Newsletter of the Parker Centre

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Issue 14, March 2002

The students of the Parker Centre make a huge contribution to the Centres research effort. This issue focuses on some of our students whose research is directly related to industry needs and is supported by industry. If this research, or similar, could be of value to you, please contact CEO Mark Woffenden (Ph: 9360 2552; e-mail: mwoffend@parkercentre.crc.org.au).

Recovering silver from lead/zinc flotation tailings

The BHP Billiton silver-lead-zinc Cannington mine in north west Queensland was the official supplier of silver for the Sydney 2000 Olympic and Paralympic Games medals. A Parker Centre Masters student has identified a way for the mine to increase its production of silver. The Cannington mine, which sponsored this research, produces silver-rich lead and zinc concentrates. Cannington is the largest single mine producer of silver in the world. The waste (the tailings) from the Cannington concentrator still contains small (but valuable) amounts of silver, lead and zinc. Michael Rohde, a MSc student at the University of Queensland, has examined different leaching systems for extracting these residual metals from the tailings. An economic process would generate additional revenue for the mine. Cyanide and thiourea were the main leaching systems studied but ferric chloride and thiosulfate were also briefly investigated as possible alternative leaching agents. The Cannington mine provided Michael with three tailings samples. We found that the samples varied in their composition and that the minerals present influenced and significantly altered the amount of silver available to a leaching system, says Michael. Different silver minerals were leached to different extents by cyanide. In addition, other minerals with which the silver minerals were associated varied from sample to sample and affected the silver extraction with cyanide. Michael also found that silver recovery depended on the leaching system used. Approximately half of the silver present was recoverable by cyanide leaching of the third tailings sample (the sample of most importance so far) but lead and zinc recoveries were low (<5%), he says. Ferric chloride showed some improvement in silver recoveries and had superior recoveries of lead and zinc. Thiourea produced much improved recoveries for silver over cyanide but recovery of lead and zinc was also less than 5%. It appears that cyanide leaching may provide a way of processing the Cannington tailings for silver, he says. However, the chemical costs are relatively high given the silver recoveries at this time. Thus careful

Michael Rohde (right) with Ben Cronin (BHP Billiton) during a visit to the Cannington mine site. recycling of the cyanide solutions will most probably be needed for successful implementation of a leaching process. While thiourea provided higher silver recoveries, it has higher costs associated with it and even with careful recycling, it is unlikely that its use would be economic. Michael says leaching the silver, lead and zinc in a single step could be possible with ferric chloride but it would be difficult to recover them from this leaching system. It is likely that recovery of all three metals would involve at least two leaching stages using different leaching agents, he says. He will now further identify the silver minerals present in different tailings samples and establish which minerals are amenable to silver extraction by which leaching agents. The results will help determine whether tailings of particular compositions can be leached and the best potential way to process leachable tailings. The support provided by the Cannington mine has included the raw material (tailings), assistance with the elemental analysis and mineralogical data on some of the samples. Mr Ben Cronin, senior metallurgist at Cannington, is one of Michaels supervisors and has helped set the direction of the research.
Michaels work is part of the Parker Centres Gold Research Program.

Congratulations to Professor Ian Ritchie, the former CEO of the Parker Centre, who has had a prestigious scientific meeting named after him. The 2003 International Symposium on Hydrometallurgy in Honour of Professor Ian Ritchie will be held in Vancouver, Canada in August 2003.

Good luck
The Parker Centre has submitted an application for the CRC Association 2002 Technology Transfer Awards which recognise outstanding examples of the transfer of CRC research results. PhD students Mitch Loan and Jennifer Lowe have applied to attend the 2002 CRC Association Conference in Sydney in May. If selected, their travel, accommodation and conference registration will be paid and they may be invited to present at a special conference session.

