が次亜塩素酸塩である白金族元素の回収方法。
（６）上記（２）に記載のＰＧＭ水酸化処理工程において、加える酸が塩酸、硫酸、硝酸、炭酸、酢酸、リン酸、蓚酸の何れか一つを含むこ白金族元素の回収方法。
（７）上記（２）に記載のＰＧＭ水酸化処理工程において、原料溶液の加熱処理が７０℃から１００℃である白金族元素の回収方法。
を提供する。
(3) A method for recovering a platinum group element, wherein a base is added to the raw material solution to adjust the liquid pH to 9 to 13 in the ammonia removing step according to (1) above.
(4) In the ammonia removal step described in (1) above,
A method for recovering a platinum group element, wherein the heat treatment of the raw material solution to which the base is added is from 70 ° C. to 100 ° C., and the treatment time is 4 hours or more.
(5) A method for recovering a platinum group element, wherein the oxidizing agent to be added is hypochlorite in the PGM hydroxylation treatment step according to (2) above.
(6) A method for recovering a platinum group element in which the acid to be added includes any one of hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, acetic acid, phosphoric acid, and oxalic acid in the PGM hydroxylation treatment step according to (2).
(7) A method for recovering a platinum group element, wherein the heat treatment of the raw material solution is 70 ° C. to 100 ° C. in the PGM hydroxylation process described in (2) above.
I will provide a.
本発明によれば、
（１）パラジウム、ロジウム、イリジウムの各白金族元素をほぼ完全に回収すること
が可能である。
（２）得られる白金族元素沈殿物を塩酸で洗浄を行うことで、イリジウム、ロジウム
の損失なしにパラジウムおよび不純物元素の洗浄除去を行うことが可能である。
（３）得られた白金族元素沈殿物を塩酸に溶解することでアンモニウムイオンおよび
アルカリ金属イオンを含まない高濃度の塩化物溶液を容易に得ることが可能である。
等を挙げることができる。
According to the present invention,
(1) It is possible to almost completely recover each platinum group element of palladium, rhodium, and iridium.
(2) By washing the resulting platinum group element precipitate with hydrochloric acid, it is possible to wash and remove palladium and impurity elements without loss of iridium and rhodium.
(3) It is possible to easily obtain a high-concentration chloride solution not containing ammonium ions and alkali metal ions by dissolving the obtained platinum group element precipitate in hydrochloric acid.
Etc.
以下本発明について、詳細に説明する。
本発明であるイリジウムの回収方法は、白金族元素を含有するアンモニウム溶液を出発原料とする。
白金族元素とは、白金、パラジウム、イリジウム、ロジウム等である。
その濃度は、白金 ３０ から １００００ｍｇ／Ｌ
パラジウム３０ から１０００００ｍｇ／Ｌ
イリジウム３０ から１０００００ｍｇ／Ｌ
ロジウム３０ から１０００００ｍｇ／Ｌ
アンモニア濃度は、０．１〜２５０ｇ／Ｌである。
The present invention will be described in detail below.
In the iridium recovery method of the present invention, an ammonium solution containing a platinum group element is used as a starting material.
The platinum group element is platinum, palladium, iridium, rhodium, or the like.
Its concentration is 30 to 10,000 mg / L of platinum.
Palladium 30 to 100,000 mg / L
Iridium 30 to 100,000 mg / L
Rhodium 30 to 100000mg / L
The ammonia concentration is 0.1 to 250 g / L.
（アンモニアの除去工程）
本発明のアンモニア除去工程では、原料溶液に塩基を添加ことで液中のアンモニアの揮発除去を行う。塩基は、例えば、水酸化ナトリウム、水酸化カリウムを使用する。
液中のアンモニアは解離性（NH4+）と非解離性（NH3）の２形態で存在しており、この両形態の割合は乖離定数と液温によって決まっている。液温が２０℃の場合、非解離性アンモニアの割合が５０％以上となるのはｐＨが９．４以上であり、ｐＨ１１では９７％程度になる。液中から揮発除去が可能であるアンモニアは非解離性アンモニアの形態であるので、塩基を添加することで液ｐＨを９以上に上げることが必要である。
好ましくは、ｐＨを９から１３である。
また加熱温度は、７０℃以上である。好ましくは、７０℃から１００℃である。
保持時間は、４時間以上である。
これにより、液中に存在するアンモニウムイオンの大部分をアンモニアとして揮発除去を行う。
(Ammonia removal process)
In the ammonia removal step of the present invention, ammonia in the liquid is removed by volatilization by adding a base to the raw material solution. As the base, for example, sodium hydroxide or potassium hydroxide is used.
