Carbon Stripping

CARBON STRIPPING THE PRACTICAL ALTERNATIVES

Presented at the International Gold Expo September 7, 1989 Reno. Nevada John L. Fast, P.E. Consulting Process Engineer Denver Mineral Engineers, Inc. Many methods are used commercially for recovering gold and silver from loaded activated carbon. The major processes include: (1) Atmospheric Zadra Stripping (2) Pressurized Zadra Stripping (3) Anglo American Research Laboratory (AARL) Method (4) Alcohol Stripping (5) Micron Elution Procedure Each process is briefly described. Variations to and combinations of the basic methods are also highlighted. The advantages and disadvantages of each procedure are discussed. I. INTRODUCTION Activated carbon has long been known to exhibit a strong affinity for the extraction of gold from cyanide solutions. It was not, however, until methods for chemically desorbing gold from loaded carbon were developed, that the process came into widespread use for gold recovery from ore. These procedures allowed the carbon to be recycled for further gold recovery.

Today, many options are available to the recovery plant designer and operator for the stripping of gold from carbon. Each method has advantages and disadvantages, which should be evaluated when deciding which process to use. II. ATMOSPHERIC ZADRA STRIPPING Atmospheric pressure Zadra stripping was the first commercially successful process developed for stripping gold from carbon. The process was developed by J. B. Zadra, and others, at the U.S. Bureau of Mines (USBM) in the early 1950s. The results of their research were first applied at Golden Cycle Gold Corporations Carlton Mill at Victor, Colorado in 1951. The results of Zadras work were published by the USBM as RI #4843 (1). This publication is still in print and is actually the foundation for the other stripping processes. The process is still widely used today because of its simplicity. The Zadra process consists of circulating a 1% sodium hydroxide and 0.1% sodium cyanide water based solution upflow through a stationary bed of loaded carbon at a flow rate of about 2 bed volumes per hour at about 200 deg-F. Gold that was previously adsorbed on the carbon as a sodium or calcium/gold cyanide ion pair (2) is desorbed from the carbon by a reversal of the adsorption kinetics. Gold is recovered from the pregnant strip solution by electrowinning onto steel wool. The gold depleted solution is then reheated and recycled to the carbon bed for reuse (see Figure 1). The process generally takes about 48 to 72 hours. Typically the gold content of carbon is reduced from 150 oz Au/ton of carbon to less than 3 oz. Au/ton of carbon. The Zadra process is characterized by simplicity of system design and operation. Mild steel equipment is normally used. Manual control is the standard. Fluctuations in flow and temperatures can reduce stripping efficiency but the only adverse effect is an extension of the required stripping cycle time. After the desorption vessel has been filled with loaded carbon and solution flow is started, the only operator attention required is periodic system checks typical of any process plant operation.

The main disadvantage of the original Zadra process is its low rate of desorption. It is much slower than the alternatives. This necessitates larger carbon inventories and larger equipment than other faster processes. Stripping temperature is the most significant operating parameter so solutions are kept as close to boiling temperature as is practical. Since many mines are at high elevations, with resultant low boiling points, the reduction in stripping rate can be significant when compared with operations at near sea level altitudes. Buildup of miscellaneous ions in solution after continued recycling also reduces stripping efficiency. To alleviate this problem, most operations routinely bleed a

fraction of their strip liquor inventory and replenish with fresh solution. The efficiency of the electrowinning cells is also significant to stripping efficiency. High levels of gold in recycled eluant result in a reduction in stripping rate as illustrated typically by Figure 2(3). III. PRESSURE ZADRA STRIPPING Continued research at the USBM revealed that the Zadra process stripping rate could be increased greatly by stripping at higher temperatures (4). A comparison of the increase in stripping rate with temperature is shown in Figure 3. To operate at higher temperatures, the process must operate at pressures higher than the vapor pressure of the solution. High pressure operation is accomplished by means of a high pressure solution pump and a stripping column pressure control regulator. In practice, a solution containing about 1% sodium hydroxide and 0.1% sodium cyanide at about 280 deg-F and 65 PSIG, is circulated through a pressure vessel filled with loaded carbon at a flow rate of 2.0 bed volumes per hour. The time required for pressure stripping is generally from 10 to 14 hours. Barren strip solution is typically pumped through a heat recovery heat exchanger and a solution heater. The solution then flows up through the bed of carbon and overflows near

the top of the stripping vessel. The solution is cooled by exchanging heat with barren solution and flows through a back pressure control valve, to the pregnant solution holding tank. Pregnant solution is pumped from the pregnant solution tank through electrowinning cells where gold is recovered by electrolysis. Barren solution is then returned to the barren solution tank for recycle (see Figure 4). High temperature limits are generally constrained by pressure and temperature

