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Metal Extractants

CRUD: How It Forms and Techniques for Controlling It

Crud is a solid-stabilized emulsion of organic and aqueous. Otherwise known as gunk, grungies or grumos, crud is a gelatinous material found in SX plant settlers. This article reviews some of the causes of crud formation and discuss different strategies for dealing with it. Impact of Crud on a Cu SX Plant Crud has been a part of copper solvent extraction since the first commercial operations began using first-generation extractants (ketoximes and unmodified aldoximes). Crud has also been a part of other metal solvent extraction circuits such as uranium the term crud is even said to have been derived from the acronym for Canadian River Uranium Deposit. Crud is significant because even average amounts hinder a plants ability to reduce its operational costs. In cases of excessive crud formation (or poor crud management) crud can also impact Cu production. A small amount of crud in an SX plant can help break up dispersion bands at weirs, but problems can occur as the amount of crud builds up in the system. As the crud moves around the SX plant, builds up in settlers, or is removed from the plant, it increases operational costs in several ways, a few of which are discussed below. Reduced Production When crud builds up to excessive levels and begins to move between stages, it compromises PLS and organic flows and reduces Cu production. Impurity Transfer When crud passes from the extract E1 stage into the strip stage, it carries with it a significant volume of PLS, including all of the Fe, Mn, and other Crud Formation1,2 Crud formation is site-specific and varies with the mineralogy and condition of the ore in leach areas. Plants have bottom crud, which collects along the floor of settlers, and interfacial crud, which typically collects at the organic/ components in the PLS. Consequently, the plant will need to bleed these impurities out of the electrolyte, thereby incurring costs associated with maintaining Cobalt, mist suppressant, and acid concentrations, and re-circulating Cu back into the leach/SX process. Similarly, if a significant amount of crud passes from the S1 stage into the extract stage, the Cu and acid from the electrolyte can impact the performance of the extract stages. Also, if excessive crud builds up in the settler it reduces the retention time of the settlers, which leads to higher entrainment. Organic Inventory Most plants pump crud out of the settlers in order to control crud levels within those units. This necessitates a higher total organic volume to operate the SX plant, due to the additional organic inventory contained within the crud treatment system. Organic Make-Up Rate Crud passing between stages can hurt stage phase separation and phase continuity. The result may be higher organic losses due to entrainment of organic in raffinate streams. Organic is lost during the crud treatment process and must be replaced. Crud that leaves the plant through the raffinate stream also carries organic, increasing the organic entrainment losses from the plant.

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CRUD, page 2
aqueous interface at the weir in the settlers, or is found suspended within the organic phase. Bottom crud is primarily comprised of solids, containing clay, quartz, or precipitated inorganic salts (e.g., gypsum) of higher molecular weight, which quickly settles to the bottom of the settler. Interfacial crud is a stabilized emulsion of aqueous, organic, and solids, sometimes containing air. Interfacial crud is the focus of discussion in this article. Crud formation occurs during the interaction of organic and aqueous solutions with various solids in SX plant mixer/settlers. Sources of the solids are: 1) suspended, sub-micron particles in the PLS feeds, 2) precipitates generated due to the change of pH conditions in the mixers, and 3) blowing dust and dirt from around the SX plant. Analysis of different crud samples from different plants, at different points in time has shown that most include the following crystalline materials Name Formula Mica (Muscovite) (K,Na)(Al, Mg, Fe)2(Si2.1Al0.9)O10(OH)2 With rapid pH changes, precipitates can form in the SX plant aqueous solutions, creating solid particles that can cause crud formation (see silica discussion). The natural pH drop during the extraction reaction is unavoidable, but the acid-shock experienced by PLS entrained into the electrolyte can be avoided by Some SX plants have shown indications of crud generation due to the presence of decayed biological matter. Humic acid from decaying vegetation may increase crud formation, so care should be taken in the preparation and placement of leach pads and solution holding ponds. Decades of operational experience and controlled laboratory tests have shown no correlation between the formation of interfacial crud containing crystalline solids and SX reagent, mixer continuity, or mixer speed. These factors can affect how the crud presents itself in the SX plant, but have not been shown to affect the quantity of crud generated. Crud can even be generated by organic solutions containing no reagent (diluent only) . Some laboratory tests have shown lower crud formation with modified aldoximes for amorphous silica cruds, which is potentially related to the improved phase separation performance and lower entrainment of colloidal silica in the organic.
1 1 1, 2, 4

