A GUIDE TO SOLVENT EXTRACTION OPERATION AND CONTROL {> February, 1975 HOLMES & NARVER, INC. ; A Resource Sciences company Aavanced Technology/Engmearing/Constwuction/Management/Maintenance & Operations 400 EAST ORANGETHORPE: AVENUE ANAHEIM, CALIFORNIA 92801A GUIDE TO SOLVENT EXTRACTION Operation And Control AE iba ode Summary of Key Elements Introduction and Process Description u Behavior Of The Mixer mr The Settler Inlet Distributor v The Selfle¥ Overflow Weira v Aqueous Feeds Flow Control vii Recycle Flow conn vu Organic Flow Control And Make-Up VII Continuous Phase Control cod Provisions For Gunk Removaloe Ne a |__4,_After the-+ “ater SUMMARY OF KEY ELEMENTS. ihe 3 Do not interchange extraction and stripping pumping mixers unless speeds and diameters.are identical (Sect. I). fabsaes Do not increase the bottom clearance of pumping mixers beyond one eighth of their diameter (Seet.. II). ©) wy Wh anil a Wade: ved Do not make any alterations to the design of settler inlet distributor (Sect. Mies iia - aiepdpitpen 8S : \Sttler-overflow_weirs-have-been-initially_levelled_and_adjusted they should not be changed during plant ope ration (Sect. IV). Limit any resetting of feed flow controllers to 3% of the flow once every ten,minutes (Sect. V).. °° When removing "gunk" with a skimmer pipe, do not pump at a flow higher than that specified (Sect. IX). ce gta 2 GAD ‘ vik ies ipo Halse tI_INTRODUCTION AND PROCESS DESCRIPTION Introduction Although the solvent extraction plant appears to be simple to understand, its design and operation depend on familiar hydraulic principles whose applicability is not immediately obvious. The purpose of this manual is to review the process and equipment in detail to permit full understanding by a novice, as well as providing a handy reference for more experienced operators. Process Description The purpose of a solvent extraction (SX) plant is to convert a weak and impure solution of a valuable metal, such as uranium or copper, into a concentrated and pure solution. (It is easy to extract the pure product from a pure, concentrated solution by further processing.) The principle on which SX works is dependent on finding a chemical reagent with five special properties. 1. It must be readily soluble in an organic carrier like kerosene It must be insoluble in water solutions. It must not chemically combine with any of the impurities in the weak solution. It must readily combine with the dissolved metal under certain conditions. 5. Under other conditions this reaction is reversed; that is, the chemical must disassociate from the metal. Properties 3 and 4 are together referred to as the selectivity of the chemical, its ability to combine with one ingredient of the weak solution, the desired metal, while rejecting combination with all other ingredients. This selectivity is a most difficult property to find, which is why reagents to date are limited to uranium, copper, nickel, and cobalt among all the commercially significant metals.If a solution of the reagent in kerosene is mixed thoroughly with a weak, impure water solution (called leach liquor), the metal combines. with the reagent, thus effectively passing from the Jeach liquor to the kerosene- reagent mix. If the total mixture then flows to a settler, it will separate into a layer of kerosene-reagent (called the organic phase) floating on the leach liquor (called the aqueous phase). The organic, now containing the metal, can be remixed with clean aqueous solution at sorne other condition, such-as adjusted acidity, to reverse the reaction and release the metal to this new aqueous phase, This restores the reagent to its original condition so that the organic can once again be contacted with leach liquor, to extract more metal. ‘The-portion-of the SX plant where metal is extracted from the leach liquor C into the organic is called the extraction section; the portion where the organic ia stripped of the metal is called the stripping section. Dia- gramatically, what goes on can be shown as: Exrecacrrod ace yan OncaNse S| ne Onecare STRIPPING : Rice Srace | ol keay Srese eee LE re Let vs now discuss this process more realistically in terms of a real plant producing copper. If copper oxide ores are washed with a weak solution $f sulfuric acid the copper will be dissolved, or leached out., Unfortunately other metale such as iron, zinc, cobalt and many others will also be dissolved. The resulting leach liquor will then contain say, one gram per liter (gpl) of copper as dissolved copper sulfate, and lesser quantities of the other metals, 1.0 gpl is only 0.1% by weight, and it is desirable to concentrate and purify it. LIX-64N is a proprietary reagent, produced by General Mills which can theoretically absorb up to 0.25 