limitations of system components, such as vessel design pressures and gasket temperature limits. USBM research indicated that increases in stripping efficiency could be achieved up to 356 deg-F. Above 356 deg-F cyanide was decomposed and metallic gold precipitated in the carbon. Plant practice generally indicates that about 300 deg-F is the upper limit for maximum stripping efficiency. Pressure stripping columns are normally sized with a height to diameter ratio of about 4 to 1. Internal solution distributors and collectors are used to provide even flow of solution throughout the carbon bed. The majority of pressure strip vessels are constructed from stainless steel, but many carbon steel vessels are providing satisfactory service. Solution flow rate has little effect on stripping efficiency in the range of 1 to 4 bed volumes per hour. Low solution flow rates produce slightly higher efficiencies in most cases, but the increase is not significant. Stripping efficiency decreases as flow rates are increased above 3 to 4 bed volumes per hour. The design solution flow rate is generally based on a compromise between reduced elution time and increased equipment costs at higher flow rates. Most columns are operated with upflow of solution, but some plants have selected to elute by downflow. The advantage to downflow is reduced potential for binding of flow distribution screens by tramp material in the carbon. Upflow operation means that the carbon bed is always flooded, and insures that the carbon is continually contacted by strip solution.

The extent of instrumentation is generally determined by operator preference. Automatic solution temperature control and column back pressure control are the minimum automation required. Solution bleeding is required to prevent the buildup of contaminants, which reduce stripping efficiency. The amount of solution bleed required varies from about 1/3 of the eluant volume per cycle, to as low as the residual eluant on the carbon during carbon transfer. Control of the amount of solution purged from the system is done either on a routine scheduled basis or by monitoring stripping efficiency and bleeding as efficiency drops. OPERATING SCHEDULE: The following is a typical operating schedule for a Pressure Zadra stripping cycle:

Load Column Elution Carbon Cooling Unload Column

SOLUTION Transfer Water 0.1% NaCN, 1% NaOH Fresh Water Transfer Water TOTAL

TIME 90 minutes 480 minutes 60 minutes 30 minutes 11 hours

IV. AARL STRIPPING The Anglo-American Research Laboratories (AARL) stripping procedure (5) was first used on a large scale in 1980 at the President Brand Gold Mine in South Africa. Since that time, its application has become standard practice in South Africa and Australia. The process involves a series of procedures generally starting with an acid wash followed by a water wash to remove residual acid. The carbon is then soaked for about 30 minutes in a solution containing about 3% sodium cyanide and 1% sodium hydroxide. High quality fresh water at about 230 deg-F is then pumped through the pressurized stripping

vessel to produce the pregnant eluant. Gold is recovered from the pregnant eluant by electrowinning and the barren eluant is discarded (See Figure 3). It is interesting to note that the Zadra stripping procedures researched by the USBM, originally envisioned presoaking carbon with a caustic cyanide solution followed by elution with deionized water. This idea was discarded in practice, in favor of the simpler one step caustic cyanide elution. The main advantage

of the AARL process is the ability to strip a batch of carbon to low gold residuals in an 8 hour shift. This offers the potential of either designing for multiple stripping cycles each day and reducing equipment sizes in new plant design, or increasing daily capacity in existing mills by stripping on additional shifts each day. Disadvantages of the AARL process include the requirement for high quality water, high water consumption, the potential for mixing acid with cyanide, and the necessity for automated controls. ACID WASHING With the AARL process, elution is normally proceeded by acid washing the carbon. Acid washing is used with all of the other stripping systems, but it is mentioned specifically with the AARL procedure, because AARL systems generally use the stripping vessel to acid wash and acid washing is, therefore, controlled as part of the stripping sequence. Acid washing has been shown to typically increase the efficiency of AARL stripping. Hydrochloric acid is always used in AARL systems with concentrations generally around 3% by volume. Acid washing is currently being done both in a separate vessel from the stripping column and in the elution vessel. Factors favoring acid washing in the elution vessel include: (1) eliminating a carbon transfer which reduces gold losses from fine carbon breakage of loaded carbon, (2) conservation of heat if hot acid washing is employed and (3) reduction in stripping cycle time by eliminating a carbon transfer. Factors favoring installation of a separate acid wash vessel include: (1) less potential for mixing acid

