CA1068116A - Process for the treatment of platinum group metals and gold - Google Patents
Process for the treatment of platinum group metals and goldInfo
- Publication number
- CA1068116A CA1068116A CA244,171A CA244171A CA1068116A CA 1068116 A CA1068116 A CA 1068116A CA 244171 A CA244171 A CA 244171A CA 1068116 A CA1068116 A CA 1068116A
- Authority
- CA
- Canada
- Prior art keywords
- metals
- precious
- residue
- aluminum
- 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.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims abstract description 47
- 230000008569 process Effects 0.000 title claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 title claims description 47
- 239000002184 metal Substances 0.000 title claims description 44
- -1 platinum group metals Chemical class 0.000 title claims description 21
- 239000010931 gold Substances 0.000 title claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims description 6
- 229910052737 gold Inorganic materials 0.000 title claims description 6
- 239000010970 precious metal Substances 0.000 claims abstract description 92
- 239000010953 base metal Substances 0.000 claims abstract description 44
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000012141 concentrate Substances 0.000 claims abstract description 42
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 37
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 23
- 239000000956 alloy Substances 0.000 claims abstract description 23
- 230000001590 oxidative effect Effects 0.000 claims abstract description 20
- 238000004090 dissolution Methods 0.000 claims abstract description 15
- 239000007800 oxidant agent Substances 0.000 claims abstract description 13
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002386 leaching Methods 0.000 claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 16
- 229910000923 precious metal alloy Inorganic materials 0.000 claims description 15
- 229910000838 Al alloy Inorganic materials 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 13
- 150000002739 metals Chemical class 0.000 claims description 13
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 12
- 229960000443 hydrochloric acid Drugs 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 239000001117 sulphuric acid Substances 0.000 claims description 9
- 235000011149 sulphuric acid Nutrition 0.000 claims description 9
- 229910052741 iridium Inorganic materials 0.000 claims description 8
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 239000002893 slag Substances 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 238000007133 aluminothermic reaction Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 150000003568 thioethers Chemical class 0.000 claims description 3
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 claims 1
- 239000004411 aluminium Substances 0.000 abstract description 20
- 239000000463 material Substances 0.000 description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 21
- 229910052697 platinum Inorganic materials 0.000 description 8
- 239000011133 lead Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 230000001419 dependent effect Effects 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 229910017060 Fe Cr Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- WNQQFQRHFNVNSP-UHFFFAOYSA-N [Ca].[Fe] Chemical compound [Ca].[Fe] WNQQFQRHFNVNSP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 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
- 238000001816 cooling Methods 0.000 description 1
- KYCIUIVANPKXLW-UHFFFAOYSA-N dimethyl-(2-phenoxyethyl)-(thiophen-2-ylmethyl)azanium Chemical compound C=1C=CSC=1C[N+](C)(C)CCOC1=CC=CC=C1 KYCIUIVANPKXLW-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- JGLNNORWOWUYFX-UHFFFAOYSA-N lead platinum Chemical group [Pt].[Pb] JGLNNORWOWUYFX-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Adornments (AREA)
Abstract
A B S T R A C T
A process for the dissolution of precious metal values in a concentrate thereof wherein the concentrate is caused to alloy with aluminium and the alloy is then leached in at least two steps, the first of which is to remove base metals and in the second of which the precious metals are dissolved using hydrochloric acid and chlorine gas as an oxidant.
A process for the dissolution of precious metal values in a concentrate thereof wherein the concentrate is caused to alloy with aluminium and the alloy is then leached in at least two steps, the first of which is to remove base metals and in the second of which the precious metals are dissolved using hydrochloric acid and chlorine gas as an oxidant.
Description
o68~6 : ``
This invention relates to a process for the treatment of mixtures of platinum group metals, gold :, ~ , and silver, and is more particularly concerned with the treatment of so-called platinum group metal concentrates such as matte leach residues and the like, and also various intermediate solid products such as leach insolubles etc. which may arise during ' j the processing of such materials.
': ' f ',, ` ` `
All commercial refining methods for the platinum group metals are basically hydrometallurgical in nature. Thus the first and key operation in these !:~
processes is the dissolution of the valuable components from the source material.
.,~;' .
~ However the platinum group metals are extremely !r' .~ ~
~` 15 difflcult to dissolve, and extended leaching periods with highly active media such as aqua regia are ; commonly used. Even under very vigorous leach conditions complete dissolution of the values is not generally ~!~,' achieved, and in particular the secondary platinum 20 metals (rhodium, r~thenium, iridium and osmium) are attacked to only a small extent. In addition the degree to which the metals dissolve is often highly variable ,; .
:
r ~ 2 ~
~0681~6 . ' ` from batch to batch and is generally dependent on the nature of the process steps to which the source material has been subjected prior to the platinum ' ' metal leaching step.
,:,:
Because of these effects it is common practice to use a multi-stage process involving both pyro-metallurgical and hydrometallurgical steps to effect dissolution of the platinum metals. One commonly used series of operations is as follows:-(1) performing an initial aqua regia leach on a ;, concentrate of platinum group metals, gold and silver;
.
This invention relates to a process for the treatment of mixtures of platinum group metals, gold :, ~ , and silver, and is more particularly concerned with the treatment of so-called platinum group metal concentrates such as matte leach residues and the like, and also various intermediate solid products such as leach insolubles etc. which may arise during ' j the processing of such materials.
': ' f ',, ` ` `
All commercial refining methods for the platinum group metals are basically hydrometallurgical in nature. Thus the first and key operation in these !:~
processes is the dissolution of the valuable components from the source material.
.,~;' .
~ However the platinum group metals are extremely !r' .~ ~
~` 15 difflcult to dissolve, and extended leaching periods with highly active media such as aqua regia are ; commonly used. Even under very vigorous leach conditions complete dissolution of the values is not generally ~!~,' achieved, and in particular the secondary platinum 20 metals (rhodium, r~thenium, iridium and osmium) are attacked to only a small extent. In addition the degree to which the metals dissolve is often highly variable ,; .
:
r ~ 2 ~
~0681~6 . ' ` from batch to batch and is generally dependent on the nature of the process steps to which the source material has been subjected prior to the platinum ' ' metal leaching step.
,:,:
Because of these effects it is common practice to use a multi-stage process involving both pyro-metallurgical and hydrometallurgical steps to effect dissolution of the platinum metals. One commonly used series of operations is as follows:-(1) performing an initial aqua regia leach on a ;, concentrate of platinum group metals, gold and silver;
.
(2) smelting the residue with litharge and a reductant to form a lead-platinum group metal alloy;
(3) parting of the lead bullion so formed with nitric acid;
' (4) leaching the residue from step (3) with aqua regia which - dissolves most of the platinum and palladium but little of the secondary platinum group metals;
(5) fusing the residue which is rich in secondary platinum group metals with sodium peroxide; and .. . .
(6) leaching of the fusion mixture with water and neutralising with hydrochloric acid to produce a chloride solution of the secondary platinum group metals.
''':'' , - , . . , , . . ., - :. . :
, . ' :
1t368116 "
Various recycle streams are also involved in the practical performance of this currently used procedure.
.
r Thus a large number of operations is involved - and a major proportion of the platinum metals is locked up in recycle streams. Many of the recycle streams are initially in the form of solutions; in order for the values contained in these streams to be ; recovered they must first be treated to render the precious metals insoluble. Commonly, reduction to metal using zinc as the reductant is employed, and this . .
operation is time consuming, expensive and not entirely , j, effective.
, . .. .
:, .
~urthermore it is commonly found with many ','"' .
