REVIEW OF CURRENT URANIUM EXTRACTION AND PROCESSING

J. Bennetts, A. de Bie and N. Yurisich

ABSTRACT
This paper reviews current practices of Uranium ore processing with a focus on Australian mines. Included in this review is the mining and ore dressing techniques that are used on Uranium ores. Also discussed is the very cost effective In-Situ leaching process used for Uranium extraction. The basic chemistry of processing the ore using leaching is considered giving comparisons between both acid and alkaline techniques. After leaching takes place solids must be separated from the liquids preparatory to the solvent extraction process. Solvent extraction and precipitation produces the Uranium cake product in a saleable form. The chemistry of solvent extraction and the precipitation process are also discussed.

INTRODUCTION
The uranium industry has grown dramatically over the past 60 years. From a few hundred tonnes prior to 1942, uranium production has expanded to 59,875 tonnes in 2009 (Assmann, 2011, slide 7). Australia has the largest uranium reserves in the world (23%) and contributes approximately 16% of the total world uranium production (Assmann, 2011, slide 11). Australia is up to date with current global Uranium processing practices. There is still much more research that can be carried out in the field of Uranium ore processing as much of the current information is sourced from the 80s and is thus out-dated. Current trends suggest that there will be an increase in demand for Uranium ore products in the future, globally and within Australia, hence the need for more current information on Uranium ore processing. The mining/extraction techniques for uranium are essentially the same as most other ore deposits around the world, however in-situ leaching is a novel uranium extraction technique. In-Situ leaching would be the preferred method of mining Uranium however it can only be used when specific geological conditions of the ore deposit are satisfied. Above-ground leaching is performed in all other cases in the form of heap leaching, agitated leaching or pressure leaching. Purification and processing of the leached liquor is carried out by solvent extraction and precipitation to form a useable uranium product.

MINING TECHNIQUES
The main mining techniques used for Uranium extraction in Australia are open pit and underground which will both be briefly discussed in this section. Conventional- Open Pit mining. Open pit mining is a commonly used technique for uranium extraction around the world (Infomine, 2012). This technique generally has a higher productivity together with lower costs and greater safety compared with underground mining. However if too much overburden or the shape of ore body dictates underground mining may be the most viable option (Gupta, 2003). Open pit mining is used at the Ranger Uranium, N.T., Australia (ERA, 2012). Dredging (type of open pit mining) is used for unconsolidated ores under shallow water or in locations with high water table. Essentially a floating mining and processing plant that produces its own moving pond as it works. Ore is brought up either by suction or a bucket line, processed aboard and dumped behind (Gupta, 2003). Conventional- Underground mining. Underground mining is generally used when the ore body is at a depth too great for open pit suggests (Darling, 2011). This type of mining comprises of digging tunnels or shafts into the earth to reach buried ore deposits. The desired economical ore is brought to the surface via some combination of shafts or tunnels,

sometimes along with waste rock also. There are a number of different underground mining techniques that can be used for uranium deposits which will depend on the shape and size of the deposit. One method is called room and pillar which would be used when large deposits extend horizontally, the pillars amounting to 25 % to the ore body being left to hold up the roof. If the deposit extends vertically, a vertical shaft is cut alongside it and horizontal galleries are driven across at various levels to the vein. The mineral content of the vein above each point is blasted down and taken out to the shaft. Another method for irregular deposits is caving which involves undercutting the deposit and blasting it so it falls into a prepared area to be transported to the surface (Gilchrist, 1980). Figure 1 below is an example of the basic underground mine design of the Olympic Dam mine setup in S.A. Once an area has been mined underground it must be filled in, which can be done with some combination of waste material. In the Olympic Dam mine this is done via stopes being backfilled with cemented aggregate of crushed waste rock, disliked mill tailings, cement and pulverised fuel ash (Infomine, 2010).