and. cyanide in the event of operator error or equipment malfunction, and (2) less rigorous requirements for materials of construction in the stripping circuit since acid proof equipment is not required. Following acid washing, the carbon is rinsed with fresh water to prevent acid and chlorides from entering the strip circuit. PRESOAK The presoak step is started by preheating the carbon with hot water. This is followed by soaking the carbon bed with hot (90 deg-C) 3 WT% NACN/1 WT% NAOH solution for about 30 minutes. Reduced elution efficiency is experienced if soak solutions concentration are less than 3% NACN but elution rates remain relatively constant with soak solution concentrations above 3% NACN. Changes in the duration of soaking time, for most carbons, has little effect on stripping efficiency. ELUTION Elution is generally performed using about 6 bed volumes of good quality water at a rate of about 2 bed volumes/hour. The quality of water used has a substantial effect on stripping efficiency with the AARL procedure. The implementation of a hot acid wash step has been shown to reduce water quality requirements to a certain degree. The stripping efficiency is virtually independent of eluant water flow rate in the range of 1 to 5 bed volumes per hour. Selection of design and operating flows is made on the basis of equipment costs and time constraints Eluant water temperature has a very significant effect on stripping efficiency.

Operation at 236 deg-F requires operating pressures of 10 to 15 PSIG to prevent flashing steam in the system. Operating temperature limits of 236 deg-F are widely specified

because of temperature limitations of the butyl rubber lining material utilized to line the strip vessel. Higher temperatures also accelerate the decomposition of cyanide. The last bed volume of eluant water is generally introduced at ambient temperature to cool the carbon for transfer out of the column. PROCESS CONTROL Due to the timed cyclical nature of the procedure, a programmable logic controller (PLC), automatic pump starting and automatic valves are generally used to time and sequence the system. Carbon is loaded and transferred manually, but the sequencing of valves and pumps during the strip cycle is controlled by the PLC. ELECTROWINNING Electrowinning of gold from the pregnant solution is done on a batch basis. The solution pH is increased to 12 by the addition of sodium hydroxide and electrowinning is started. Solution is circulated through electrowinning and back to the pregnant solution tank until acceptable barren levels are achieved. The solution is then discarded. OPERATING SCHEDULE: The following is a typical operating schedule for an AARL stripping cycle:

Load column Acid Wash Water Rinse Pre Heat Pre Soak Elution Cooling Carbon Transfer

SOLUTION Carbon 3% HCl Potable Water Potable Water 3%NaCN,1%NaOH Potable Water Potable Water Transfer Water TOTAL

TIME 90 minutes 20 minutes 90 minutes 30 minutes 30 minutes 180 minutes 30 minutes 30 minutes 7 hours 50 minutes

V. ALCOHOL STRIPPING Further research at the USBM showed that the atmospheric pressure Zadra stripping cycle can be made to operate much faster by the addition of alcohol to the strip solution (6). Figure 6 shows the dramatic laboratory results obtained by adding 20% ethyl alcohol to a Zadra solution. Several different alcohols were investigated. Methanol, ethanol, and Isopropanol were all found to increase the gold desorption rate. Ethanol and methanol were found to perform almost equally, but were substantially better that Isopropanol. In plant operation alcohol stripping normally requires about 12 to 16 hours to strip carbon to less than 3 oz. Au per ton of carbon. This is achieved at flow rates in the range of 2 bed volumes per hour operating in series flow with electrowinning cells. The main drawback to the alcohol stripping process is the potential for fires. Fires have been reported at several alcohol stripping operations. The electrowinning section is especially vulnerable to fires because of the potential for sparks. Ethanol is generally used rather than methanol. This is due to ethanols greatly lower health risks from exposure to vapors. There are, however, isolated examples of operations using methanol. Ethylene or propylene glycol are frequently used, rather than alcohol, to increase the speed of atmospheric pressure Zadra stripping (7). Typical strip times with glycol are 24 to 36 hours. Glycols are generally used, rather than alcohols, because they are virtually

uninflammable. The disadvantages of glycols are their inferior strip rate increase and higher costs. A typical glycol stripping solution contains 20 to 25 wt% ethylene or propylene glycol, and 2 wt% sodium hydroxide. Sodium cyanide is sometimes added to the solution but it is frequently unnecessary. The solution is heated to about 190 deg-F and pumped through the carbon stripping vessel at a flow rate of about 2 Bed Volumes per hour. Gold and silver