Ammonia in the liquid exists in two forms, dissociative (NH4 +) and non-dissociable (NH3), and the ratio of both forms is determined by the detachment constant and the liquid temperature. When the liquid temperature is 20 ° C., the ratio of non-dissociable ammonia is 50% or more when the pH is 9.4 or more, and at pH 11, it is about 97%. Ammonia, which can be volatilized and removed from the liquid, is in the form of non-dissociable ammonia, so it is necessary to increase the liquid pH to 9 or more by adding a base.
Preferably, the pH is 9 to 13.
The heating temperature is 70 ° C. or higher. Preferably, it is 70 to 100 ° C.
The holding time is 4 hours or more.
As a result, most of the ammonium ions present in the liquid are volatilized and removed as ammonia.
（残余のアンモニアの除去工程）
本発明のＰＧＭ水酸化処理工程では、アンモニア揮発除去を終了した液に対し酸化剤を添加する。
酸化剤としては、空気、酸素含有ガス、過酸化水素等であるが、好ましくは、次亜塩素酸塩を用いる。
これにより、残余のアンモニアを窒素ガスとして酸化分解することで除去を行う。アンモニアが残存していると、白金族元素の水酸化反応が不充分となり回収率が低下する。
（水酸化物の形成工程）
次に酸を添加し、液ｐＨを９より低下させる。
白金族元素の水酸化物形成時の液ｐＨが９より高いとイリジウムの一部が水酸化物錯イオンを形成することで沈殿しなくなり、一方、ｐＨが５より低いと水酸化物を形成しないので沈殿しない。
より好ましくは、ｐHは、7〜9である。
酸としては、塩酸、硫酸、硝酸、炭酸、酢酸、リン酸、蓚酸の何れか一つを用いる。
酸（例えば塩酸）添加後、酸化剤（例えば次亜塩素酸塩）を添加することでイリジウムは３価から４価に酸化されて水酸化イリジウムとして沈殿する。徐冷後、濾過により水酸化イリジウムを回収する。
最終的な白金族元素の回収率は９０％以上、特にパラジウム、イリジウムの回収率は９９％程度に達する。
(Residual ammonia removal process)
In the PGM hydroxylation process of the present invention, an oxidizing agent is added to the liquid that has been removed from the ammonia volatilization.
Examples of the oxidizing agent include air, oxygen-containing gas, hydrogen peroxide, and the like, but hypochlorite is preferably used.
Thus, the remaining ammonia is removed by oxidative decomposition using nitrogen gas. If ammonia remains, the hydroxylation reaction of the platinum group element becomes insufficient and the recovery rate decreases.
(Hydroxide formation process)
Next, an acid is added to lower the liquid pH from 9.
If the pH of the platinum group element hydroxide is higher than 9, a portion of iridium will not precipitate due to the formation of hydroxide complex ions, whereas if the pH is lower than 5, no hydroxide will be formed. So it will not precipitate.
More preferably, the pH is 7-9.
As the acid, any one of hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, acetic acid, phosphoric acid, and succinic acid is used.
By adding an oxidizing agent (for example, hypochlorite) after adding an acid (for example, hydrochloric acid), iridium is oxidized from trivalent to tetravalent and precipitates as iridium hydroxide. After slow cooling, iridium hydroxide is recovered by filtration.
The final platinum group element recovery rate is 90% or more, and in particular, the palladium and iridium recovery rates reach about 99%.
以下に実施例をもって本発明を説明するが、実施例によって限定されるものではない。図１に、本発明の一態様を示す。図１に沿ってより具体的に本発明を説明する。 The present invention will be described below with reference to examples, but the present invention is not limited to the examples. FIG. 1 illustrates one embodiment of the present invention. The present invention will be described more specifically with reference to FIG.
（実施例１）
出発原料として、表１に示す塩化物溶液２０Ｌを使用した。
アンモニア濃度は２５ｇ／Ｌであった。
以下に原料溶液に含まれる主要な白金族元素の分析値を表１示す。
As a starting material, 20 L of a chloride solution shown in Table 1 was used.
The ammonia concentration was 25 g / L.
Table 1 shows analysis values of main platinum group elements contained in the raw material solution.
（アンモニア除去処理）
固体水酸化ナトリウム２ｋｇを該溶液に投入し、８５℃に加熱、１０時間保持を行った。液ｐＨは１２まで上昇した。加熱中は水分蒸発による液量減少を補うために純水を補った。加熱処理後の液中のアンモニア濃度は１ｇ／Ｌ未満に低下した。
(Ammonia removal treatment)
2 kg of solid sodium hydroxide was added to the solution, heated to 85 ° C. and held for 10 hours. The liquid pH rose to 12. During heating, pure water was supplemented to compensate for the decrease in liquid volume due to water evaporation. The ammonia concentration in the liquid after the heat treatment decreased to less than 1 g / L.