AJ Parker CRC for Hydrometallurgy Murdoch University Murdoch Western Australia 6150 Phone (08) 9360 2552 Fax: (08) 9310 8481 http://www.parkercentre.crc.org.au

Solving the paragoethite precipitation puzzle

Pasminco Ltds Hobart Smelter uses the paragoethite process to remove iron (by precipitation) from zinc solutions prior to zinc metal recovery by electrolysis. However, Mitch Loan has discovered that the paragoethite precipitate is not in fact paragoethite. By working out the precipitates true identity and also how precipitation occurs, Mitch has found clues to developing methods for more effective removal of iron. Mitch is a Parker Centre PhD student based at Curtin University. He is undertaking this research in collaboration with Pasminco. When the paragoethite process is working well, the precipitate produced can be readily filtered from the zinc solution. But minor variations in operating conditions can generate precipitates with undesirable characteristics, resulting in poor filtration and washing of the filter cake. Mitch says this can create problems if the paragoethite stage either limits zinc recovery or becomes the bottleneck of the plant. Its just a residue but it can have a limiting effect on the plant. To improve the process, Pasminco needed to first understand what was happening during iron precipitation, and this is where Mitch came in. To understand how to crystallise something, you need to know what you are dealing with and no-one knew what type of iron compound(s) make up paragoethite, says Mitch. The process was termed paragoethite because it was believed that goethite, an iron oxy-hydroxide, could be formed by precipitating iron present in the ferric [iron(III)] state from dilute solutions. But theres no such thing as paragoethite, its a misnomer. Goethite is usually produced by oxidising zinc plant solutions containing iron in the ferrous [iron(II)] state. Mitch used a range of spectroscopic and chemical techniques to analyse the precipitate. He found that while the residue is made up of a number of insoluble (non-precipitated) components and precipitated components, the precipitated iron oxy-hydroxide ferrihydrite is the major iron component. Ferrihydrite has a unique precipitation mechanism, Mitch says. The initial crystals cant grow any bigger than tiny particles. But by sticking to each other and other types of particles, they can bulk up to become much larger particles. The downside is this aggregation can create holes, producing porous sponge-like ferrihydrite particles which soak up water and filter poorly. Controlling the aggregates to produce more compact, less porous particles with lower moisture content would increase filterability. So, how can this be achieved? To find out, Mitch has been carrying out precipitation experiments using plant solutions and a computer controlled continuous crystalliser, a vessel which simulates Pasmincos paragoethite precipitation circuit. He has investigated how operating conditions affect particle growth, size, shape, composition and filterability. In addition to determining the operating limits, Mitch has shown that careful control of factors such as pH, mixing and the amounts of certain components can help to produce a more compact residue with limited porosity. So, weve developed a set of rules for optimising the process and some concepts for improving the process, he says. But the improvements still need to be proven before they go into the plant. Further work on making the particles less porous is planned. Mitch says he will also do some experiments that just focus on ferrihydrite by using synthetic solutions. Mitchs research was assisted by a three month stint at Pasminco during 2001. He spent some time on the Hobart plant and then at Pasmincos R&D facility in Newcastle. In Newcastle, Mitch worked on several pilot plants which Pasminco uses to test changes before they are implemented on the real plant. We were looking at different changes which would influence the paragoethite circuit, he says. Pasminco has supported this PhD project by providing information, plant samples, funding for equipment and Dr Mike Newmans time as one of Mitchs PhD supervisors. Dr Ross Gordon Cooper, a former Parker Centre PhD student who now works at the Pasminco Hobart Smelter, is also providing assistance. My work may be relevant to other hydrometallurgical industries where iron is precipitated, for example as goethite because its likely this is also actually ferrihydrite, says Mitch. Mitch Loan with the continuous crystalliser that simulates Pasmincos paragoethite precipitation circuit. flowsheet page 2
Mitchs work is part of the Parker Centres Crystallisation Research Program.