, precious metal bearing source materials that a large proportion of the base me~al content cannot be effectively separated out before the platinum group metal leach by, for example, a milder leach such as sulphuric acid leaching. These base metals therefore contaminate the ~ .
leach liquors containing the precious metals and render both refining operations and recycle considerably more difficult ~ '' .
i:
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-"~ , , .
1~681~6 - .
It is the object of this invention to overcome the above difficulties in platinum refining by providing:-(1) a process whereby a large proportion of the. base metal content of the feed material can be effectively leached from the precious metal content before the leaching of the precious : metals themselves, and/or (2) a process whereby a large proportion of the precious metal content of the feed material can . 10 be dissolved in a single leach using chlorine as , the oxidant and hydrochloric acid as the dissolving medium, and/or . ., :
-. (3) a process whereby liquid recycle streams containing precious metals can be easily processed to recover the precious metal content without an intermediate zinc reduction step, by achieving reduction ~. during base metal removal.
,.' ~ :.
In this specification for the sake of clarity the term "precious metals" will be applied to mixtures of some or all of the platinum group metals and which may in : addition contain gold and/or silver. The term "base metals"
as used herein includes all metals other than the "precious metals".
, . . :. . : ~ . : - -. -~ `
In accordance with this invention there is provided a process for obtaining, by the action of an acid and an oxidizing agent, a solution of precious metals present in a precious metal concentrate which contains iridium, ruthenium or both, together with base metals said process comprising the steps of: (1) heating the precious metal concentrate together with aluminum at a temperature of at least about 1000 C, and for a length of time sufficient to form a precious metal/aluminum alloy, (2) leaching - 10 the alloy with acid under conditions other than strongly oxidizing conditions to dissolve the base metals yielding a residue containing the major portion of the precious "
metals therein, (3) separating the residue from the leach - liquor, and thereafter, (4) leaching the residue under 15 strong oxidizing conditions with acid and an oxidant to dissolve at least a major portion of the iridium and ruthenium together with any other precious metals present in said residue.
,. .
; Further features of the invention provide for the 20 alloy to be subjected initially to a leaching step adapted to remove base metals and for the precious metals to be recovered subsequently by a second leach step carried out under strong oxidizing conditions and for the base metal leach to be performed in two stages, the first of which is 25 carried out by weak acid under reducing conditions and the second of which is carried out under conditions suitable for the dissolution of copper.
The aluminium precious metal alloy preferably has an ... .
~ 6 -. . .
. ~ . .
-.,~ . ~, ~ '.
...,.~.
~ .
: 1068116 .. ~~aluminium to precious metal ratio of between about 10:1 and 1:1.
The formation of 'he aluminium alloy can be accom-:. plished in a number of ways but it is most efficiently - 5 performed according to one of three techniques which ;: are applicable to concentrates of various grades and compositions as follows:-tl) Concentrates having a high precious metal content (above about 50%) and which is essentially ,.
:
. ' ' . ~ ' , :'. ' ." , ,. .
:
:i~ .
.:
- 6a -" ~
.; ' ,. ~
,~ , ~106~3116 , metallic in character (e.g. lead bullion residue after parting) may be treated as follows:-(a) The material may be simply melted together with an equal weight of aluminium at a temperature in excess of 1000 C under a protective atmosphere to reduce oxidation of the aluminium.
(b) The material may be mixed with a small proportion (5~ - 25%) by weight of a suitable base metal oxide or sulphide, preferably ., ferric oxide or ferrous sulphide and sufficient aluminium powder, preferably a weight equal to the concentrate. This mixture is then ignited by a suitable technique where-upon the base metal oxide and the aluminium ' react, and the aluminothermic reaction so initiated provides sufficient heat to accomplish the alloying.
~,..
i~ (2) Concentrates having a medium precious metal content ;' 20 (between about 30~ and 50~) with a high base metal content but where silica is present in low ~,; concentrations (less than 5%) or is preferably absent. This may be treated in similar fashion to the above except that often sufficient base ~"~, 25 metal oxides or sulphides are already present in .. ,:,-~.~
,; .:
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~ -7-:,, , , - ~,:, : , ;, ~ . .~ . . . .. :
- . : ' . :
,, : , . : . .:
,: .. ., : :
. ~ , - . ' ' .
: " . : .
, ~ ~ 1C3681~6 :. .
the material to render the addition of further ~- ferric oxide or ferrous sulphide unnecessary.
~- Addition of some flux such as calcium oxide (CaO) may be helpful in rendering the aluminium oxide formed in the reaction soluble in the base metal leach. Certain matte leach residuesand initial '~ leach residues fall into this class of concentrate.
. ~ .
' (3) Material of medium or low precious metal content (precious metal content of less than 30%) with ,.. . .
high base metal content and high silica content.
The preferred technique here is to form an inter-mediate alloy of precious metals and iron which is then alloyed further with aluminium to form i: ,.
typically an alloy containing about 30% Fe, , 15 30% Al, 30% precious metals and 10% other base ;~ metals such as Ni, Pb, Cu etc. This operation is ~ typically but not necessarily carried out in an ~, . .
~; arc furnace as follows:-. . .
~'~ (a) The concentrate is mixed with carbon and lime, pelletised, and roasted at about 800 C to ,............................................................................ .
~, reduce any precious metal oxides to metal.
(b) The roasted material is smelted together with scrap iron in an arc furnace to produce an alloy of roughly 50% precious metal content .. ..
, 25 and a calcium-iron silica slag which is low ~,~ in precious metals.
~:, i; -8-': , ' ' . ,~, . ' . . . ~ . .
.:, ' , . .., ': ", , ','' ,. . ' "~ . . . ": ' `'` . '' ' "" '~' '', ',:
.
1al681~6 (c) The slag is poured off and aluminium scrap is added to the iron alloy in sufficient quantity to form an alloy of roughly 30% Al content.
This technique applies especially to concentrates of high silica content and low precious metal content , .. ...
`~' such as certain matte leach residues but of course could be applied in other cases as well.
In all the above cases the alloy so formed is preferably treated as follows:-10 (1) The aluminium and iron content of the alloy are leached together under highly reducing c-onditions, using weak acid to do the leaching. Any recycle streams that are acidic and contain precious metal values can be used in this step. Very effective , 15 cementation of the precious metal values has been ~ experienced and the exhausted leach liquor will ; contain very low precious metal values.
` (2) The residue from the first leach is then subjected to ~; a more intensive leach at a potential sufficient to ; , l 20 dissolve copper. Many known methods are available for , ~ .
doing this and in particular the controlled potential leach system of Falconbridge (Journal of Metals, May 1975 p 6-9 "The recovery of nickel copper and a precious ' ~ metal concentrate from high grade precious metal mattes"
: ..
,~, 25 L.R. Hougan, H. Zacharissen) using chlorine gas as ' the oxidant would be applicable here.
~' .
, _g_ - .
. , .
.
~ ~ .
~068~6 ;~:
(3) The residue from the second leach is then : :
leached in hydrochloric acid of commercial . strength (about 10 Molar) using chlorine gas as ~.
the oxidant. Leaching has been found to be rapid and complete and the leach residue~ if present, : consists of insolubles such as silica andalumina with low precious metal content, typically . less than 5000 ppm total precious metals.
Various experiments conducted thus far will now ; 10 be described in order to demonstrate the operation of ~ the invention.
.~. Example I
~:; The concentrate treated here was a moderately rich platinum . group metal concentrate obtained from a copper-nickel matte ,. . .
leach plant and which analysed roughly 30% precious metals -.
(platinum group metals + Au + Ag) and approximately 30%
;: base metal~ the remainder being oxygen, sulphur and silica.
. .