Another technology used in underground mining is the disposal of tailings in paste form, consisting of higher amounts of solids. This is suitable for disposal under water, minimising radiation exposure (NEA/IAEA Report, 1993). In Saskatchewan, Canada, a new technology of nonentry mining is being developed for extracting high grade ore in underground mines. Primary removal by box hole boring, remote box hole stoping, or jet boring methods, all of which rely on remotely operated equipment. This allows workers to stay away from the ore body and associated high levels of radiation (NEA/IAEA Report, 1993).

ORE DRESING
Uranium, like most ores needs to be crushed, ground and sized to achieve sufficient liberation of the economic mineral from the gangue before chemical treatment (Stockholm, 2011). Crushing Crushing the ore means breaking it apart into smaller pieces via machines such as; jaw crushers, gyratory crushers and cone crushers (Gilchrist, 1980). These machines accept the ROM ore in through a wide feed opening and then crush the ore until it can pass through a gap of desired size. Each machine has different characteristics, in regards to the amount of mass that can be processed per hour, sized reduction, hardness capabilities and energy efficiency. For example the Ranger mine crushes its ore in a crushing and screening circuit to less than 19 millimetres and uses both a primary and secondary crusher (ERA, 2012). In the case of Olympic Dam, the primary crushing is done underground by a gyratory crusher (World-nuclear, 2012). Grinding After initial crushing operations the particle size can be further reduced by grinding. Water is typically added to the crushed ore, which is then fed into a grinder, which could be a ball, SAG, tube, pebble or rod mill crushers (Gilchrist, 1980).

Figure 1. Olympic Dam mine setup. Source:http://www.infomine.com/minesite/minesite .asp?site=olympicdam

Milling efficiency Lower grade ore usually mean smaller grains of the uranium mineral in the ore rock. This ore then has to be ground to a finer mesh, in order to liberate the smaller uranium grains from the rock matrix. This means the energy input of grinding per tonne of ore increases the finer it is ground (Leeuwen, 2007).

PROCESSING
The current accepted resource processing steps consist of leaching to bring uranium into solution, concentration and purification of dissolved uranium, and precipitation of the concentrated and purified dissolved uranium into a suitable chemical intermediate suita product. Leaching The leaching process in the mining of uranium is the treatment of ores with suitable solvents (acids or alkalis) to convert uranium contained in the ore to water-soluble ores species (IAEA, 1993, p. 75). The soluble selection of oxidant is dependent on the amount of acid solubles (carbonates) present in the ore body. As a general guide, if the ore contains more than 7-9% of eral 7 carbonates or if acid consumption exceeds 68 kg/t of ore, alkaline leaching is preferred as the amount of acid consumed by the carbonates becomes too costly (IAEA, 1993, p. 75). Sulphuric acid is used for leaching l whenever possible as it has faster reaction kinetics and higher uranium recoveries with most ores (Taylor, 2010, p. 71). Carbonate leaching is more selective than acid leaching (and hence a higher product purity is obtained), and is beneficial in cases when treating c highly calcareous ores which would consume large amounts of acid. One example of such conditions is the Wiluna Uranium Project in Western Australia, where the Uranium is found calcrete/clay hosted carnotite minerals (Kenny et al., 2010, p. 6-17). Acid leaching at , Wiluna has a very high acid consumption rate (700 kg/t); therefore an alkaline leaching process is needed. lkaline Leaching Chemistry There are two valency states in which uranium occurs naturally which are the hexavalent form for which the oxide form is UO3, and the tetravalent form, for which the oxide form is UO2. The aim of leaching is to dissolve hexavalent uranium minerals (U6+) and to convert tetravalent uranium minerals (U4+) to the hexavalent form. Only U6+ compounds dissolve readily in acidic and rea alkaline carbonate solutions, whereas lower valence uranium compounds do not. For leaching to occur, an oxidant is required. In the leaching process, the solid

