EP1061144A1 - Method of preparing high purity gold from precious metal bearing nitrate solutions - Google Patents
Method of preparing high purity gold from precious metal bearing nitrate solutions Download PDFInfo
- Publication number
- EP1061144A1 EP1061144A1 EP00111133A EP00111133A EP1061144A1 EP 1061144 A1 EP1061144 A1 EP 1061144A1 EP 00111133 A EP00111133 A EP 00111133A EP 00111133 A EP00111133 A EP 00111133A EP 1061144 A1 EP1061144 A1 EP 1061144A1
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- European Patent Office
- Prior art keywords
- solution
- gold
- nitrate
- precious metal
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- 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
- C22B11/00—Obtaining noble metals
Definitions
- the invention relates to a method for producing gold of high purity from nitrate-containing Precious metal solutions.
- a method for producing a gold powder from particles of certain Size and shape revealed which is characterized in that a gold salt solution with a reducing agent, namely 1) hydroquinone or bromine, chlorine or low Alkyl substitution products of hydroquinone or mixtures thereof or 2) oxalic acid, one Alkaline salt of oxalic acid or mixtures thereof or 3) combinations of 1) and 2) in the presence of a protective colloid is reduced at a temperature in the range of 20 to 100 ° C.
- a reducing agent namely 1) hydroquinone or bromine, chlorine or low Alkyl substitution products of hydroquinone or mixtures thereof or 2) oxalic acid, one Alkaline salt of oxalic acid or mixtures thereof or 3) combinations of 1) and 2) in the presence of a protective colloid is reduced at a temperature in the range of 20 to 100 ° C.
- the problem that arises is in particular in providing a process for producing high purity gold using just a few steps.
- the nitrate in the noble metal solution is destroyed in a first step, for example by adding a reducing agent to the heated solution.
- the gold ions are then reduced to gold by adding an acidic Fe 2+ solution, the concentration of H + of the Fe 2+ solution being at least 4 mol / l.
- the precious metal solution previously prepared free of nitrates has a concentration of H + ions of at least 4 mol / l.
- step b that is to say the addition of an acidic Fe 2+ solution to the nitrate-free prepared noble metal solution, is carried out in a potential-controlled manner, since in this way the end of the reduction is relatively easy to recognize and targeted process control is thus possible.
- nitrate destruction with formic acid or ascorbic acid is carried out because these substances specifically reduce nitrate to NO, but not gold ions.
- the end of the reduction is announced by a significant drop in potential.
- the end point is at 560 mV vs. Pt // Ag / AgCl to determine the necessary purity of the gold while at the same time to achieve optimal gold yield.
- the residual gold content in the mother liquor was 7 ppm or 0.08% of the gold used.
- the purity of the gold sponge produced meets the 99.99% fine gold criteria according to the Amercian standard.
- the following were found as impurities by means of GDL analysis: Ag 11 ppm Cu 1 ppm Pt ⁇ 3 ppm Fe 12 ppm Pd 25 ppm Mg ⁇ 2 ppm Rh ⁇ 1 ppm Mn ⁇ 1 ppm Ru ⁇ 1 ppm Ni ⁇ 1 ppm Al ⁇ 1 ppm Pb ⁇ 3 ppm Be ⁇ 1 ppm Sb ⁇ 5 ppm Bi ⁇ 5 ppm Si 15 ppm Ca ⁇ 1 ppm Sn ⁇ 5 ppm Cd ⁇ 5 ppm Te ⁇ 5 ppm Co ⁇ 3 ppm Zn 2 ppm Cr 1 ppm Total: 67 ppm corresponding to> 99.99% gold purity.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
Es wird u. a. ein Verfahren zur Herstellung von Gold hoher Reinheit aus nitrathaltigen Edelmetall-Lösungen vorgestellt, mit folgenden Schritten: a) Nitratzerstörung in der Edelmetall-Lösung, b) eine Gold-Ionen-reduzierende Zugabe einer sauren Fe<2+>-Lösung, deren Konzentration an H<+>-Ionen mindestens 4 mol/l beträgt, zur in Schritt a) aufbereiteten Lösung, deren Konzentration an H<+>-Ionen mindestens 4 mol/l beträgt.It is u. a. presented a process for the production of gold of high purity from nitrate-containing precious metal solutions, with the following steps: a) nitrate destruction in the precious metal solution, b) a gold ion-reducing addition of an acidic Fe <2 +> solution, the concentration of which H + + ions is at least 4 mol / l to the solution prepared in step a), the concentration of H + + ions of which is at least 4 mol / l.