A sample of this material was firstly leached in 12M hydro-chloric acid using chlorine as the oxidant and the following percentage dissolutions were obtained:-Pt Pd Rh Ru Ir 80.8% 70.7% 32-7% 14.6% 64.8%
. These results were improved considerably by performing a reduction roast prior to leaching on another sample of the ''',~ , ,, , . .
' ' --10-, .- . - . . ,. . . : . .. ,: . .. , ~ : :, : :
-- ::
r- `
106~116 ~, , ' .
material, but complete dissolution coul.d still not be obtained, the percentage dissolutions being as follows:-.~: Pt Pd Rh Ru Ir 98.4% 98-3% 81.9% 52.4% 96.9%
A third sample of the material was then aluminother-. mically reduced with an equal weight of aluminium powder, by mixing the two ingredients and igniting the mixture by ;. heating to about 1000 C. The reacted material was firstly :
~:: leached with 12M hydrochloric aci.d in order to remove -: 10 aluminium and base metals, and thereafter with 12M .
. hydrochloric acid with Cl2 as the oxidizing agent in order to dissolve the platinum group metals. The results obtained upon leaching the reacted mass were as follows:-: Pt Pd Rh Ru Ir ;` 15 99.6% 99.4% 87.8% 96.9% 96.9%
,. , ~ ;
.! Thus the residue left after leaching was significantly .',~;, . ...
. poorer in platinum group metal content and in practice .~:; co.uld be recycled to the matte smelting furnace.
:
~!. "
, .
: Example II
~'4 20 The concentrate used in this example was similar to that .:
described above but had a lower precious metal content (~ 20%), and was very much more refractory in nature.
Results obtained on the raw material on leaching with 12M
.,.~ , .
,, " , . . ~ . ~ . ' ' ~. ', , '', , '' . ~ "' ': ' ,".
' ' ' , ~ , ., , ' , . ' ' ' I . .
1~681~6 : hydrochloric acid with C12 were as follows:-..
. Pt Pd Rh Ru Ir 63.9% 53.7~ 3-9% 16.4~45. 2%
In this case, treating the material by means of a reducing roast prior to leaching did not produce as marked an improvement as in Example I, the results being the following percentage dissolutions:-i Pt Pd Rh Ru Ir 89.2~ 94.2% 38.1% 3.4% 16.5%
However, after aluminothermic reduction had been carried out in a manner identical to that described in Example I, very good subsequent dissolutions were obtained:-; : ,.
Pt Pd Rh Ru Ir 99-3% 99.4% 97.6% 95.6~ 87.3 ., This example also illustrates that base metals can be removed almost completely before HCl/C12 leaching by . leaching in sulphuric acid, under oxidizing conditions.
. The following percentage diqsolutions were found to be typical:-Cu Ni Fe Cr Al ; 91.2% 85 - 5% 87.7% 25.5% 95%
. . .
The amount of platinum group metals dissolved together :' :
`~ with the base metals was negligibly small.
,.', . ''~
' ' ' `~ -12-.
: : :
lQ68~16 Example III
.
Ths concentrate treated here was a secondary platinum group concentrate obtained from the parting and aqua regia treatment of lead bullion obtained as above described, and this contained about 60% platinum group metals, 20% lead and 20% other base metals.
Both dlrect leaching with HClJC12 and leaching in the same way following hydrogen reduction of this material proved to be almost completely ineffective, as shown below:-, 10 Ru Rh Ir no pre-treatment 0~ 18.5~ 2.2 hydrogen reduction pre-treatment 5.7% 14.6% 6.7%
;
A sample of this concentrate was then treated by mixing ". 15 it with an equal weight of aluminium powder, and 20%
; by weight FeS. This mixture was ignited by heating at :~.
1000C and the reacted mass leached firstly in 200 g/l sulphuric acid to remove the base metals and aluminium and subsequently in 12M HCl/C12. The percentage : 20 dissolutions obtained after leaching for two hours were as follows:-Ru Rh Ir .
89.6% 92.9%95.8%
~ .
This experiment was repeated on a larger scale and it was found that almost all of the base metals added and ':;
. .
, ' '~.;
:: -13-'~''' . - . ' ' ,: . ,,, . . ~ . ; ' .
': - :. :.: .
.: . , .
- , : . .:
~C~681~6 .:
~` originally present were leached in the sulphuric acid leach. Subsequent HCl/C12 leaching for two hours gave similar dissolutions, viz:-~:;
Ru Rh Ir 90.8% 93.1% 90.3%
.'''' ,~.
A third test on this concentrate was condu~ted wherein 5 kg of concentrate were treated in a similar fashion ; to the above. The alloy was subjected to an initial leach in lOM HCl with the addition of 500 g ~e203 until ~ 10 the precious metals just started to dissolve. Filtration : was effected immediately and showed on analysis 45 ppm precious metals, 7 g/l Fe, 3 g/l Pb and 120 ppm Cu.
;.,: .
Leaching in lOM HCl/Cl2 was then effected and was continued for eight hours as opposed to the two hour leach times above. The extension of the leach time increased the ... .
percentage dissolved substantially to that given below:-. ~"
~ Ru Rh Ir '3~ 99.1~ 99.5% 99.3%
This leach liquor contained 54 g/l precious metals, 150 ppm Cu and 1,6 g/l of other base metals thus illustrating that :.
the majority of base metals had been removed.
The above leach procedure was carried out in a two step , ~- manner as opposed to the preferred three step procedure i set out above. The results of the three step procedure are, at this time, not available but the following are the .. , ~'.
' .
; -14-,, ~ , :
~068116 reasons for preferring a separate copper leach. In the leaching of iron, aluminium and similar base metals strongly reducing conditions are present when the alloy is leached with ~Cl or H2S04 solution. Thus in that leach step there is virtually no possibility of dissolving precious metals. In the second step in which copper would be leached more oxidizing conditions exist thereby increasing the chance of precious metals being dissolved Also, a substantially smaller vessel is required to effect the subsequent copper leach thereby resulting in smaller volumes of leach liquor to be treated for dissolved precious metals. The conditions in each stage of a two stage initial leach can be optimised and a plant can more readily be efficiently designed.
Example IV
This example illustrates an alternative method of perfor-ming the invention. A concentrate similar to that used in Example III was mixed with an equal weight of aluminium powder, and the mixture melted in a muffle furnace at 1000C for two hours. The molten mass was allowed to cool and then leached with 200 g/l H2S04 to remove the aluminium and base metals and the residue was dissolved in 12M HCl/C12.
The percentage dissolutions obtained in this case were : ~ . . :. : : :
.. , : . . . , :. ~ . . . . , ::
~ ~ .
:
10~116 .. . .
as follows:- .
Ru Rh Ir ~- 95.6~ 91.5% 96-3%
; ~.~. ., . ' Example V
A concentrate containing about 20% precious metals, o :' ,~ 16~ silica and 14~ iron oxides was heated at 800 C with ~: carbon for one hour. The amount of carbon added is dependent on the iron and platinum group metals that are present as-oxides. ~he peried of roas*ing -i-s!dependent - -~
: 10 on the kinetics of the reduction process and this will vary with temperature, composition, particle size and the mineralogy of the material.
The reduced material was cplit into two batches~ each of ; which was treated as follows.
' ! .
- 15 The reduced material together with lime (CaO) in an amount ~, of about 1 part was melted at 1600 C; iron scrap was .1 , . .:
~', added and the melt cooled. The metal was separated from the slag and alloyed with aluminium in the ratio of ` 0,4:1 Al:precious metal alloy at 1600C by first melting the metal and adding solid aluminium to the metal. After .. . .
cooling the aluminium alloy was leached in concentrated - (lOM) HCl acid and the residue leached in concentrated (lOM) HCl and C12. After this leach there was no residue .,.. ~ , .
remaining. The recovery of the various platinum group . :
metals in the final leach liquors is given in the following . - , .