gpl of copper per 1% of concentration in one Titer of organic. It can be stripped nearly free of copper by a solution of + 150 gpl of sulfuric acid (H2S04) even if this solution already contains 25 Gr 30 gpl of copper. Thus if a 5% LIX-64N in kerosene is used, it has the capability of absorbing nearly all of the copper in the leach liquorOne problem is that the more copper in the organic, the more difficult is the further absorbtion of copper. Also the less copper in the aqueous, the harder it is to abnorb thie last fraction. This difficulty is overcome by replacing the single mixing-settling stage previously described with a multiplicity of stages with the leach liquor flowing from, Stage #1 to #2 to #3 but the organic flows from #3 to ¥2 to #1, or counter currently, thus: ANT RAC On 5 AEE » SZrev0e eS J ete! Lil teteeel Letaed Le! ret Uc? ed Mie! het EN bet ak Ce Sco ek - ' iO vee OREAMIC This means that the leach liquor in stage 3 which contains the least amount of copper is being extracted with the most powerfully reacting organic, because it also contains the least copper. Similarly, the stripping section is also multistage, usually containing two stages. The rich organic from extraction stage #1 flows to strip stage #] and then to #2 while the strong acid solution flows first to strip #2 and then to #1 again counter currently. In discussing extraction above we stated that one liter of 5% LIX-64N was capable of extracting the copper from one liter of leach liquor. This implies that the ratio of organic to aqueous flows was 1:1, or the 0/A ratio, as it is called, is 1, Thus for a given leach liquor flow the organic flow in extraction is fixed, which fixes it of course for the whole plant, which means also for stripping. : mye Mixers and settlers operate well at 0/A' ratios of 1, but for the strip section, if the strong acid solution has the same flow aa the organic it will only have the same gain in copper concentration as the Joss in copper in the leach liguor, namely 1 gpl. In other words the enrichment of this solution might only be from 30 gpl to 31 gpl which is ueually uneconomic from the view- point of further operations downstream, A 20 gpl increase to 50 gpl may be preferred, corresponding to a reduction in flow of the acid solution to only 1/20 of that of the organic, or an overall atrip 0/A ratio of 20.of the other, is maintaining an plant is thus: seacy J Ligerr 7 The effective mixing of the two ‘streams, one of which is 20 times the size very difficult. The problem may be solved by adding a recycle line from the aqueous outlet of each stage back to the mixer inlet of that stage. 'If the recycle flow is established at 19 times the normal aqueous flow the O/A ratio is reduced to ] within the stage, while still overall O/A of 20, The schematic diagram of the whole XTRA CTYON | Racecar’ Arew acura 7 al Laan Sremewe | the terminology a Rien Here Sore “SCereretr Lewes used. glee Bae Weegee) 2 [Purr TOMER Oncante sce oncaue Troven oncanse ee. Diserestan BIND Aourans Cnvsariow Oncanre Laan here Sot war Each of the five "boxes" above represents a stage of extraction or stripping. The lines interconnecting the boxes represent piping, and each box is really composed of a mix tank, mechanically driven pumping mixer, and a settler. Although physical configurations vary, the diagram below represents a vertical section through a conventional stage, and provides a reference to Aeuaces HEIR Dra pi Dea wore Boor |I BEHAVIOR OF THE MIXER i ‘The mixer consists of a mix tank and a pumping mixer mounted in it. Unlike the usual paddle blade type of stirrer, located in the center of the tank, the SX mixer is a solid disc, with radial vanes mounted on its under side, and located very close to the bottom of the mix tank directly over the inlet. It thus resembles a centrifugal pump, and functions in exactly the same manner. While it mixes the organic and aqueous which passes through it, it also produces a positive head. This is essential for proper operation. There are three reasons why pumping is required: onGANse 6 Siitiee PINT URE ovcanie Agueous 5 1, Inthe diagram, Hyp is the height of the mixture in the mix tank and inlet boot. Ho is the height of the organic phase in the drawoff trough and piping from the adjacent settler, Hois always a little Jess than Hm because of small losses of liquid level as the liquid flows through the settler. 