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Gold hoher Reinheit aus nitrathaltigen Edelmetall-Lösungen.The invention relates to a method for producing gold of high purity from nitrate-containing Precious metal solutions.
In DE-Z.: T. Havlik u.a.: The leaching behaviour of tetrahedrite concentrate in nitrate solution" in: Metall, 52, 1998, 4, Seiten 210 bis 213, ist u. a. offenbart, dass aus Nitratlösungen Metalle in Anwesenheit von Eisenionen besonders gut durch Zementation herauslösbar sind.In DE-Z .: T. Havlik and others: The leaching behavior of tetrahedrite concentrate in nitrate solution "in: Metall, 52, 1998, 4, pages 210 to 213, discloses, inter alia, that metals can be removed particularly well from nitrate solutions in the presence of iron ions by cementation.
In DE 21 54 093 wird u. a. ein Verfahren zur Herstellung eines Goldpulvers aus Teilchen bestimmter Grösse und Gestalt offenbart, das dadurch gekennzeichnet ist, dass man eine Goldsalzlösung mit einem Reduktionsmittel, nämlich 1) Hydrochinon oder Brom-, Chlor- oder niedrig Alkyl-Substitutionsprodukte von Hydrochinon oder Gemischen davon oder 2) Oxalsäure, einem Alkalisalz von Oxalsäure oder Gemischen davon oder 3) Kombinationen von 1) und 2) in Gegenwart eines Schutzkolloids bei einer Temperatur in dem Bereich von 20 bis 100 °C reduziert.In DE 21 54 093 u. a. a method for producing a gold powder from particles of certain Size and shape revealed, which is characterized in that a gold salt solution with a reducing agent, namely 1) hydroquinone or bromine, chlorine or low Alkyl substitution products of hydroquinone or mixtures thereof or 2) oxalic acid, one Alkaline salt of oxalic acid or mixtures thereof or 3) combinations of 1) and 2) in the presence of a protective colloid is reduced at a temperature in the range of 20 to 100 ° C.
Es ist seit langem bekannt, Gold hoher Reinheit mittels SO2 aus nitrathaltigen Edelmetall-Lösungen zu gewinnen. Nachteilig bei diesen Verfahren ist die Notwendigkeit, die erhaltenen Produkte mehrfach umzulösen. Die hierdurch anfallende Vielzahl der einzelnen Verfahrensschritte bedingt einen hohen Kosten- und Zeitaufwand.It has long been known to obtain high purity gold from nitrate-containing precious metal solutions using SO 2 . A disadvantage of these processes is the need to redissolve the products obtained several times. The resulting large number of individual process steps requires a high cost and time.
Aus dem Vorgenannten ergibt sich das Problem, mit Hilfe eines neuartigen Verfahrens die oben genannten Nachteile zumindest teilweise zu beseitigen. Das sich ergebende Problem liegt insbesondere darin, ein Verfahren zur Herstellung von Gold hoher Reinheit bereitzustellen, das mit wenigen Arbeitsschritten auskommt. The problem arises from the above, with the help of a novel method the above to at least partially eliminate the disadvantages mentioned. The problem that arises is in particular in providing a process for producing high purity gold using just a few steps.
Dieses Problem wird erfindungsgemäß durch ein Verfahren nach Anspruch 1 gelöst.According to the invention, this problem is solved by a method according to claim 1.
Beim erfindungsgemäßen Verfahren wird in einem ersten Schritt das in der Edelmetall-Lösung befindliche Nitrat zerstört, beispielsweise durch Zugabe eines Reduktionsmittels in die aufgeheizte Lösung. Anschließend werden die Goldionen durch Zugabe einer sauren Fe2+-Lösung zu Gold reduziert, wobei die Konzentration an H+ der Fe2+-Lösung mindestens 4 mol/l beträgt. Die vorher nitratfrei aufbereitete Edelmetall-Lösung weist eine Konzentration an H+-Ionen von mindestens 4 mol/l auf.In the method according to the invention, the nitrate in the noble metal solution is destroyed in a first step, for example by adding a reducing agent to the heated solution. The gold ions are then reduced to gold by adding an acidic Fe 2+ solution, the concentration of H + of the Fe 2+ solution being at least 4 mol / l. The precious metal solution previously prepared free of nitrates has a concentration of H + ions of at least 4 mol / l.