~- table:-: `: j '~,.,:
, . , - .. .. .
. . : . : : . .
1068~16 T A B L E
. ~
., Pt Pd Rh Ru Os Ir Au . . _ _ . Precious metals in head sample mass % 1,11 6,40 2,99 6,51 1,43 0,44 670pE
.. (") (") (") (") (") (") (") .. _ ~, - _ ~ _ ____ .
Precious metals in in slag (ppm) _ 2434 __~
.'' , _ =- ( 9120 ) - = =_ Precious metals in HCl leach liquor (Ppm) .~_(4 3) '.' I _ _ Precious metals in HClJC12 leach liquor . (ppm) 700 5063 2019 4438 850 3].5 1600 . (743) (5583)(2019` (4775`(835) (330) (l7l4) ~.' .. Precious metals recovered in slag % ~_ _ 3.% _ _ ." . _ I
'.'^ _ .: Precious metals I recovered in alloy ;~ % by difference ~_ _ 97% _ _ ;.; (98. 6%) ,,., ....
; Precious metals recovered in alloy ~;: (calculated from :i: HCl/C12 leach solutio~
. values) e~109,3% -3 ; . (108,1%) ,.,., I
:. -i ~, ~. -17-:
:~ f , .. .
The discrepancies in the reco~ery of precious metals -which are quite obvious were due to assay errors. The figures given in parentheses are for the second half of the initial reduced material.
. .
Example VI ~
, . .
Finally the operation of the use of a precious metal containing simulated recycle stream was tested in order to observe the cementation effects with the aluminium , alloy.
40 litre~ of an imitation recycle stream of approximately 2M HCl and containing Ru Rh Pd Pt Ir 6000 ppm 5031 ppm 735 ppm 3 ppm 1250 ppm were contacted with 1 Kg of crushed aluminium-precious metal alloy. The alloy had a particle size of 100% minus inch mesh and the contacting was effected at 60 C for , six hours.
The solution was filtered off and found to contain:-Ru Rh Pd Pt Ir ~;~ 20 1,5 ppm N.D. 0,4 ppm N.D. 6 ppm ,.~ .
~' (N.D. means not detectable) ., , Thus cementation apparently occurred with a high degree of efficiency.
, ', :~ :.
' " ' .
~ -18-- . . , ~068~16 ,, . The above tests which have been carried out demonstrate that a process according to the invention will operate effectively in use. It will be noted that where hydrochloric acid has been used the strength was either lOM or 12M. As will be apparent to those skilled in the art any strength acid may be used with the more dilute acids simply taking longer to produce the desired effect. Also, any strength sulphuric acid could be used up to a maximum strength of about 500 g/l.
The invention therefore provides a process having : . the following characteristics:-:' :` (1) ~t allows the base metal content to be removed prior to the platinum group metal leach by leaching with ;' dilute sulphuric acid or hydrochloric acid, and : 15 (2) It lncreases the leachability of the platinum ;' group metals in an oxidizing hydrochloric acid leach to ,..... . .
a very great extent, so that in effect total dissolution can be achieved.
,~ , The process may be applied to any platinum group ~' 20 metal rich material arising at any stage of the conven-; tional refining process, and in particular can be readily ,;, .
applied to the following materials:-.. (1) feed material to the refinery, thus eliminating ., `. : :
',; ' , ! i --1 9--: ' ': ,,: , ' ' : , . ', .: : . , , ' ' ' : . , , , ~ ! ' , , ' ' , ' .' " :" ' ' ' : . . . . : -: .: : ' ' ',, :.:' . '.. , . : . ' ' ' .. ' ' ~. ' ' ' .` ' : ': ' :' ', ,: .~ . ' ' : ' ' . ' ' , ' ' : ' , ~- ' ~ 68116 : . ...
the need for subsequent treatment of the residue. In . practice, because platinum group metals are so valuable, .~ this residue, if present at.all, although low inplatinum group metals content, would be recycled to a point earlier in the process such as the matte smelter, (2) the residue from the primary leach, and ~ (3) the residue from the parting and aqua regia leaching of the lead bullion in which use of the method is a replacement for the potentially hazardous sodium peroxide fusion.
' . I .
`' ~
d ' I ~
, .,'~i: ' .
. I
. 1 ' .
. ~ .
" 'i .
.~, ' j .
" . ',"; ' ., .', ' '' . : ' ~ : " ~' ` '. ' ' ; :, ,: ' ',' ' ... . .. . . . . . .. . . . . . . . . .
' (4) leaching the residue from step (3) with aqua regia which - dissolves most of the platinum and palladium but little of the secondary platinum group metals;
(5) fusing the residue which is rich in secondary platinum group metals with sodium peroxide; and .. . .
(6) leaching of the fusion mixture with water and neutralising with hydrochloric acid to produce a chloride solution of the secondary platinum group metals.
''':'' , - , . . , , . . ., - :. . :
, . ' :
1t368116 "
Various recycle streams are also involved in the practical performance of this currently used procedure.
.
r Thus a large number of operations is involved - and a major proportion of the platinum metals is locked up in recycle streams. Many of the recycle streams are initially in the form of solutions; in order for the values contained in these streams to be ; recovered they must first be treated to render the precious metals insoluble. Commonly, reduction to metal using zinc as the reductant is employed, and this . .
operation is time consuming, expensive and not entirely , j, effective.
, . .. .
:, .
~urthermore it is commonly found with many ','"' .
, precious metal bearing source materials that a large proportion of the base me~al content cannot be effectively separated out before the platinum group metal leach by, for example, a milder leach such as sulphuric acid leaching. These base metals therefore contaminate the ~ .
leach liquors containing the precious metals and render both refining operations and recycle considerably more difficult ~ '' .
i:
:. ~ . . . ,, :
',.'' ' :, ' ~
-"~ , , .
1~681~6 - .
It is the object of this invention to overcome the above difficulties in platinum refining by providing:-(1) a process whereby a large proportion of the. base metal content of the feed material can be effectively leached from the precious metal content before the leaching of the precious : metals themselves, and/or (2) a process whereby a large proportion of the precious metal content of the feed material can . 10 be dissolved in a single leach using chlorine as , the oxidant and hydrochloric acid as the dissolving medium, and/or . ., :
-. (3) a process whereby liquid recycle streams containing precious metals can be easily processed to recover the precious metal content without an intermediate zinc reduction step, by achieving reduction ~. during base metal removal.
,.' ~ :.
In this specification for the sake of clarity the term "precious metals" will be applied to mixtures of some or all of the platinum group metals and which may in : addition contain gold and/or silver. The term "base metals"
as used herein includes all metals other than the "precious metals".
, . . :. . : ~ . : - -. -~ `
In accordance with this invention there is provided a process for obtaining, by the action of an acid and an oxidizing agent, a solution of precious metals present in a precious metal concentrate which contains iridium, ruthenium or both, together with base metals said process comprising the steps of: (1) heating the precious metal concentrate together with aluminum at a temperature of at least about 1000 C, and for a length of time sufficient to form a precious metal/aluminum alloy, (2) leaching - 10 the alloy with acid under conditions other than strongly oxidizing conditions to dissolve the base metals yielding a residue containing the major portion of the precious "
metals therein, (3) separating the residue from the leach - liquor, and thereafter, (4) leaching the residue under 15 strong oxidizing conditions with acid and an oxidant to dissolve at least a major portion of the iridium and ruthenium together with any other precious metals present in said residue.
,. .