（残余のアンモニア除去処理）
該アンモニア除去処理液を８５℃に加熱し、５％次亜塩素酸ソーダ１Ｌを２時間かけて添加を行った。これにより、残余のアンモニアを窒素ガスとして酸化分解することで除去できた。
この時、液ＯＲＰ値はスタート時の−２００ｍＶ以下から３００ｍＶ程度まで上昇した。
（水酸化物の形成工程）
次に８５℃加熱状態を維持しつつ濃塩酸約１Ｌを１時間かけて添加した。液ｐＨは８まで低下した。
次に８５℃加熱状態を維持しつつ５％次亜塩素酸ソーダ１Ｌを２時間かけて添加を行った。これにより、イリジウムは３価から４価に酸化され、イリジウムは水酸化物を形成する。
液ｐＨは７．５まで低下し、液ＯＲＰは６００ｍＶ程度まで上昇した。
５％次亜塩素酸ソーダ添加終了後、徐冷し、室温まで下がった後、濾過を行い白金族水酸化物の回収を行った。濾液の分析値を以下表２に示す。
上記のｐHとORPの変化を図２に示す。
The ammonia removal treatment liquid was heated to 85 ° C., and 1 L of 5% sodium hypochlorite was added over 2 hours. Thus, the remaining ammonia was removed by oxidative decomposition as nitrogen gas.
At this time, the liquid ORP value increased from −200 mV or less at the start to about 300 mV.
(Hydroxide formation process)
Next, about 1 L of concentrated hydrochloric acid was added over 1 hour while maintaining the 85 ° C. heating state. The liquid pH dropped to 8.
Next, 1 L of 5% sodium hypochlorite was added over 2 hours while maintaining the 85 ° C. heating state. Thereby, iridium is oxidized from trivalent to tetravalent, and iridium forms a hydroxide.
The liquid pH decreased to 7.5, and the liquid ORP increased to about 600 mV.
After completion of the addition of 5% sodium hypochlorite, the mixture was gradually cooled to room temperature, and then filtered to recover the platinum group hydroxide. The analytical values of the filtrate are shown in Table 2 below.
The change in pH and ORP is shown in FIG.
Claims (7)
該溶液にアルカリ剤を添加し、加熱処理を行うことにより液中のアンモニウムイオンの大部分をアンモニアとして揮発除去を行うアンモニア除去工程
該アンモニア除去処理液を加熱し、酸化剤を添加し、残余のアンモニアを窒素として酸化分解を行い、
さらに塩酸を加え、液ｐＨを７から９に調整を行い、酸化剤を添加することで白金族元素を水酸化物として沈殿処理すること
からなることを特徴とする白金族元素の回収方法。 In a method for recovering a platinum group element from an ammonium solution containing the platinum group element,
An ammonia removing step of adding an alkaline agent to the solution and performing a heat treatment to volatilize and remove most of the ammonium ions in the solution as ammonia. The ammonia removing treatment solution is heated, an oxidizing agent is added, and the remaining amount is removed. Oxidative decomposition using ammonia as nitrogen,
A method for recovering a platinum group element, further comprising adding hydrochloric acid, adjusting the solution pH to 7 to 9, and adding an oxidizing agent to precipitate the platinum group element as a hydroxide.
原料溶液に加える塩基は水酸化ナトリウム、水酸化カリウムの何れか一つを含むことを特徴とする白金族元素の回収方法。 In the ammonia removal step according to claim 1,
A method for recovering a platinum group element, wherein the base added to the raw material solution contains any one of sodium hydroxide and potassium hydroxide.
原料溶液に塩基を加え、液ｐＨを９から１３とすることを特徴とする白金族元素の回収方法。 In the ammonia removal step according to claim 1,
A method for recovering a platinum group element, wherein a base is added to a raw material solution to adjust the pH of the solution to 9 to 13.
塩基を加えた原料溶液の加熱処理が７０℃から１００℃であり、処理時間が４時間以上であることを特徴とする白金族元素の回収方法。 In the ammonia removal step according to claim 1,
A method for recovering a platinum group element, wherein the heat treatment of the raw material solution to which the base has been added is from 70 ° C to 100 ° C, and the treatment time is 4 hours or more.
加える酸化剤が次亜塩素酸塩であることを特徴とする白金族元素の回収方法。 In the PGM hydroxylation process according to claim 2,
A method for recovering a platinum group element, wherein the oxidizing agent to be added is hypochlorite.
加える酸が塩酸、硫酸、硝酸、炭酸、酢酸、リン酸、蓚酸の何れか一つを含むことを特徴とする白金族元素の回収方法。 In the PGM hydroxylation process according to claim 2,
A method for recovering a platinum group element, wherein the acid to be added contains any one of hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, acetic acid, phosphoric acid, and oxalic acid.
原料溶液の加熱処理が７０℃から１００℃であることを特徴とする白金族元素の回収方法。
In the PGM hydroxylation process according to claim 2,
A method for recovering a platinum group element, wherein the heat treatment of the raw material solution is from 70 ° C to 100 ° C.
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