Von besonderem Vorteil ist es, wenn die Reduktion des Schrittes b), also die Zugabe einer sauren Fe2+-Lösung zur nitratfrei aufbereiteten Edelmetall-Lösung, potentialgesteuert durchgeführt wird, da auf diese Art und Weise das Ende der Reduktion relativ leicht zu erkennen und somit eine gezielte Verfahrenssteuerung möglich ist.It is particularly advantageous if the reduction in step b), that is to say the addition of an acidic Fe 2+ solution to the nitrate-free prepared noble metal solution, is carried out in a potential-controlled manner, since in this way the end of the reduction is relatively easy to recognize and targeted process control is thus possible.
Weiterhin ist es von Vorteil, wenn die Nitratzerstörung mit Ameisensäure oder Ascorbinsäure durchgeführt wird, da diese Substanzen spezifisch Nitrat zu NO reduzieren, nicht jedoch Goldionen.Furthermore, it is advantageous if the nitrate destruction with formic acid or ascorbic acid is carried out because these substances specifically reduce nitrate to NO, but not gold ions.
Die Nitratzerstörung wird vorteilhafterweise bei einer Temperatur von T = + 80 ° C bis + 90 °C durchgeführt, um so eine effiziente Zerstörung des Nitrats zu gewährleisten.The nitrate destruction is advantageously at a temperature of T = + 80 ° C to + 90 ° C carried out so as to ensure efficient destruction of the nitrate.
Schließlich wird die in Schritt a) aufbereitete Lösung, also die nitratfrei gemachte Edelmetall-Lösung, vor Zugabe der Fe2+-Ionen-Lösung auf eine Temperatur von T = + 60 °C aufgeheizt, da auf diese Art und Weise das Gold feinkörniger und mit weniger Einschlüssen ausfällt.Finally, the solution prepared in step a), ie the nitrate-free precious metal solution, is heated to a temperature of T = + 60 ° C. before adding the Fe 2+ ion solution, since in this way the gold is finer-grained and fails with fewer inclusions.
Das nachfolgende Beispiel dient zur Erläuterung der Erfindung.The following example serves to explain the invention.
-
Goldlösung in Königswasser
c(Au) = 33,508 g/l, c(Pd) = 9,861 g/l, c(Pt) = 10,612 g/lGold solution in aqua regia
c (Au) = 33.508 g / l, c (Pd) = 9.861 g / l, c (Pt) = 10.612 g / l - Eisen(II)sulfat, techn. FeSO4 . 7 H20 in 10 n HCl gelöstIron (II) sulfate, techn. FeSO 4 . 7 H 2 0 dissolved in 10 N HCl
- Salzsäure, techn., 10 nHydrochloric acid, technical, 10 n
- Ameisensäure, techn., 85 %Formic acid, technical, 85%
In einem heizbaren 1 l Laborreaktor mit Rückflußkühler und Glasrührer wurden 500 ml der goldhaltigen Ausgangslösung vorgelegt und mit 285 ml konz. Salzsäure versetzt, um eine Säurenormalität von 4 mol/l einzustellen. Anschließend ist die Lösung unter Rühren auf eine Temperatur von 100 °C erhitzt und die Temperatur während der Ameisensäurezugabe gehalten worden. Nun wurden mit Hilfe einer Schlauchpumpe über eine Zeitraum von 1 Stunde 45 ml Ameisensäure zudosiert. Während der Ameisensäurezugabe traten intensive NOx-Dämpfe auf, die am Ende der Nitratzerstörung nicht mehr zu beobachten waren. Das Redoxpotential ist während der Ameisensäurezugabe von einem Anfangspotential von 854 mV vs. Pt//Ag/AgCl auf einen Endwert von 723 mV vs Pt//Ag/AgCl abgefallen. Die Lösung wurde im Anschluß auf Raumtemperatur abgekühlt.In a heatable 1 liter laboratory reactor with reflux condenser and glass stirrer, 500 ml of the gold-containing starting solution and 285 ml conc. Hydrochloric acid added to an acid normality of 4 mol / l. The solution is then brought to a temperature with stirring heated from 100 ° C and the temperature maintained during the addition of formic acid been. Now, with the help of a peristaltic pump, 45 ml Formic acid added. Intensive NOx vapors occurred during the addition of formic acid, which could no longer be observed at the end of the nitrate destruction. The redox potential is during the formic acid addition from an initial potential of 854 mV vs. Pt // Ag / AgCl dropped to a final value of 723 mV vs Pt // Ag / AgCl. The solution was subsequently on Cooled to room temperature.