; Further features of the invention provide for the 20 alloy to be subjected initially to a leaching step adapted to remove base metals and for the precious metals to be recovered subsequently by a second leach step carried out under strong oxidizing conditions and for the base metal leach to be performed in two stages, the first of which is 25 carried out by weak acid under reducing conditions and the second of which is carried out under conditions suitable for the dissolution of copper.
The aluminium precious metal alloy preferably has an ... .
~ 6 -. . .
. ~ . .
-.,~ . ~, ~ '.
...,.~.
~ .
: 1068116 .. ~~aluminium to precious metal ratio of between about 10:1 and 1:1.
The formation of 'he aluminium alloy can be accom-:. plished in a number of ways but it is most efficiently - 5 performed according to one of three techniques which ;: are applicable to concentrates of various grades and compositions as follows:-tl) Concentrates having a high precious metal content (above about 50%) and which is essentially ,.
:
. ' ' . ~ ' , :'. ' ." , ,. .
:
:i~ .
.:
- 6a -" ~
.; ' ,. ~
,~ , ~106~3116 , metallic in character (e.g. lead bullion residue after parting) may be treated as follows:-(a) The material may be simply melted together with an equal weight of aluminium at a temperature in excess of 1000 C under a protective atmosphere to reduce oxidation of the aluminium.
(b) The material may be mixed with a small proportion (5~ - 25%) by weight of a suitable base metal oxide or sulphide, preferably ., ferric oxide or ferrous sulphide and sufficient aluminium powder, preferably a weight equal to the concentrate. This mixture is then ignited by a suitable technique where-upon the base metal oxide and the aluminium ' react, and the aluminothermic reaction so initiated provides sufficient heat to accomplish the alloying.
~,..
i~ (2) Concentrates having a medium precious metal content ;' 20 (between about 30~ and 50~) with a high base metal content but where silica is present in low ~,; concentrations (less than 5%) or is preferably absent. This may be treated in similar fashion to the above except that often sufficient base ~"~, 25 metal oxides or sulphides are already present in .. ,:,-~.~
,; .:
'',;
~ -7-:,, , , - ~,:, : , ;, ~ . .~ . . . .. :
- . : ' . :
,, : , . : . .:
,: .. ., : :
. ~ , - . ' ' .
: " . : .
, ~ ~ 1C3681~6 :. .
the material to render the addition of further ~- ferric oxide or ferrous sulphide unnecessary.
~- Addition of some flux such as calcium oxide (CaO) may be helpful in rendering the aluminium oxide formed in the reaction soluble in the base metal leach. Certain matte leach residuesand initial '~ leach residues fall into this class of concentrate.
. ~ .
' (3) Material of medium or low precious metal content (precious metal content of less than 30%) with ,.. . .
high base metal content and high silica content.
The preferred technique here is to form an inter-mediate alloy of precious metals and iron which is then alloyed further with aluminium to form i: ,.
typically an alloy containing about 30% Fe, , 15 30% Al, 30% precious metals and 10% other base ;~ metals such as Ni, Pb, Cu etc. This operation is ~ typically but not necessarily carried out in an ~, . .
~; arc furnace as follows:-. . .
~'~ (a) The concentrate is mixed with carbon and lime, pelletised, and roasted at about 800 C to ,............................................................................ .
~, reduce any precious metal oxides to metal.
(b) The roasted material is smelted together with scrap iron in an arc furnace to produce an alloy of roughly 50% precious metal content .. ..
, 25 and a calcium-iron silica slag which is low ~,~ in precious metals.
~:, i; -8-': , ' ' . ,~, . ' . . . ~ . .
.:, ' , . .., ': ", , ','' ,. . ' "~ . . . ": ' `'` . '' ' "" '~' '', ',:
.
1al681~6 (c) The slag is poured off and aluminium scrap is added to the iron alloy in sufficient quantity to form an alloy of roughly 30% Al content.
This technique applies especially to concentrates of high silica content and low precious metal content , .. ...
`~' such as certain matte leach residues but of course could be applied in other cases as well.
In all the above cases the alloy so formed is preferably treated as follows:-10 (1) The aluminium and iron content of the alloy are leached together under highly reducing c-onditions, using weak acid to do the leaching. Any recycle streams that are acidic and contain precious metal values can be used in this step. Very effective , 15 cementation of the precious metal values has been ~ experienced and the exhausted leach liquor will ; contain very low precious metal values.
` (2) The residue from the first leach is then subjected to ~; a more intensive leach at a potential sufficient to ; , l 20 dissolve copper. Many known methods are available for , ~ .
doing this and in particular the controlled potential leach system of Falconbridge (Journal of Metals, May 1975 p 6-9 "The recovery of nickel copper and a precious ' ~ metal concentrate from high grade precious metal mattes"
: ..
,~, 25 L.R. Hougan, H. Zacharissen) using chlorine gas as ' the oxidant would be applicable here.
~' .
, _g_ - .
. , .
.
~ ~ .
~068~6 ;~:
(3) The residue from the second leach is then : :
leached in hydrochloric acid of commercial . strength (about 10 Molar) using chlorine gas as ~.
the oxidant. Leaching has been found to be rapid and complete and the leach residue~ if present, : consists of insolubles such as silica andalumina with low precious metal content, typically . less than 5000 ppm total precious metals.
Various experiments conducted thus far will now ; 10 be described in order to demonstrate the operation of ~ the invention.
.~. Example I
~:; The concentrate treated here was a moderately rich platinum . group metal concentrate obtained from a copper-nickel matte ,. . .
leach plant and which analysed roughly 30% precious metals -.
(platinum group metals + Au + Ag) and approximately 30%
;: base metal~ the remainder being oxygen, sulphur and silica.
. .
A sample of this material was firstly leached in 12M hydro-chloric acid using chlorine as the oxidant and the following percentage dissolutions were obtained:-Pt Pd Rh Ru Ir 80.8% 70.7% 32-7% 14.6% 64.8%
. These results were improved considerably by performing a reduction roast prior to leaching on another sample of the ''',~ , ,, , . .
' ' --10-, .- . - . . ,. . . : . .. ,: . .. , ~ : :, : :
-- ::
r- `
106~116 ~, , ' .
material, but complete dissolution coul.d still not be obtained, the percentage dissolutions being as follows:-.~: Pt Pd Rh Ru Ir 98.4% 98-3% 81.9% 52.4% 96.9%
A third sample of the material was then aluminother-. mically reduced with an equal weight of aluminium powder, by mixing the two ingredients and igniting the mixture by ;. heating to about 1000 C. The reacted material was firstly :
~:: leached with 12M hydrochloric aci.d in order to remove -: 10 aluminium and base metals, and thereafter with 12M .
. hydrochloric acid with Cl2 as the oxidizing agent in order to dissolve the platinum group metals. The results obtained upon leaching the reacted mass were as follows:-: Pt Pd Rh Ru Ir ;` 15 99.6% 99.4% 87.8% 96.9% 96.9%
,. , ~ ;
.! Thus the residue left after leaching was significantly .',~;, . ...
. poorer in platinum group metal content and in practice .~:; co.uld be recycled to the matte smelting furnace.
:
~!. "
, .
: Example II
~'4 20 The concentrate used in this example was similar to that .:
described above but had a lower precious metal content (~ 20%), and was very much more refractory in nature.
Results obtained on the raw material on leaching with 12M
.,.~ , .
,, " , . . ~ . ~ . ' ' ~. ', , '', , '' . ~ "' ': ' ,".
' ' ' , ~ , ., , ' , . ' ' ' I . .
1~681~6 : hydrochloric acid with C12 were as follows:-..