Weve developed a set of rules for optimising the process and some concepts for improving the process

Helping a local nickel producer to improve leaching

Aleks Nikoloskis PhD research has identified a potential cause of the relatively low recoveries of nickel and cobalt from the leaching of pre-reduced nickel laterite ores. Higher recoveries may now be possible. This research has been conducted in close collaboration with Queensland Nickel (QNI) Ltds Yabulu refinery, located near Townsville in north Queensland. The Yabulu plant uses the Caron process to extract nickel and cobalt from laterite ores, a process involving reduction of the ore by roasting at about 750oC followed by leaching with ammonia-ammonium carbonate solution at atmospheric pressure and about 45oC. The other commercial method for processing laterite ores is pressure acid leaching (PAL) which involves leaching the ore with sulfuric acid at about 250oC and 4000kPa pressure. Worldwide, four plants use the Caron process and four plants use the PAL process, including three newer plants in WA. The Caron process has been improved since first commercialised in 1944 but compared to pressure acid leaching, it still suffers from low recoveries. They normally extract about 75-85% of the nickel and 4555% of the cobalt, says Aleks. So, in order to stay competitive, they have to find some way to further improve recoveries. But its difficult to tackle the recovery problem unless you have established the reasons for the low recoveries, Aleks says. His PhD project is shedding light on the leaching mechanism by which the iron alloy grains (containing the nickel and cobalt) formed in the reduction stage dissolve. This understanding has identified factors limiting the leaching and should assist in developing alternative strategies for leaching which increase recovery. The project has involved laboratory and on-site work during three visits to the Yabulu plant. His experiments are designed to reflect the conditions in the plant. Aleks is using electrochemical techniques to study the leaching mechanisms. Electrochemical reactions are chemical reactions in which electrons are transferred. The leaching of nickel and cobalt by the Caron process is an electrochemical process, he says. It involves oxidation [loss of electrons] of the metal and reduction [gain of electrons] of the oxidising agent. His electrochemical studies have focused on the dissolution of synthetic iron-nickel-cobalt alloys (that simulate the dissolving iron alloy grains at the plant) in solution which mimics the plant leaching solution. He has made some significant new discoveries. One is that, unlike previously thought, reduction of water is not a major component of the dissolution process. More importantly, he found that there is passivation of the surface of the dissolving iron alloys under certain conditions. Passivation is the formation of a surface layer which prevents electron transfer, thus blocking leaching. We believe that passivation is contributing to the low recoveries of nickel and cobalt in the Caron process, says Aleks. His work suggests there are two different passive

Aleks Nikoloski undertaking electrochemical studies of the dissolution of synthetic iron-nickelcobalt alloys. layers which can form one is mixed iron-nickel-cobalt sulfide from reduction of thiosulfate ions and the other is iron oxide from reduction of oxygen. The thiosulfate is generated in the leaching process from sulfide in the ore and from high sulfur fuel oil used in the reduction stage. Aleks has proved that passivation also occurs in the leaching plant at Yabulu. However, this passivation appears to be the type promoted by oxygen. It is likely thiosulfate is not causing passivation on the plant because the time during which thiosulfate can act is not long enough to create a passive layer, he says. He is now investigating how to overcome the passivation caused by oxygen. This passivation can occur during the leaching step which uses air (where oxygen is the main agent oxidising the iron alloy grains) if oxygen concentrations are particularly high. Aleks believes tight control of the air addition and the oxidising state of the leaching solution would help prevent passivation. Aleks says his PhD project is strongly supported by QNI. This support includes providing maintenance funds and access to the plant and plant personnel during on-site visits. In addition, he has on-going consultations with QNIs Principal Development Chemist Mr John Fittock who is one of his supervisors. Aleks was already quite familiar with the Yabulu plant before starting his PhD at Murdoch University in 1999 as he worked for QNI during 1998. Aleks also undertook his Honours project within the Parker Centre. In September last year, he was awarded the 2001 GB OMalley Medal by the Australasian Institute of Mining and Metallurgy (AusIMM). Aleks received this medal, AusIMMs highest student award, for the paper he presented on his Honours research at the 7th Mill Operators Conference.
Alekss work is part of the Parker Centres Leaching, Reduction & Separation Processes Research Program.