Die Lösung nach der Nitratzerstörung wurde in ein Becherglas überführt, wobei beobachtet wurde, daß bereits eine geringe Menge Gold ausgefallen war. Der Rückstand wurde komplett mit der Lösung in das Becherglas gegeben. Es ergab sich ein Lösungsvolumen von 1500 ml. Nun wurde auf dem Magnetrührer auf 60 °C aufgeheizt und unter ständiger Potentialkontrolle innerhalb von 2 Stunden 495 ml 0,5 n FeSO4-Lösung mit Hilfe einer Schlauchpumpe zudosiert. Das Redoxpotential fiel während der Reduktion von einem Anfangswert von 723 mV vs. Pt//Ag/AgCl auf den Endwert von 560 mV vs. Pt//Ag/AgCl ab. Nach Erreichen des Redoxpotentials von 560 mV vs. Pt//Ag/AgCl wurde die Eisensulfatzugabe gestoppt. Es wurde auf Raumtemperatur abgekühlt und der Rührer ausgeschaltet. Zum Teil haftete das ausreduzierte Gold am Rührer bzw. an der Redoxelektrode an, der Hauptteil jedoch befand sich am Boden des Becherglases. Der ausreduzierte Au-Schwamm wurde über eine Nutsche abfiltriert und mit 100 ml VE-Wasser gewaschen. Es wurden feine, blättrige Goldflitter erhalten. Diese wurden im Trockenschrank bei 100 °C getrocknet (Auswaage: 16,74 g) und zur Reinheitsanalyse per Röntgenfluoreszenz gegeben. Das Filtrat und das Waschwasser wurden vereinigt, gemischt, ausgelitert (2000 ml) und eine Standard-DCP-Analyse veranlaßt.The solution after the nitrate destruction was transferred to a beaker, and it was observed that a small amount of gold had already precipitated out. The residue was completely added to the beaker with the solution. The result was a solution volume of 1500 ml. The mixture was then heated to 60 ° C. on a magnetic stirrer and 495 ml of 0.5 n FeSO 4 solution were metered in with the aid of a peristaltic pump with constant monitoring of the potential over the course of 2 hours. The redox potential fell during the reduction from an initial value of 723 mV vs. Pt // Ag / AgCl to the final value of 560 mV vs. Pt // Ag / AgCl. After reaching the redox potential of 560 mV vs. Pt // Ag / AgCl the iron sulfate addition was stopped. It was cooled to room temperature and the stirrer was switched off. Some of the reduced gold adhered to the stirrer or redox electrode, but the main part was at the bottom of the beaker. The reduced Au sponge was filtered off through a suction filter and washed with 100 ml of demineralized water. Fine, flaky gold flakes were obtained. These were dried in a drying cabinet at 100 ° C. (weight: 16.74 g) and given for purity analysis by means of X-ray fluorescence. The filtrate and wash water were combined, mixed, filtered (2000 ml) and a standard DCP analysis was carried out.
Es werden für die nachfolgende Versuchsauswertung folgende Reaktionsgleichungen zugrunde
gelegt:
Für die Nitratzerstörung wurden in diesem Versuch für 500 ml Ausgangslösung 45 ml 85%ige Ameisensäure verbraucht. Am Ende der Nitratzerstörung war wenig Gold ausgefallen, welches jedoch nicht separat gehalten werden braucht.For the nitrate destruction in this experiment, 45 ml of 85% strength were used for 500 ml of starting solution Formic acid consumed. At the end of the nitrate destruction, little gold had failed but does not need to be kept separately.
Das Ende der Reduktion kündigt sich durch einen deutlichen Potentialabfall an. Der Endpunkt ist bei 560 mV vs. Pt//Ag/AgCl festzulegen, um die nötige Reinheit des Goldes bei gleichzeitiger optimaler Goldausbeute zu erzielen.The end of the reduction is announced by a significant drop in potential. The end point is at 560 mV vs. Pt // Ag / AgCl to determine the necessary purity of the gold while at the same time to achieve optimal gold yield.