. Pt Pd Rh Ru Ir 63.9% 53.7~ 3-9% 16.4~45. 2%
In this case, treating the material by means of a reducing roast prior to leaching did not produce as marked an improvement as in Example I, the results being the following percentage dissolutions:-i Pt Pd Rh Ru Ir 89.2~ 94.2% 38.1% 3.4% 16.5%
However, after aluminothermic reduction had been carried out in a manner identical to that described in Example I, very good subsequent dissolutions were obtained:-; : ,.
Pt Pd Rh Ru Ir 99-3% 99.4% 97.6% 95.6~ 87.3 ., This example also illustrates that base metals can be removed almost completely before HCl/C12 leaching by . leaching in sulphuric acid, under oxidizing conditions.
. The following percentage diqsolutions were found to be typical:-Cu Ni Fe Cr Al ; 91.2% 85 - 5% 87.7% 25.5% 95%
. . .
The amount of platinum group metals dissolved together :' :
`~ with the base metals was negligibly small.
,.', . ''~
' ' ' `~ -12-.
: : :
lQ68~16 Example III
.
Ths concentrate treated here was a secondary platinum group concentrate obtained from the parting and aqua regia treatment of lead bullion obtained as above described, and this contained about 60% platinum group metals, 20% lead and 20% other base metals.
Both dlrect leaching with HClJC12 and leaching in the same way following hydrogen reduction of this material proved to be almost completely ineffective, as shown below:-, 10 Ru Rh Ir no pre-treatment 0~ 18.5~ 2.2 hydrogen reduction pre-treatment 5.7% 14.6% 6.7%
;
A sample of this concentrate was then treated by mixing ". 15 it with an equal weight of aluminium powder, and 20%
; by weight FeS. This mixture was ignited by heating at :~.
1000C and the reacted mass leached firstly in 200 g/l sulphuric acid to remove the base metals and aluminium and subsequently in 12M HCl/C12. The percentage : 20 dissolutions obtained after leaching for two hours were as follows:-Ru Rh Ir .
89.6% 92.9%95.8%
~ .
This experiment was repeated on a larger scale and it was found that almost all of the base metals added and ':;
. .
, ' '~.;
:: -13-'~''' . - . ' ' ,: . ,,, . . ~ . ; ' .
': - :. :.: .
.: . , .
- , : . .:
~C~681~6 .:
~` originally present were leached in the sulphuric acid leach. Subsequent HCl/C12 leaching for two hours gave similar dissolutions, viz:-~:;
Ru Rh Ir 90.8% 93.1% 90.3%
.'''' ,~.
A third test on this concentrate was condu~ted wherein 5 kg of concentrate were treated in a similar fashion ; to the above. The alloy was subjected to an initial leach in lOM HCl with the addition of 500 g ~e203 until ~ 10 the precious metals just started to dissolve. Filtration : was effected immediately and showed on analysis 45 ppm precious metals, 7 g/l Fe, 3 g/l Pb and 120 ppm Cu.
;.,: .
Leaching in lOM HCl/Cl2 was then effected and was continued for eight hours as opposed to the two hour leach times above. The extension of the leach time increased the ... .
percentage dissolved substantially to that given below:-. ~"
~ Ru Rh Ir '3~ 99.1~ 99.5% 99.3%
This leach liquor contained 54 g/l precious metals, 150 ppm Cu and 1,6 g/l of other base metals thus illustrating that :.
the majority of base metals had been removed.
The above leach procedure was carried out in a two step , ~- manner as opposed to the preferred three step procedure i set out above. The results of the three step procedure are, at this time, not available but the following are the .. , ~'.
' .
; -14-,, ~ , :
~068116 reasons for preferring a separate copper leach. In the leaching of iron, aluminium and similar base metals strongly reducing conditions are present when the alloy is leached with ~Cl or H2S04 solution. Thus in that leach step there is virtually no possibility of dissolving precious metals. In the second step in which copper would be leached more oxidizing conditions exist thereby increasing the chance of precious metals being dissolved Also, a substantially smaller vessel is required to effect the subsequent copper leach thereby resulting in smaller volumes of leach liquor to be treated for dissolved precious metals. The conditions in each stage of a two stage initial leach can be optimised and a plant can more readily be efficiently designed.
Example IV
This example illustrates an alternative method of perfor-ming the invention. A concentrate similar to that used in Example III was mixed with an equal weight of aluminium powder, and the mixture melted in a muffle furnace at 1000C for two hours. The molten mass was allowed to cool and then leached with 200 g/l H2S04 to remove the aluminium and base metals and the residue was dissolved in 12M HCl/C12.
The percentage dissolutions obtained in this case were : ~ . . :. : : :
.. , : . . . , :. ~ . . . . , ::
~ ~ .
:
10~116 .. . .
as follows:- .
Ru Rh Ir ~- 95.6~ 91.5% 96-3%
; ~.~. ., . ' Example V
A concentrate containing about 20% precious metals, o :' ,~ 16~ silica and 14~ iron oxides was heated at 800 C with ~: carbon for one hour. The amount of carbon added is dependent on the iron and platinum group metals that are present as-oxides. ~he peried of roas*ing -i-s!dependent - -~
: 10 on the kinetics of the reduction process and this will vary with temperature, composition, particle size and the mineralogy of the material.
The reduced material was cplit into two batches~ each of ; which was treated as follows.
' ! .
- 15 The reduced material together with lime (CaO) in an amount ~, of about 1 part was melted at 1600 C; iron scrap was .1 , . .:
~', added and the melt cooled. The metal was separated from the slag and alloyed with aluminium in the ratio of ` 0,4:1 Al:precious metal alloy at 1600C by first melting the metal and adding solid aluminium to the metal. After .. . .
cooling the aluminium alloy was leached in concentrated - (lOM) HCl acid and the residue leached in concentrated (lOM) HCl and C12. After this leach there was no residue .,.. ~ , .
remaining. The recovery of the various platinum group . :
metals in the final leach liquors is given in the following . - , .
~- table:-: `: j '~,.,:
, . , - .. .. .
. . : . : : . .
1068~16 T A B L E
. ~
., Pt Pd Rh Ru Os Ir Au . . _ _ . Precious metals in head sample mass % 1,11 6,40 2,99 6,51 1,43 0,44 670pE
.. (") (") (") (") (") (") (") .. _ ~, - _ ~ _ ____ .
Precious metals in in slag (ppm) _ 2434 __~
.'' , _ =- ( 9120 ) - = =_ Precious metals in HCl leach liquor (Ppm) .~_(4 3) '.' I _ _ Precious metals in HClJC12 leach liquor . (ppm) 700 5063 2019 4438 850 3].5 1600 . (743) (5583)(2019` (4775`(835) (330) (l7l4) ~.' .. Precious metals recovered in slag % ~_ _ 3.% _ _ ." . _ I
'.'^ _ .: Precious metals I recovered in alloy ;~ % by difference ~_ _ 97% _ _ ;.; (98. 6%) ,,., ....
; Precious metals recovered in alloy ~;: (calculated from :i: HCl/C12 leach solutio~
. values) e~109,3% -3 ; . (108,1%) ,.,., I
:. -i ~, ~. -17-:
:~ f , .. .
The discrepancies in the reco~ery of precious metals -which are quite obvious were due to assay errors. The figures given in parentheses are for the second half of the initial reduced material.
. .
Example VI ~
, . .
Finally the operation of the use of a precious metal containing simulated recycle stream was tested in order to observe the cementation effects with the aluminium , alloy.
40 litre~ of an imitation recycle stream of approximately 2M HCl and containing Ru Rh Pd Pt Ir 6000 ppm 5031 ppm 735 ppm 3 ppm 1250 ppm were contacted with 1 Kg of crushed aluminium-precious metal alloy. The alloy had a particle size of 100% minus inch mesh and the contacting was effected at 60 C for , six hours.