IN SITU LEACHING
Another strategy for Uranium recovery is know as In known Situ leaching or ISL. ISL bypasses the need for mining and ore dressing as previously mentioned. Successful ISL of uranium initially requires the identification of suitable, below-water-table sedimentary deposits in table which uranium is confined in permeable rock by impermeable layers (Darling, 2011). ISL involves leaving the ore underground and recovering the miner minerals by dissolving them and pumping the pregnant solution to the surface where the minerals can be recovered. Little surface disturbance and no tailing or waste rock generated. The ore body must be permeable to the liquids used, and located so that they do not contaminate ground water away from the ore body. Once pregnant solution is returned to the surface, the uranium is recovered in much the same way as in any i other uranium plant (Gupta, 2003). Leaching chemistry will be covered in the Processing section in more detail. Figure 2 below is an example of the basic ISL process that is carried out at the Beverley Uranium mine in S.A.

Uranium deposit Figure 2: Beverley ISL Source: http://www.world-nuclear.org/info nuclear.org/info /Australia_Mines/emines.html#olympic

uranium can be dissolved using either an acid or alkali (carbonate) medium. Acid Leaching Chemistry In its hexavalent form, uranium goes directly into solution in the presence of an acid as shown in the following reaction: UO3 + 2 H+ UO22+ + H2O

In an alkaline medium, ferric ions cannot be maintained which is largely responsible for the very different conditions required compared with acid leaching. Carbonate leaching calls for higher temperatures and pressures to increase the oxidation reaction rate. A longer leaching time and a finer ore grind are often required. The alkali leaching process can be represented as UO2 + 0.5 O2 UO3 Na4UO2(CO3)3 + 2 NaOH

Sulphuric acid is used in most acidic leaching processes as it is a cheap strong acid. In its tetravalent form (UO2), uranium requires oxidizing to the more soluble hexavalent form. In general terms, this occurs under acid and alkaline conditions via the following equation: UO2 + 2 H+ + 0.5 O2 UO22+ + H2O

UO3 + 3 Na2CO3 + H2O

Oxidation of UO2 in an acidic medium can also occur due to the presence of ferric ions in solution. UO2 + 2 Fe3+ UO22+ + 2 Fe2+

Here, air or permanganate is typically used to provide the needed oxygen (Kirk, 2006). As the reaction results in the generation of hydroxide ions, bicarbonate is used as a buffer to control the pH. If the pH increases too much, the uranium can precipitate out of solution. The overall reaction is: UO2 + 0.5 O2 + Na2CO3 + 2 NaHCO3 H2O Leaching Processes There are several different leaching techniques such as in situ leaching, heap leaching, agitated leaching and pressure leaching (in-situ leaching is covered in a previous section). The selection of leaching process is dependent on several factors such as ore grade and tonnage. In situ leaching and heap leaching are largely restricted to ores with mineralogical characteristics that allow access to the uranium mineral over a sufficiently long period, such as highly permeable sandstone formations. Heap Leaching In heap leaching, ore is crushed to expose the uranium minerals and is then loaded onto large pads with a small gradient (for runoff) that are typically lined with plastic. The leaching solution is distributed on top of the heaps Na4UO2(CO3)3 +

To maintain the dissolution of UO2, Fe3+ ions must be replenished by the oxidation of Fe2+, which can be achieved with manganese dioxide as the oxidant and hydrogen ions via the following reaction: 2 Fe2+ + MnO2 + 4 H+ 2 Fe3+ + Mn2+ + 2 H2O

Oxidation of Fe2+ can also be achieved with the use of other oxidants such as sodium chlorate (Used at Olympic Dam, S.A.) or Caros acid (H2SO5). (Haque et al., 1987, p. 229) Once uranium is in its soluble hexavalent form (UO22+), the uranyl ion forms a stable complex with the sulphate ion. UO22+ + 3 SO42[UO2(SO4)3]4-