Die zugesetzte Menge Eisensulfatlösung (495 ml) mit 0,5 mol/l entspricht nach Gleichung (3) einer theoretischen Goldmenge von 16,25 g. Im Versuch wurden 16,74 g Gold ausreduziert, so daß die tatsächlich benötigte Menge Eisensulfat ca. 97 % der Stöchiometrie entspricht.The added amount of iron sulfate solution (495 ml) with 0.5 mol / l corresponds to equation (3) a theoretical amount of gold of 16.25 g. In the experiment, 16.74 g of gold was reduced, so that the amount of iron sulfate actually required corresponds to approximately 97% of the stoichiometry.
Der Restgehalt Gold in der Mutterlauge betrug 7 ppm oder 0,08 % des eingesetzten Goldes.
Die Reinheit des erzeugten Goldschwammes erfüllt die Kriterien von Feingold 99,99 % nach
dem Amercian Standard. Es wurden als Verunreinigungen mittels GDL-Analyse festgestellt:
Claims (5)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19928028A DE19928028C1 (en) | 1999-06-18 | 1999-06-18 | High purity gold is recovered from nitrate solution by nitrate decomposition to obtain a highly acidic solution from which gold is recovered by ferric ion addition |
DE19928028 | 1999-06-18 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1061144A1 true EP1061144A1 (en) | 2000-12-20 |
EP1061144B1 EP1061144B1 (en) | 2003-10-29 |
Family
ID=7911782
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00111133A Expired - Lifetime EP1061144B1 (en) | 1999-06-18 | 2000-05-24 | Method of preparing high purity gold from precious metal bearing nitrate solutions |
Country Status (4)
Country | Link |
---|---|
US (1) | US6331200B1 (en) |
EP (1) | EP1061144B1 (en) |
DE (2) | DE19928028C1 (en) |
ZA (1) | ZA200003019B (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0073108A1 (en) * | 1981-08-12 | 1983-03-02 | Robert Henry Perrin | A process for the recovery of metals |
JPH05222465A (en) * | 1992-02-10 | 1993-08-31 | Sumitomo Metal Mining Co Ltd | Method for removing nox from palladium-containing solution |
JPH09272927A (en) * | 1996-04-08 | 1997-10-21 | Sumitomo Metal Mining Co Ltd | Removing method of nitrogen oxides from palladium-containing solution |
RU2120485C1 (en) * | 1997-07-03 | 1998-10-20 | Щелковский завод вторичных драгоценных металлов | Method of removing platinum metals from material containing these metals |
-
1999
- 1999-06-18 DE DE19928028A patent/DE19928028C1/en not_active Expired - Fee Related
-
2000
- 2000-05-24 EP EP00111133A patent/EP1061144B1/en not_active Expired - Lifetime
- 2000-05-24 DE DE50004219T patent/DE50004219D1/en not_active Expired - Lifetime
- 2000-06-15 ZA ZA200003019A patent/ZA200003019B/en unknown
- 2000-06-16 US US09/595,123 patent/US6331200B1/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0073108A1 (en) * | 1981-08-12 | 1983-03-02 | Robert Henry Perrin | A process for the recovery of metals |
JPH05222465A (en) * | 1992-02-10 | 1993-08-31 | Sumitomo Metal Mining Co Ltd | Method for removing nox from palladium-containing solution |
JPH09272927A (en) * | 1996-04-08 | 1997-10-21 | Sumitomo Metal Mining Co Ltd | Removing method of nitrogen oxides from palladium-containing solution |
RU2120485C1 (en) * | 1997-07-03 | 1998-10-20 | Щелковский завод вторичных драгоценных металлов | Method of removing platinum metals from material containing these metals |
Non-Patent Citations (3)
Title |
---|
DATABASE WPI Section Ch Week 199339, Derwent World Patents Index; Class E36, AN 1993-309447, XP002147907 * |
DATABASE WPI Section Ch Week 199801, Derwent World Patents Index; Class M25, AN 1998-004405, XP002147909 * |
DATABASE WPI Section Ch Week 200012, Derwent World Patents Index; Class M25, AN 2000-135514, XP002147908 * |
Also Published As
Publication number | Publication date |
---|---|
ZA200003019B (en) | 2001-01-09 |
EP1061144B1 (en) | 2003-10-29 |
US6331200B1 (en) | 2001-12-18 |
DE50004219D1 (en) | 2003-12-04 |
DE19928028C1 (en) | 2000-08-17 |
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