The solution was filtered off and found to contain:-Ru Rh Pd Pt Ir ~;~ 20 1,5 ppm N.D. 0,4 ppm N.D. 6 ppm ,.~ .
~' (N.D. means not detectable) ., , Thus cementation apparently occurred with a high degree of efficiency.
, ', :~ :.
' " ' .
~ -18-- . . , ~068~16 ,, . The above tests which have been carried out demonstrate that a process according to the invention will operate effectively in use. It will be noted that where hydrochloric acid has been used the strength was either lOM or 12M. As will be apparent to those skilled in the art any strength acid may be used with the more dilute acids simply taking longer to produce the desired effect. Also, any strength sulphuric acid could be used up to a maximum strength of about 500 g/l.
The invention therefore provides a process having : . the following characteristics:-:' :` (1) ~t allows the base metal content to be removed prior to the platinum group metal leach by leaching with ;' dilute sulphuric acid or hydrochloric acid, and : 15 (2) It lncreases the leachability of the platinum ;' group metals in an oxidizing hydrochloric acid leach to ,..... . .
a very great extent, so that in effect total dissolution can be achieved.
,~ , The process may be applied to any platinum group ~' 20 metal rich material arising at any stage of the conven-; tional refining process, and in particular can be readily ,;, .
applied to the following materials:-.. (1) feed material to the refinery, thus eliminating ., `. : :
',; ' , ! i --1 9--: ' ': ,,: , ' ' : , . ', .: : . , , ' ' ' : . , , , ~ ! ' , , ' ' , ' .' " :" ' ' ' : . . . . : -: .: : ' ' ',, :.:' . '.. , . : . ' ' ' .. ' ' ~. ' ' ' .` ' : ': ' :' ', ,: .~ . ' ' : ' ' . ' ' , ' ' : ' , ~- ' ~ 68116 : . ...
the need for subsequent treatment of the residue. In . practice, because platinum group metals are so valuable, .~ this residue, if present at.all, although low inplatinum group metals content, would be recycled to a point earlier in the process such as the matte smelter, (2) the residue from the primary leach, and ~ (3) the residue from the parting and aqua regia leaching of the lead bullion in which use of the method is a replacement for the potentially hazardous sodium peroxide fusion.
' . I .
`' ~
d ' I ~
, .,'~i: ' .
. I
. 1 ' .
. ~ .
" 'i .
.~, ' j .
" . ',"; ' ., .', ' '' . : ' ~ : " ~' ` '. ' ' ; :, ,: ' ',' ' ... . .. . . . . . .. . . . . . . . . .
Claims (14)
1. A process for obtaining, by the action of an acid and an oxidizing agent, a solution of precious metals present in a precious metal concentrate which contains iridium, ruthenium or both, together with base metals said process comprising the steps of:
(1) heating the precious metal concentrate together with aluminum at a temperature of at least about 1000° C, and for a length of time sufficient to form a precious metal/aluminum alloy, (2) leaching the alloy with acid under conditions other than strongly oxidizing conditions to dissolve the base metals yielding a residue containing the major portion of the precious metals therein, (3) separating the residue from the leach liquor, and therafter, (4) leaching the residue under strong oxidizing conditions with acid and an oxidant to dissolve at least a major portion of the iridium and ruthenium together with any other precious metals present in said residue.
(1) heating the precious metal concentrate together with aluminum at a temperature of at least about 1000° C, and for a length of time sufficient to form a precious metal/aluminum alloy, (2) leaching the alloy with acid under conditions other than strongly oxidizing conditions to dissolve the base metals yielding a residue containing the major portion of the precious metals therein, (3) separating the residue from the leach liquor, and therafter, (4) leaching the residue under strong oxidizing conditions with acid and an oxidant to dissolve at least a major portion of the iridium and ruthenium together with any other precious metals present in said residue.
2. A process as claimed in claim 1 in which the precious metal/aluminum alloy contains copper therein and is initially leached with acid under strong reducing conditions to remove the majority of base metals and yield a first residue, the first residue is then leached with acid to selectively dissolve copper providing a second residue, and the second residue is thereafter leached under strong oxidizing conditions to dissolve the precious metals contained therein.
3. A process as claimed in claim 1 in which the leach for the removal of the majority of the base metals in step (2) is hydrochloric or sulphuric acid.
4. A process as claimed in claim 3 in which the acid is contained in a recycle stream together with small amounts of precious metals which are cemented out during the leaching procedure of step (2).
5. A process as claimed in claim 1 in which dissolution of the precious metals in step (4) wherein concentrated hydrochloric acid and chlorine gas is used as an oxidant.
6. A process as claimed in claim 1 in which the precious metal concentrate contains more than 30% by weight precious metals and less than about 5% silica, and the formation of the precious metal/aluminum alloy of step (1) is effected by mixing the concentrate with sub-divided aluminum to provide a precious metal/aluminum mixture and then heating the mixture to form a molten alloy.
7. A process as claimed in claim 6 in which the heating is conducted in a protective atmosphere to reduce oxidation of the aluminum.
8. A process as claimed in claim 6 in which the concentrate contains an amount of base metal oxides or sulphides to enable the mixture when heated to undergo a highly exothermic aluminothermic reaction.
9. A process as claimed in claim 6 in which a base metal oxide, sulphides or both are added to the mixture to enable the mixture when heated to undergo a highly exothermic aluminothermic reaction.
10. A process as claimed in claim 1 in which the precious metal concentrate contains less than about 30% by weight precious metals and iron, the precious metal/aluminum alloy formed in step (l) by initially forming an iron-precious metal alloy, removing silica in the slag thus formed and adding the required aluminum to such iron alloy.
11. A process as claimed in claim 1 in which the aluminum alloy has an aluminum to precious metal weight ratio of from 10:1 to 1:1.
12. A process for the treatment and recovery of a previous metal concentrate and a base metal or metals, said concentrate containing precious metals selected from the group consisting of platinum group metals, gold silver and mixtures thereof wherein the base metals are first removed and the precious metals present in the concentrate are substantially completely recovered, said process including the successive steps of:
(a) heating a precious metal concentrate containing iridium, ruthenium or both with aluminum at a temperature of at least about 1000° C and for a length of time sufficient to form an aluminum/precious metal alloy, the ratio of aluminum to precious metal in said alloy in a weight ratio of about 10:1 to 1:1;
(b) selectively leaching the aluminum/precious metal alloy of step (a) with hydrochloric or sulphuric acid to dissolve the base metal and aluminum from the alloy while a major portion of the precious metals remain in the residue yielding a precious metal-rich residue and a leach liquor;
(c) separating the leach liquor from the residue of step (b); and (d) subjecting the separated residue to hydro-chloric acid and chlorine gas as an oxidant thereby dissolving the precious metals contained in said residue.
(a) heating a precious metal concentrate containing iridium, ruthenium or both with aluminum at a temperature of at least about 1000° C and for a length of time sufficient to form an aluminum/precious metal alloy, the ratio of aluminum to precious metal in said alloy in a weight ratio of about 10:1 to 1:1;
(b) selectively leaching the aluminum/precious metal alloy of step (a) with hydrochloric or sulphuric acid to dissolve the base metal and aluminum from the alloy while a major portion of the precious metals remain in the residue yielding a precious metal-rich residue and a leach liquor;
(c) separating the leach liquor from the residue of step (b); and (d) subjecting the separated residue to hydro-chloric acid and chlorine gas as an oxidant thereby dissolving the precious metals contained in said residue.