Crud Control Operational experience and lab tests have shown that little can be done to prevent the formation of crud, aside from eliminating solid particles. However, controlling the solids entering the SX plant can be very difficult due to the nature of the ore body, leach systems and PLS feed systems. Thus, although crud cant be avoided, plants have developed different techniques for controlling its effects. Limit Formation of Solids The most desirable way to deal with crud is to limit or control its formation. Because crud formation is primarily related to the presence of sub-micron sized particles in the PLS feeds, this is difficult to accomplish. Operations typically try to minimize solid particles in the PLS by increasing the time in feed ponds to allow for natural settling of the particles or by introducing flocculants into PLS ponds to help aid the flocculation and settling of the particles.

China Clay (Kaolinite) Al2Si2O5(OH)4 Jarosite KFe3(SO4)2(OH)6 Quartz crystalline SiO2

minimizing aqueous entrained in the loaded organic. Techniques used to minimize A in O entrainment include: running the mixer in aqueous continuity increasing settler retention time of the organic by increasing the depth of the organic in the settler using physical media/equipment to aid coalescence (picket fences, etc.) slowing mixer speeds to increase mixer droplet sizes controlling crud movement between stages so that it does not separate too quickly and affect the mixer emulsion separation removing any organic contamination through clay treatment to avoid build-up of large dispersion bands and flooding of the organic weir The electrolyte-related pH shock can potentially occur to a smaller degree in an extract stage if there is a significant entrainment of electrolyte entering the stage. This may be due to electrolyte entrainment in the stripped organic, or passing of crud from the strip to extract stage (carrying 40-60% electrolyte).

CRUD, page 3
Removing Crud Interfacial crud generally collects at the interface of the organic and aqueous phases at the weir in SX plant mixer/settlers. Most operations use diaphragm pumps to remove the crud directly from the settlers. Some plants have developed pumping suction systems that remove crud from multiple locations across the weir at one time, with an adjustment system to move the inlets up and down as needed. Other plants have operators use a single pump line and manually move to different parts of the settler and suction crud at different depths. Some plants remove crud from the settlers by flooding the organic off of the settler and collecting it in tanks. Clean organic is returned directly to the plant and the remaining crud is treated. Caution: this technique causes significant amounts of aqueous to pass with the crud into the next process step, along with the organic. This may cause contamination, depending on what the step is. Crud is not always found at the organic/aqueous interface. It can be dispersed throughout the organic phase, and is sometimes seen floating on top of the organic. Techniques used to help promote compaction of crud at the organic/aqueous interface include: - running the mixer in organic continuity - minimizing any air being pulled into the mixer either through high mixer agitation or through organic/aqueous feed lines - avoiding build-up of dispersion bands - increasing organic settler retention time Air Layers on Particles
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removal of the air boundary layer. At one commercial SX operation, the additive proved successful at reducing the volume of crud formation and resulted in compaction of the crud at the interface. Unfortunately, the same results were not able to be produced at other commercial SX operations where the additive was tried. Crud Treatment Once the crud is removed from the system it must be treated so that the organic can be recovered. Techniques vary at different operations, but all include some basic physical force used to separate the organic /solid/aqueous, such as a centrifuge, filter press, or agitated tank2, 3, 4. Plants have developed different techniques to help aid in the separation of the organic from the solids and aqueous within these systems. The CODELCO process3 consists of adding excess organic to a tank where the crud and organic are mixed at a low speed for an extended time under organic continuous conditions. Gibraltar Mines2 uses steam to heat up the solutions and aid in separation in a centrifuge. Other plants have added electrolyte to the crud in agitated tanks to aid in separation. There are articles4 mentioning the testing of surfactants within the crud treatment process to aid in separation, but no reference has been found past the trial stage to indicate that this approach was successful. As stated above, plants treat crud in a variety of ways. However, the key is to minimize the cost of treatment while maintaining production rates. When choosing a treatment method, be sure to consider the economics associated with stopping production to remove crud, as opposed to processing the crud while the plant is in operation. Graphs 1 and 2 show the loss of production for two plants when using different methods of processing crud. Each plant operates under different parameters. However, the two examples show that an eight-hour shut down is equivalent to running one week at 10% reduction or running three days at 15% reduction in flow. When choosing a method for crud control, it is important to take into consideration additional costs for increased bleed rates and loss of revenue from downtime.