Alkaline Leaching Chemistry

Figure 3: Heap Leaching (Iles and Pugh, 2010, p. 5)

by sprayers or drippers. The percolated leach solution is then collected for further processing (See figure 3). Solution grade can be built up by recirculation of leach solution or by a counter current heap system (Taylor, 2010, p. 59). Heap leaching is significantly cheaper than traditional milling processes as no milling is required and no mechanical or other agitation is required (Iles, 2011). Low costs allow for lower grades of uranium deposits to

be mined.
As the minerals are leached at atmospheric temperatures, only easily recoverable material will be leached to commercially viable extents (Iles, 2011). Recoveries are generally in the 50-80% range. Heap leaching is generally only feasible for oxide ore deposits. Oxidation of sulphide deposits occur by weathering, therefore oxide deposits are found close to the earths surface. Heap leaching operations are currently used at a few sites in China, Niger and Brazil, and have been proposed at several other sites such as the Wiluna Project in Western Australia (Diehl, 2011) and at Ranger in the Northern Territory by 2013 (Sinclair and Nott, 2010, p. 7). Agitated leaching Agitated atmospheric leaching is the most common ore treatment process other than in situ leaching (Taylor, 2010, p. 40). Agitation can be provided by either pneumatic or mechanical methods. In the mechanical method of agitation, motor-driven impellers are used. Equipment is expensive and requires high maintenance costs. The size, dimensions and lining of a mechanically agitated tank can vary greatly, however should be cylindrical with a vertical axis. A widely accepted form of agitation is by the pneumatically agitated leaching vessels known as pachucas (Figure 4).

Figure 4: Simplified Diagram of a Pachuca Vessel. (Gupta and Singh, 2003, p. 94) These consist of a vertical cylindrical vessel with a central tube that is open at both ends. Compressed air is admitted into the central pipe and the pulp is then circulated up the central tube and down the annular space. Agitation intensity is low, leading to lower abrasion. The admitted air also aids oxidation. Due to mild agitation by use of the pneumatic process, it has longer reaction times in comparison to the mechanical method. A two-stage counter-current leaching method has been developed which has the advantage of being able to recover unused leaching reagents (Figure 5).

Figure 6: Pressure leaching autoclave diagram. (Taylor, 2010, p. 50) Acidic pressure leaching can be used for uranium ores which contain sulphidic minerals such as pyrite (Figure 6) It is carried out in an autoclave, with a temperature range of 130-200C (Figure 6). The sulphides present allow leaching without any reagent except for oxygen at elevated temperature and pressure. Sulphuric acid and ferric sulphate are generated in situ by the reaction of oxygen with sulphides. The reaction proceeds more rapidly at higher temperatures and with the increased solubility of oxygen at increased pressure (Merritt, 1971, p. 80-82). Some advantages of the pressure leaching process include improved extraction, decreased operation costs, and a decreased amount of impurities and free acid in the leach solution. Alkaline pressure leaching is also carried out in an autoclave. The use of increased temperature and pressure significantly increases reaction rates by up 12 Times. Temperatures and pressures for this process are approximately 110-150 C and 700 kPa respectively. Sodium carbonate can be used as the oxidant; however ammonium carbonate can also be used. Ammonium carbonate has a lower alkalinity than sodium carbonate and therefore reaction rates are lower. The advantage of using ammonium carbonate is that the ammoniumuranyl carbonate complex decomposes at 100 C. This allows direct steam stripping of the pregnant leach solution. The gaseous ammonia and carbon dioxide generated can be recovered and recycled to the leaching circuit. Although alkaline pressure leaching circuits have previously been operated in USA, Canada, France and Germany, there are no current plants in operation (Taylor, 2010, p. 53).

Figure 5: Two-stage counter-current leaching method. (Gupta and Singh, 2003, p. 95) Strong acid and oxidant are added are added in the second stage of leaching. After the second stage of leaching, solid-liquid separation is carried out. The barren solids are discarded and the dissolved uranium and unused reagents are brought to the primary stage. In the primary leaching stage, fresh solids are introduced without any extra addition of reagents. After the primary leaching stage, solid-liquid extraction is carried out and the concentrated pregnant solution is sent off for further processing. Pressure leaching Temperature is a key variable in the uranium leaching processes as it influences reaction kinetics. Increasing the temperature of the leaching operation reduces the reaction time required, thus increasing the capacity of the equipment. An increase in temperature also leads to higher acid/oxidant consumption as the chemical response of waste minerals also increases, as well as increased corrosion of equipment. Heating is usually accomplished by direct steam injection into the slurry. Additional heat also enters the system from the grinding process, as well as from the dilution of sulphuric acid.