13. A process for the treatment and recovery of a precious metal concentrate and a base metal or metals, said concentrate containing precious metals selected from the group consisting of platinum group metals, gold, silver and mixtures thereof wherein the base metals are first removed and the precious metals present in the concentrate are substantially completely recovered, and said process including the successive steps of:
(a) heating a precious metal concentrate containing iridium, ruthenium or both with aluminum at a temperature of at least about 1000° C and for a length of time sufficient to form an aluminum/precious metal alloy, the ratio of aluminum to precious metal in said alloy in a weight ratio of about 10:1 to 1:1;
(b) selectively leaching the aluminum/precious metal alloy of step (a) with hydrochloric or sulphuric acid to dissolve the base metal and aluminum from the alloy while a major portion of the precious metals remain in the residue yielding a precious metal-rich residue and a leach liquor;
(c) separating the leach liquor from the residue of step (b); and (d) subjecting the separated residue to hydro-chloric acid and chlorine gas as an oxidant thereby dissolving the precious metals contained in said residue.
(a) heating a precious metal concentrate containing iridium, ruthenium or both with aluminum at a temperature of at least about 1000° C and for a length of time sufficient to form an aluminum/precious metal alloy, the ratio of aluminum to precious metal in said alloy in a weight ratio of about 10:1 to 1:1;
(b) selectively leaching the aluminum/precious metal alloy of step (a) with hydrochloric or sulphuric acid to dissolve the base metal and aluminum from the alloy while a major portion of the precious metals remain in the residue yielding a precious metal-rich residue and a leach liquor;
(c) separating the leach liquor from the residue of step (b); and (d) subjecting the separated residue to hydro-chloric acid and chlorine gas as an oxidant thereby dissolving the precious metals contained in said residue.
14. A process for the treatment and recovery of a precious metal concentrate and a base metal or metals, said concentrate containing precious metals selected from the group consisting of platinum group metals, gold, silver and mixtures thereof, wherein the base metals are first removed and the precious metals present in the concentrate are substantially completely recovered, said process including the successive steps of;
(a) heating a precious metal concentrate containing iridium, ruthenium or both with aluminum at a temperature of at least about 1000° C and for a length of time sufficient to form an aluminum/precious metal alloy also containing copper therein, the ratio of aluminum to precious metal in said alloy in a weight ratio of about 10:1 to 1:1;
(b) selectively leaching the aluminum/precious metal alloy of step (a) under reducing conditions to dissolve and remove a major portion of the base metals in the leach liquor leaving a concentration of the precious metal values as a residue;
(c) separating the leach liquor from the residue of step (b);
(d) selectively dissolving copper contained in the residue of step (c) with acid forming a copper-containing leach liquor and a residue;
(e) separating the leach liquor from the residue of step (d); and (f) leaching the residue of step (e)with acid under strong oxidizing conditions to dissolve the precious metals contained therein.
(a) heating a precious metal concentrate containing iridium, ruthenium or both with aluminum at a temperature of at least about 1000° C and for a length of time sufficient to form an aluminum/precious metal alloy also containing copper therein, the ratio of aluminum to precious metal in said alloy in a weight ratio of about 10:1 to 1:1;
(b) selectively leaching the aluminum/precious metal alloy of step (a) under reducing conditions to dissolve and remove a major portion of the base metals in the leach liquor leaving a concentration of the precious metal values as a residue;
(c) separating the leach liquor from the residue of step (b);
(d) selectively dissolving copper contained in the residue of step (c) with acid forming a copper-containing leach liquor and a residue;
(e) separating the leach liquor from the residue of step (d); and (f) leaching the residue of step (e)with acid under strong oxidizing conditions to dissolve the precious metals contained therein.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ZA00750593A ZA75593B (en) | 1975-01-29 | 1975-01-29 | A process for the treatment of mixtures of platinum group metals and gold |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1068116A true CA1068116A (en) | 1979-12-18 |
Family
ID=25568593
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA244,171A Expired CA1068116A (en) | 1975-01-29 | 1976-01-26 | Process for the treatment of platinum group metals and gold |
Country Status (8)
Country | Link |
---|---|
JP (1) | JPS5823449B2 (en) |
BE (1) | BE838029A (en) |
CA (1) | CA1068116A (en) |
DE (1) | DE2602827C2 (en) |
FR (1) | FR2299411A1 (en) |
GB (1) | GB1481295A (en) |
NO (1) | NO141444C (en) |
ZA (1) | ZA75593B (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4685963A (en) * | 1978-05-22 | 1987-08-11 | Texasgulf Minerals And Metals, Inc. | Process for the extraction of platinum group metals |
US4295881A (en) * | 1979-04-23 | 1981-10-20 | Texasgulf Inc. | Process for extraction of platinum group metals from chromite-bearing ore |
ZA807646B (en) | 1979-12-31 | 1982-02-24 | Johnson Matthey Co Ltd | Refining of refractory materials |
DE3279625D1 (en) * | 1981-09-16 | 1989-05-24 | Matthey Rustenburg Refines | Recovery of platinum group metals from scrap and residues |
DE3279726D1 (en) * | 1981-09-16 | 1989-07-06 | Matthey Rustenburg Refines | Recovery of precious metals from leach residues |
AU2008334953B2 (en) * | 2007-12-10 | 2013-09-19 | Prior Engineering Services Ag | Recovery of metal, espacially silver, from metal chlorides by hydrogen reduction |
RU2532697C2 (en) * | 2013-02-28 | 2014-11-10 | Общество с ограниченной ответственностью Научно-исследовательский и проектный институт "ТОМС" | Method of processing silver-containing concentrates |
JP6585955B2 (en) * | 2015-07-31 | 2019-10-02 | Jx金属株式会社 | Method for separating Ru, Rh and Ir from a selenium platinum group element-containing material |
CN114703375A (en) * | 2022-03-04 | 2022-07-05 | 金川集团股份有限公司 | Method for removing impurities in high-iron-content noble metal alloy |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE350598C (en) * | 1919-09-30 | 1922-03-21 | Carl Wilhelm Drais | Process for the recovery of precious metal from precious metal-containing residues, in particular scratch ash |
DE843015C (en) * | 1943-03-06 | 1952-07-03 | Basf Ag | Process for dissolving platinum metals |
US2946677A (en) * | 1958-11-24 | 1960-07-26 | Oregon Metallurgical Corp | Treatment of alloys containing iron group metals |
US3920790A (en) * | 1973-08-02 | 1975-11-18 | Swarsab Mining | Separating and purification of platinum group metals and gold |
-
1975
- 1975-01-29 ZA ZA00750593A patent/ZA75593B/en unknown
-
1976
- 1976-01-26 NO NO760228A patent/NO141444C/en unknown
- 1976-01-26 CA CA244,171A patent/CA1068116A/en not_active Expired
- 1976-01-27 DE DE2602827A patent/DE2602827C2/en not_active Expired
- 1976-01-28 FR FR7602279A patent/FR2299411A1/en active Granted
- 1976-01-29 GB GB349576A patent/GB1481295A/en not_active Expired
- 1976-01-29 JP JP51008823A patent/JPS5823449B2/en not_active Expired
- 1976-01-29 BE BE163894A patent/BE838029A/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
FR2299411B3 (en) | 1979-04-27 |
FR2299411A1 (en) | 1976-08-27 |
GB1481295A (en) | 1977-07-27 |
NO141444C (en) | 1980-03-12 |
JPS51125626A (en) | 1976-11-02 |
DE2602827C2 (en) | 1987-01-02 |
DE2602827A1 (en) | 1976-08-05 |
JPS5823449B2 (en) | 1983-05-16 |
NO760228L (en) | 1976-07-30 |
ZA75593B (en) | 1976-09-29 |
BE838029A (en) | 1976-07-29 |
NO141444B (en) | 1979-12-03 |
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