values are recovered from the pregnant solution by electrowinning and the barren solution is reheated and recycled through the stripping vessel. Glycol consumption is typically in the range of 20 to 40 gallons, per ton of carbon stripped. VI. MICRON STRIPPING The most recently developed stripping procedure being used commercially was developed at Micron Research, in Australia (8). The Micron method involves pretreatment of loaded carbon, with a caustic cyanide solution followed by elution with an alcohol mixture. The Micron elution procedure takes advantage of the enhanced stripping rate achieved with alcohol, but confines the alcohol to the closed stripping unit. Fire dangers are reduced quite substantially, as the pregnant eluant that is subsequently processed for gold recovery does not contain alcohol. The elution unit is configured like a packed bed distillation tower with a heater on the base of the column, an overhead condenser, a reflux pump and the loaded carbon functioning as the tower packing. Loaded carbon is first presoaked with sodium cyanide/sodium hydroxide solution. The presoak solution is drained from the carbon bed and an alcohol solution is added to the vessel. The unit is then switched to the batch distillation mode. Within a few hours, the alcohol is concentrated in the overhead condenser tank. The tower bottoms solution is then free of alcohol and loaded with gold solution which has been stripped by the refluxing action in the column. The Micron process consists of the following operations (See Figure 7): (1) Presoak The carbon is first soaked in a solution of 1 to 2 % sodium hydroxide and 5 to 10 % sodium cyanide at ambient temperature. Carbons with particularly high concentrations of

gold, silver, or copper may require solutions containing up to 20% sodium cyanide. The solution is then drained from the carbon until free of excess moisture. (2) Desorption About 0.5 Bed Volume of alcohol is added after the carbon bed has drained. Methyl alcohol is used in the majority of applications, but ethanol is occasionally applied. Acetonitrile may be substituted for the alcohol, but its higher cost generally discourages its use. Heat is then applied to the base of the desorption vessel. Organic vapors rise through the carbon bed and are condensed in the overhead condenser. The condensate is pumped back to the top of the carbon bed and is sprayed on the carbon. The downflowingcondensate washes the gold values from the carbon particles into the boiler section below. (3) Alcohol Recovery When desorption is completed, as indicated by gold solution concentration reaching a constant level in the column boiler, alcohol recovery commences. The condensate recycle spray is stopped and the alcohol is allowed to boil out of the pregnant solution. The boiling is terminated when the temperature in the boiler rises to the boiling point of the water solution. The pregnant liquor is then drained from the desorption vessel. The carbon is then steam stripped to recover residual alcohol. The Micron process produces a very concentrated eluant free of alcohol, with gold and silver values two or three times higher than those in the loaded carbon. This is in direct contrast with the Zadra and AARL procedures, which produce eluant concentrations one or two orders of magnitude lower. The high solution grades make recovery methods such as chemical precipitation and aluminum foil electro-deposition very attractive. The micron eluted carbon also appears to have a somewhat higher level of activity than carbon eluted by other methods. This may reduce the need to reactivate carbon as frequently at some operations.

The entire stripping cycle takes about 8 hours. Over 20 licenses for this process have been issued, but none are in the United States. VII. VARIATIONS There are numerous variations to, and combinations of, the basic processes as illustrated by the following: (1) Glycol or alcohol are sometimes added to pressure strip or AARL strip operations to increase stripping rates. (2) A caustic/cyanide presoak may be used in a Zadra system. (3) A hot water wash is sometimes used at the end of a pressurized Zadra strip to gain some of the advantage of the water elution used in AARL stripping. (4) In situations where large amounts of copper load onto carbon with the gold and silver, a two stage strip may be beneficial. Copper may often be selectively eluted with a cold caustic/cyanide solution. This is then followed by one of the standard stripping methods.

(5) Carbon is normally stripped batch wise, but moving bed continuous elution systems have occasionally been used with both Zadra and AARL

procedures. (6) Electrowinning may be done under pressure to avoid repressuring solution on each pass through the carbon. (7) Zinc precipitation may be substituted for electrowinning. VIII. CONCLUSIONS & RECOMMENDATIONS Each new project should be evaluated individually to determine the best procedure for the particular ore and site specific circumstances.

In general atmospheric pressure Zadra stripping is favored for smaller projects where the increased size of equipment can be justified by a simplification of the system. It may also be preferred for areas where extreme ease of maintenance and operability are a priority due to a lack of skilled manpower. The pressurized Zadra system has recently been the preferred process in the United States for most medium to large sized projects. This is due to its significant cost advantage over atmospheric pressure Zadra systems. The AARL process is the preferred process in Australia and South Africa, except where water balance or water quality problems exist. Several recent United States projects have also elected to use AARL systems. The AARL process should definitely be considered for large projects with sophisticated operators. Alcohol stripping has generally fallen out of favor due to the flammability concerns. Glycol stripping frequently is used to increase capacity in existing Zadra operations, but economics usually favor conversion to pressure stripping if continuing operation is planned.