URANIUM EXTRACTION.
Once the uranium has been leached out of the ore bearing slurry it is generally in one of two forms. If an alkali leaching process was used then the uranium is present as Na4[UO2(CO3)3], if acid leaching-[UO2(SO4)3]4. The slurry will undergo a simple solid liquid separation so that only the uranium liquor passes through to the extraction. Solvent extraction is the main method used to extract the uranium from this pregnant liquor. It has the advantage of being a continuous process as opposed to the semi-batch/batch process that the majority of resin/ion exchange processes become and has much lower capital cost than the other methods. It is highly efficient and can be fairly easily automated. Acidic Solvent Extraction There are several steps in the solvent extraction process. The stages are: extraction; scrubbing; stripping and finally precipitation. The whole purpose of this stage is to produce an aqueous solution to selectively precipitate out only the uranium. There are many methods for each of these, this section will concentrate on the main ones used by industry today. If the uranium has been leached using acid then tertiary amines are the most effective and commonly used extracting agent. The initial interaction between the complex uranium ion and the amine solution proceeds as follows2(R3NH)2SO4 + [UO2(SO4)]34(R3NH4)UO2(SO4)3+SO42After this initial extraction the pregnant organic solution then needs to be stripped. Several reagents can be used for this step including chlorides, nitrates, sulphate, carbonates, hydroxides and in some cases dilute acids. As carbonates are such good stripping agents, when using an alkali as the leaching agent you have to be careful that no carbonates are present earlier in the process, lest all the uranium gets filtered out before it reaches the precipitation tanks. Following on the example above if ammonium sulphate is used as a stripper the following reaction takes place.

(R3NH4)UO2(SO4)3+SO42- + (NH4)4UO2(SO4)3+ 2H2SO4.

2(NH4)2SO4

4R3N+

The solvent can then be recycled back to the initial extraction stage after being acidified. 2 R3N+ H2SO4 2(R3NH)2SO4. This greatly lowers the cost of reagents for the process. Below is a diagram that displays the overall process neatly.

Figure 7: Acidic Solvent Extraction (Uranium Extraction Technology pg185) Quaternary amines act as strong bases and are capable of operating at high pH levels, this makes them ideal for extracting uranium that has been leached using alkalis as shown bellow. 2(R4N)2CO3+UO2(CO3)3-4 (R4N)4UO2(CO3)3+2CO3-2 Precipitation There are several different ways to precipitate out the uranium. If you have an alkali solution then adding caustic, acidifying removing CO2 and then neutralising with a base or hydrogen reduction are all viable paths to take. Using caustic is the most economical way and the simplest (resulting in lower capital and operational costs). The caustic soda reacts with the carbonate ion and in the presence of excess caustic will go on to form sodium diurinate which precipitates out.

2Na4UO(CO3)3 + 6NaOH Na2U2O7 + 6Na2CO3 + 3H2O It is general practice to ensure an excess of NaOH to make sure that the equilibrium stays on the right and doesnt shift left.

After the uranium has been precipitated out it is dried (sometimes roasted) to dehydrate it. Then it is packed into drums for transport as yellow cake.