2. Also and more important, the specific gravity of the organic is less than that of the mixture. In terms of pressure head of water developed by Ho, the head is Hjjz0 = Ho (S.G.)o-while the head corresponding to the mix is Hy30 = Hm (SG)m 3, Finally if flow is to take place, frictional losses in the piping must be overcome. Therefore the pumping head, which must be developed by the mixer is Hpymping = Um (8-G-Im - Hg (S-G)o + 4Pipe friction Pumping head developed increases with both diameter of the impeller and speed of the impeller. Since (SG)m in the stripping stages ie usually different from (higher than) the extraction stages, the diameter and/orspeed may be slightly different. Do not interchange extraction and stripping mixers unless speeds and diameters are the same. Shims may be provided to adjust the height of the mixer relative to the mix tank, Up toa clearance of about D/8 little difference in performance is observed, although theoretical considerations suggest that organic losses are minimized by making the clearance as large as possible. Beyond D/8, however, a serious decrease in pumping head may result. Do not increase the clearance beyond D/8. (D is the impeller diameter.) The mix tank itself provides residence time for the transfer of metal between the organic and ‘aqueous fluids. ‘One characteristic of mixing two immiscible (mutually insoluble) liguids is'that the organic forms droplets suspended in the aqueous, or vice versa, but almost never both ways at once. The phase formirig the droplets is called the dispersed phase. The other is called the continuous phase. The viscosity of the continuous phase slows the separation of the droplets of the dispersed phase in the settler. As the aqueous phase is usually less viscous than the organic phase, faster settling may result if the aqueous phase is made continuous. On the other hand, solvent losses are less when mixers operate organic continuous. Thus in any plant there is a preferred mode of operating aqueous continuous or organic continuous, which may differ from one stage to the next. A description of the instrumentation, provided to determine which phase is continuous, is included in section VIII. Also included there is the method of changing the phase which is continuous should,this be necessary.UI THE SETTLER INLET DISTRIBUTOR Because the settler vessel is relatively wide compared with the mix tank outlet a means of distributing the flow across the full width is required, to ensure that the settler performs effectively. The distributor is a partition installed across the settler, with narrow horizontal or vertical slots. A second partition a few inches downstream of the first, has wider slots, staggered with respect to the slots in the first baffle. | —Because_of the fluid resistance to_passing through-the-slots—in-the first. baffle, the incoming mixture tends to divide itself uniformly among the narrow slots and along their length. \ The second baffle slows down the jet effect of the first baffle slots. Its slots are wider to avoid producing a new jet action. Any damage or plugging of the upstream baffle can seriously affect the performance of the settler. Similarly, repair or replacement should adhere exactly to the original design.IV THE SETTLER OVERFLOW WEIRS In the settler the incoming mixture distributed uniformly over the width, flows slowly down the length, separating into an upper organic layer and a lower aqueous layer. A narrow layer of mixed material, called the dispersion band, separates the two clear liquid layers. At the downstream end the organic layer overflows the lip of the organic drawoff trough, which runs the full width of the settler. This lip is called the organic weir. The organic weir is usually not adjustable in any way. The settler when initially installed in the plant is adjusted to ensure that this weir is dead tevel-—This assures that the 1low Over if if Uniform across the seltler width. This uniform withdrawal of liquid is as important to good settler operation as the inlet distributor producing uniform feed to the settler. In some plants the organic weir is adjustable. This facilitates leveling of the weir on initial installation of the settler and re-leveling later on if differential settlement of the foundation should occur. The only function of the adjustment is to permit this leveling. The aqueous phase flows under the organic drawoff trough and then over the aqueous weir, The latter is adjustable in height over at least several inches In addition to permitting Jeveling of the weir, this adjustment in height establishes the location of the interface in the settler, as explained below once’ DISPEL Kee v pica ooae Learnt Bann a4 Agueovs In the diagram the organic and aqueous phases are shown overflowing their respective weirs and a line has been drawn representing ihe interface elevation if there were no dispersion band. We've labelled this line the reference elevation, Its true that liquid seeks its own level, but when two different liquids, of different densities are present, the levels may be different. Here we can