Air that enters a mixer can come from the atmosphere above the mixer or from adjacent weirs whose solutions feed the mixer (air pulled in from vortexes at mixer or weir exits). Another source of air that can influence the behavior of crud in settlers is a boundary layer of air on the solid particles themselves. Due to different localized mineralologies, particles can have hydrophobic and hydrophilic areas. Such hydrophobic areas likely have portions that are not completely wetted by the PLS and contain a thin layer of air that is adsorbed to the surface. Limited success has been achieved by adding a special surfactant to the SX system that is attracted to these hydrophobic areas, and provides a new layer that allows complete wetting and

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Plant Parameters: Feedgrade Cu % Recovery PLS flow-rate Liters/min

$80,000 Cost to Operation $70,000 $60,000 $50,000 $40,000 $30,000

Plant A 2.13 g/l 90 8,000

Conclusions Crud results from the formation of a stable emulsion between organic, aqueous and a solid particle. The solid particle is typically a sub-micron size crystalline material that comes from leaching or blowing dust. Crud has been a part of SX operations since the use of the firstgeneration extractants ketoximes and un-modified aldoximes. Crud is even formed with organic solutions that contain only diluent, and no reagent. Crud generation is not related to the presence of modifiers, as proven by laboratory tests and commercial experience at SX plants around the world. Physical factors in the SX plant affect how the crud behaves in the circuit (and can impact the perceptions of crud generation). Controlling the presence of solids that enter the SX plant and lead to crud formation is difficult. Consequently, most plants focus on controlling the crud that accumulates in the settlers, rather than preventing its formation. Most plants pump the crud from the settlers to remove it from the system and then use some physical force to separate the organic from the aqueous and solids. It is critical to assess the economics (i.e., the effect on copper revenue) of shutting down versus treating while in operation.
References 1. Dalton, Maes, and Severs, Aspects of Crud Formation in Solvent Extraction Systems, Presented at the Annual Meeting of the Arizona Conference of AIME, Tucson, AZ, 1983. 2. Burniston, Greenshields, and Tetlow, Crud Control in Copper SX Plants, Engineering and Mining Journal, January 1992, pg. 32-35. 3. Jenkins, Whitman, Witt, and Gort Utilization of Surfactants to Separate Solids from Organics in SX, Reagents for Better Metallurgy, 1994, pg. 349-357. 4. Gonzalez, Helleon, Mungia, Operacion de Decantadora Centrifuga en Extracticion por Solventes, Avances en Metalurgia 2001, XI Congreso Internacional de Metalurgia, May 2001, pg. 271-280. 5. Tetlow, Practical Aspects of Solvent Extraction, ACORGA Beijing Seminar, December 2001.

Downtime Assessment versus Crud Control Processing/ Plant A

$Loss of Production for 7 days Added Bleed cost

Cost to Operation

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$40,000
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(Price of copper: US$1.40 /lb.)

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Cost to Operation

% Recovery $60,000
$40,000 $30,000

$Loss of Production for 7 days

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90

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$50,000 Aqueous flowrate lts./min

9750

Cost to Operation

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$50,000

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$20,000 $80,000 $10,000 $70,000 $0 $60,000

Downtime Assessment versus Crud Control Processing/ Plant B

$Loss of Production for 7 days Added Bleed cost

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Feed grade Cu
$70,000

10

15

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20

Added Bleed cost

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35

$80,000

1.85 gpl

Downtime Assessment versus Crud Plant Parameters: Plant B Control Processing/

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Plant B

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$20,000 $80,000 $10,000 $70,000 $0 $60,000

Downtime Assessment versus Crud Control Processing/ Plant A

$Loss of Production for 7 days Added Bleed cost

(Price of copper used: US$1.40/Lb.)

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6/21/06

MCT-1102

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