CONCLUSION
One method to precipitate out the Uranium from an acidic solution is to use hydrogen peroxide. UO2SO4 + H2O2 +2H2O UO42H2O +H2SO4 UO4 is the most stable hydrate form after drying. This reaction is very dependent on keeping the pH of the solution between 2.5 and 4. For this reason a base will be slowly added to neutralise the acid that forms. Several minerals can cause the extraction process great difficulty in the selectivity of Uranium. Molybdenum is extracted preferably over uranium in amine reactions. If the uranium ore has a high amount of molybdenum contained inside it then the uranium can be selectively stripped using a chloride solution, then the molybdenum can be removed from the effluent solution using a carbonate. If there is sufficiently high concentrations of iron: 5g Fe3+ per 1g Mo per liter (Merritt, 1971) then the addition of lime will precipitate out an iron-molybdenum solid that holds nearly all of the molybdenum. If the molybdenum is left in the solution it will build up in the amine solution and retard the extracting process. Chlorine can also be a problem as it can precipitate out the uranium during the leaching process where it will get dumped to tailings after the solid-liquid separation. The chlorine can come from many sources, the main places it contaminates from are process water, the use of excessive sodium chlorate additions in the oxidative leach and the recycling of process water containing amounts of chloride (Uranium Extraction Technology). Zirconium can cause a problem during the stripping section by forming a crud, this can be suppressed by the addition of phosphate. Vanadium also can be an issue, but this will precipitate out in a similar way to molybdenum. The technology used to mine and extract Uranium from its ores hasnt changed greatly in the last few decades. However new research in the ion/resin exchange areas are opening up new possibilities in terms of different types of ores that can be processed economically. The Uranium industry should be strong and steady well into the future as nuclear energy becomes a more attractive green energy source.

REFERENCES
Ashbrook, G.M.Ritcey A.W. 1979. Solvent Extraction: Principles and Applications to Process Metallurgy. New York: Elsevier Scientific Publishing Company. Assmann, S. 2012. Metallurgical Processes 252: Uranium, Curtin University . C. Dinsea , N. Baglana, C. Cossonneta, J.F. Le Dub, Z. Asfaric, J. Vicensc. 1998. Solvent Extraction of U(Vi) from Media Containing Competing Anions and Metal Cations by a Calix[6]Arene Bearing Carboxy Groups. Journal of Alloys and Compounds. Darling, P, 2003. SME mining Engineering handbook, 3 Edition. The Society for Mining, Metallurgy, and Exploration Inc. Diehl, P. 2011. Uranium Heap Leachin. http://www.wise-uranium.org/uhl.html Energy Resources of Australia Ltd. 2012. Uranium Processing at Ranger. http://www.energyres.com.au/ documents/Uranium_Processing.pdf Gilchrist, J D, 1980. Extraction Metallurgy .Great Britain. Global Info Mine. 2012. All operating Mine Sites. http://www.infomine .com/minesite/. Gupta, C. and Singh, H. 2003. Uranium resource processing: secondary resources. New York: Springer. Haque, K.E., Laliberte, J.J. and Pruneau, J. 1987. Batch and counter-current acid leaching of uranium ore. Hydrometallurgy, vol. 17. IAEA (International Atomic Energy Agency). 1993. Uranium Extraction Technology: Technical Reports Series No. 359. Vienna. Iles, M. and Pugh, L. 2010. EPBC Act Triggers, Approvals and Information Needs: A case study for the proposed heap leach facility at Ranger. AusIMM Uranium Conference 2010. Kenny, D. and Dombrose, E. 2010. Wiluna Uranium Project Process Development. AusIMM Adelaide, Toro Energy Limited Leeuwen, J, S. 2008. Nuclear Power the energy Balance. Chaam: Netherlands. www.stormsmith.nl
rd

Merritt, R. C. 1971. The Extractive Metallurgy of Uranium. Colorado: School of Mines Research Institute. Seidel, D.C. Extracting Uranium from Its Ores. IAEA BULLETIN 23, no. 2. Sinclair, G. and Nott, M. 2010. Applying Heap Leach Technology to the Treatment of Ranger Ores AusIMM International Uranium Conference. Stockton, N. 2012. Mineral Processing Methods 1, slide 3-4, Curtin University. Taylor, A. 2010. Uranium Ore Processing Short Course, Alta Metallurgical Services. World Nuclear Association. 2012. Australias Uranium Mines. http://www.world-nuclear.org/ info/Australia_ Mines/emines.html#olympic .