say that the pressure along the reference elevation is constant, because below it the liquid is aqueous upstream of both weirs. But this pressure upstream of the organic weir is produced by an organic depth Dorg, and upstream of the aqueous weir this pressure is produced by an aqueousBut a pressure produced by a given depth of liquid is the depth multiplied by the density of the liquid, and since the pressure along the reference line is constant, then ' pressure-= Dorg (density) org and pressure = Daq (densitylaq or Dorg (densjtylorg = Daq (density)aq (density)org ee = or _Daq= Dors_igensityiog Since specific gravity is the density divided by the density of water, the ratio of densities shown above can be replaced with the ratios of the respective specific gravities (5. Gor, ag Assume that we wish to hold the interface at 9" below the liquid surface in the interface. The organic liquid has a specific gravity of 0.82 and the aqueous in extraction, a specific gravity of 1.01 then Dag = (se ) =7.3" or Dag = Dorg Lor ‘This says that if the aqueous weir is adjusted to (9"-7. 3"=) 1.7" below the organic weir, the 9" interface will be maintained. Suppose the organic flow ie increased by 10% (see Section VII). If the surface starts to rise, more organic overflows its weir until the organic outlet flow exactly corresponds to its new inlet flow. This surface rise will typically be about 0.1!) As no change has been made in the aqueous flow its level over its weir is unchanged. The difference in elevation of the overflow liquid surfaces is now 1.7" represented by the weir height difference, plus the 0.1" increase in organic liquid height, or Dorg = 1-8 4Daq Since Dorg (SGlorg = Pag (SSlag Then (1.8 + Daqi (SGlorg = Dag (SGaq or, substituting in the (SG) values, 1.476 4-82 Dag = 1-01 Dag LW?C solving for Dag it proves to be 7.77" then Dorg = 7.77 41.4" = 9.17" The location of the interface has thus moved down 0,17"-0.1" = 0.07" from its initial position. Thus it may be seen that the difference in weir elevations essentially establishes the interface level as constant regardless of flow variation, and has no effect on the flow rate. Note that the electrolyte in the strip section has a spécific gravity more 82 17 Dag = "x = 6.3" Therefore here the aqueous weir must be (9-6.3=) 2.7" below the organic weir. Once the weirs have been adjusted to their correct height and levelled they should not be changed during plant operation. Wea |——typicatty 117; thus-for-the-strip-stages =V AQUEOUS FEEDS FLOW CONTROL The leach liquor to the plant may flow through one train of extraction stages or it may be split among two or more parallel trains. In any case for each train,it flows through a flow measuring device connected to a throttling valve by means of a flow controller. The latter permits setting a desired flow rate. The actual flow fate is continuously measured and the valve is automatically adjusted to maintain the measured rate at the desired rate (set point). If the flow is controlled to extraction stage #1, then in time the aqueous overflow from stage #1 must be exactly the same as the incoming flow, | l l ] ] ] the-Hiquid-s-incompressible-—Fhusy p-the-Frow-to-stageH—fises——! it also to stage #2 and to stage #3. The same principle applies on stripping. The lean electrolyte to each train is on flow control. As flow to strip stage #2 is fixed, the same electrolyte flowrate also applies to strip stage #1. Recycle flow of electrolyte, within the stage, cannot affect the requirement that the liquid flow to the stage is exactly equalled by the flow from the stage. To avoid plant upset, if flows are to be changed, it is desirable to limit h change to a few percent of the flow at a time, with ten minutes or 60 between successive changes. Monitor 0/A ratio to avoid phase inversion, as described in Section Vill.VI RECYCLE FLOW CONTROL In the strip section, the flow rate of lean electrolyte to the stages is usually only some 5% of the organic flow rate. This results in an enrichment of the small stream, in terms of concentration change, of some 20 times as much as the depletion of the large stream. For example, if the leach liquor to the extraction train contains 1 gpl of copper and the organic flow/aqueous flow ratio is 1, the organic picks up 1 gpl as it is contacted with the leach liquor, When the organic flows to the strip stages, if the lean electrolyte flow is only 5% of the organic flow, the Jean electrolyte will have its concentration enriched by 20 gpl of copper. This low flow high concentration stream is more economical to process Tarther than would be a high low low concentration stream, reducing the costs of heat exchangers,pumps and piping. However, mixing of organic and aqueous is more effective