We believe that passivation is contributing to the low recoveries of nickel and cobalt in the Caron process

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Targeting bacterial leaching of gold sulfide ores

We thought that the bacteria would chew through everything but if you just used the ferric ions, you could get selective leaching of the arsenopyrite, says Rosie. The columns were used to test this hypothesis. The crushed ore was analysed before being put in the columns to make sure both columns had the same gold grades and the same arsenic and sulfur levels. The columns both sat in a controlled temperature bath at 35oC which kept the bacteria happy. The columns were run for two months. The amount of arsenic and iron that came out into solution over time was measured. We assumed that arsenopyrite is the only mineral in the ore containing arsenic, so the arsenic in solution gave us a good indication of how much of the arsenopyrite had dissolved, Rosie says. The iron in solution came from oxidised pyrite and arsenopyrite. Rosie compared the iron to arsenic ratio in the solution from each column. The results showed that while the arsenopyrite was selectively oxidised in both columns, the ferric ion leach was more selective for arsenopyrite. Before running the columns, the crushed ore used to fill the columns had been leached with cyanide to determine the percentage of gold extraction. After the column leaching had finished, Rosie repeated the cyanide leach tests on the ore in the columns. Unfortunately, neither the bacterial leach nor the ferric leach gave an improved gold extraction, she says. It is possible that only a small proportion of the gold was actually associated with the arsenopyrite, so even though this mineral was selectively oxidised, it did not improve the gold recovery. Rosie also carried out some experiments on a mineral concentrate of the sulfides from Sunrise Dam to further study the ferric leach. Using a reactor that holds the ratio of ferrous to ferric ions (how oxidising the conditions are) at a constant level, she investigated how changing the temperature, and other variables, affected the rate of mineral breakdown. For a refractory ore in which the gold is predominantly associated with arsenopyrite, a ferric leach process could be set up on a gold plant by growing the bacteria in a separate stage and using the resulting ferric ion-containing solution for selective leaching. The ferrous ion-containing solution after leaching would be recycled back for the bacteria to regenerate the ferric ions. The advantage of this setup would be that because the two parts are separate, the optimal ferric leach temperature could be varied with respect to the optimal temperature in the bacterial stage. This Honours project continued Rosies earlier association with Sunrise Dam. She did vacation work on the gold mine during her Mineral Science undergraduate course.
Rosies work was part of the Parker Centres Gold Research Program.

Rosie Daniels with the reactor that holds the ratio of ferrous to ferric ions at a constant level.

A small component of the Sunrise Dam Gold Mines orebody is refractory, which means the gold is locked up within the sulfide mineral matrix of the ore and cannot be completely extracted with cyanide. So, Sunrise Dam funded research by Honours student Rosie Daniels to look for a way to free the gold from this ore. Refractory gold ores need oxidative treatment (eg roasting, bacterial oxidation or pressure oxidation) to oxidise the sulfides. This breaks up the mineral matrix, letting the cyanide dissolve the exposed gold. Owned by AngloGold Australasia Ltd, Sunrise Dam Gold Mine is located near Laverton, north of Kalgoorlie. The refractory ore at Sunrise Dam contains both arsenopyrite (FeAsS) and pyrite (FeS2), the main sulfide minerals associated with refractory gold ores worldwide. Initial analysis indicated the gold in this ore was predominantly associated with the arsenopyrite. A process which only targeted the arsenopyrite would be useful in treating such an ore. We wanted to develop a process that selectively breaks down the arsenopyrite so we can get the gold out without having to treat all of the material in the ore, says Rosie. Bioleaching (bacterial oxidation) uses rock-eating bacteria, which live on a mineral diet by oxidising sulfides. Rosie says the Murdoch University researchers with whom she did Honours think there are two ways in which these bacteria work. In the direct method, the bacteria bind all over the surface and chomp away at the ore, she says. In the indirect method, ferric [iron(III)] ions oxidise the sulfides and are converted to ferrous [iron(II)] ions which the bacteria turn back into ferric ions. So, this latter method is a chemical leaching where the bacteria are continually generating the oxidising reagent. Rosies main experiments involved column leaching with two tall columns of crushed refractory ore from Sunrise Dam. Solution was trickled through each column, collected at the bottom and recycled. The solution added to one column contained the bacteria while ferric ions but no bacteria were added to the other column to mimic the indirect method.

THE PARKER CENTRE WAS ESTABLISHED AND IS SUPPORTED UNDER THE AUSTRALIAN GOVERNMENTS COOPERATIVE RESEARCH CENTRES PROGRAM

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