if they are closer to being similar volumes. For this reason the design usually incorporates recycle piping which permits excess aqueous flow to be recovered from the aqueous trough and returned to the mix tank inlet. Basic control of recycle flow is by a butterfly valve in the recycle line which in the fully open position provides’an excessive recycle flow, and in the closed position reduces the flow to zero. A flow meter is not provided as little adjustment is required once the valve has been mitially set. Instead the valve is adjusted to produce the desired O/A ratio in the mix tank, The latter is measured by the use of a glass or transparent plastic tube called dip tube, which is inserted by hand down into the mix tank. The open top end of the tube is then closed by finger, thumb, or cork, and the tube filled with mixture, is withdrawn and the mix allowed to separate in the tube, The height of the resulting organic Jayer vs. the height of the aqueous layer is equal to the O/A ratio in the mix tank. If the ratio is not that desired, the valve is adjusted slightly, and after sufficient delay to permit the system to come to equilibrium the dip tube test is repeated. Some difficulty may arise on the original start up. Organic and aqueous, from different sources both flow to each mixer inlet; at their junction point they are at the same pressure. But consider strip stage #2. The organic is flowing by gravity from the organic trough in strip scttler #1. ‘The aqueous is flowing from two sources (1) 5% on flow control of lean electrolyte and (2) 95% from the aqueous trough as recycle.If the organic level in #1 trough is at ite normal point, the proper aqueous level in the #2 trough is several feet below it, assuming the butterfly valve is wide open, in order that the condition of equal pressure at 2 mixer inlet be met. This aqueous level is below the bottom of the aqueous trough, and as Iean electrolyte enters the #2 strip mixer, if an equal amount is i not drawn off to strip mixer #1, the level of the recycle liquid in its i draw off pipe will rise. This will cause the organic level in strip settler i #1 to rise, eventually flooding. | The answer, of course is to start the unit with an operator stationed at the recycle valve and with,the valve nearly closed. After a level has been established in the aqueous overflow, the valve can be opencd a little more Cj te hole thetevel-conistant-—Fhe-syste m-is-inherently-stable-as-a-shght ————|— rise in aqueous trough level increases the static head available, increasing i the recycle flow slightly, and increasing the drawoff stream also, which will | bring the aqueous trough level down again. 4 \ To simplify startup on some plants, an adjustable baffle in the aqueous drawoff trough splits the aqueous weir flow into recycle flow and net drawoff. This permits initial startup with the butterfly valve open,and by adjusting the baffle the liquid available for recycle can be slowly increased over several hours, the valve being slowly closed to maintain the desired O/A ratio as checked by dip tube. ! A hole in this baffle permits the liquid on the recycle side to eventually adjust to the proper level and maintain it.VU ORGANIC FLOW CONTROL AND MAKEUP ! Most-plants are equipped with an organic surge tank, from which the organic is pumped to strip stage #1 from which it flows successively to i : strip stage #2, and thence to extraction stages #3, #2, and #1. From J the settler of extraction #1, it flows by gravity to the surge tank, thus ' completing the loop. A flow controller is installed on the pump discharge line to strip stage #1, | similar to that on the aqueous feed lines (see Section V), Asthe organic liquid is incompressible, the same flow must overflow the outlet weir as enters the mixer, so fixing the flow to strip #1 fixes it to strip #2, and at ‘so-or-through-the-whole-cirewit: | A small amount of organic is entrained in the raffinate Jeaving extraction : stage #3 as very fine droplets. The quantity does not normally excecd 100 parts per million, or about one-tenth of a gallon of organic per 1000 gallons of raffinate or leach liquor. If a plant handles 1000 gpm of leach liquor, over a 24 hour period this corresponds to up to 144 gallons of organic lost with the raffinate. Since the organic flow is maintained constant, this Joss results in a slowly decreasing level in the surge tank, which is made jup intermittently (or semi-continuously) by addition of : new solvent and reagent. Although for large plants the use of an organic surge tank is a great convenience, for smaller plants it may be omitted since it is not really essential. In such a plant the organic from extraction stage #1 flows directly to the mixer inlet of strip stage #1. Predicting that flow or controlling it may at firet appear impossible; the secret lies in control of the organic inventory. | Assume a plant is to process 100 gpm of Jeach liquor, with an extraction 0/A ratio of 1 both overall and within the stage; then the desired organic | flow in extraction is also 100 gpm. Such a plant has a normal inventory of about 5000 gallons of organic. Suppose on initia] start up, with the aqueous overflow weirs properly adjusted (see Section IV) we fill in only | 4700 gallons of organic. Then we start the aqueous flows at their proper rates, and start up the pumping mixers. In time as the equipment fills up'the exit aqueous flows from each stage will equal the entrance flows, : and the aqueous systems are now at a steady state. Now if a dip tube test is taken (see Section VI) of the extraction mixers, : it wil] be found that the 0/A ratio is only about 0.7, Slowly adding more 7 organic to the system, with repeated testing by dip tube of all the extraction stages will bring the 0/A ratio up to the desired value of 1.0. At each addition, the strip section recycle should be checked and adjusted accordingly.Se a will have solvent Josses up to about decrease in the 0/A ratios. jation of 0/A ratio to not more Note that this hypothetical plant 15 gallons/day. These losses will appear 35 8 Makeyp of organic once day will limit the var! than - 1%.VII “CONTINUOUS PHASE CONTROL ‘As described in Section Il, for each stage of extraction and stripping there is a preferred modé of operation; either aqueous continuous or organic continuous. ‘Asa general rule, the first extraction stage and the last strip stage should operate aqueous continuous, and all other stages operate organic continuous, but requirements of specific plants may vary from this. Since water solutions are good, conductors of electricity and oils are not, a mixture of oil droplets in water solution (aqueous continuous) ty ado ad is tu iu on js conductive, while organic continuous is non-conductive. This property is used to determine the continuous phase. If a low voltage power source is connected through a light bulb to a meta] probe, and the other power lead is connected to another probe, and the probes are immersed in the mix tank, if the mixture between the probes is aqueous continuous, the circuit is completed and the bulb lights. ‘Alternately, if the mix is organic continuous, the circuit is not completed by immersing the probes and the bulb remains dark. If the organic flow is appreciably larger than the aqueous flow, say an O/A ratio of 1.5, the mixer will operate organic continuous. On the other hand, if the O/A ratio is 0.67, then the excess aqueous will guarantee that the mixer wil] operate aqueous continuous. However, for an O/A ratio near 1.0, the mixer will operate cither way. What determines the mode of operation? It is dependent on which mode started first, as, if the mixer starts aqueous continuous, it wil] continue in that mode, and if it starts organic continuous, it will continue to operate that way. On initial start up, after flow rates and operating levels are established at their proper values, all mixers should be checked for which phase is operating continuous by using the conductivity probe described above. On most plants a probe is installed permanently on each mix tank; if one is not provided, a portable unit may be dipped into the mix tank. For each mixer operating incorrectly, it will be necessary to invert the phases. This is accomplished by sharply reducing the flow to the mixer of the present continuous phase, and then slowly restoring it to normal.winiw ed u aaa wea For example, if a mixer is running aqueous continuous and should be running organic continuous, a temporary reduction of aqueous flow will result in the mixer "seeing" a high O/A ratio, causing it to shift to organic continuous operation. Restoring the aqueous flow to normal reduces the O/A ratio to 1.0 again, but the mixer continues organic continuous. On most plants; the interruption of flow is accomplished by valves provided in the organic and/or aqueous feed lines to each mixer. For strip stages where the recycle flow is larger than the feed, a reduction of aqueous. flow is best accomplished by shutting off this recycle flow. (For these recycle valves, the original position before closure should be noted, so that it can be exactly duplicated when the | "valve ts re-opened, |The valve shouldbe shut tor five secongs then ——————— opened, rapidly at first and then slower and slower, over the next twenty to thirty seconds. The conductivity probe only senses the phase continuity of the liquid at the probe, and it may take a few minutes before the phase inversion attempt can be shown to be successful. If after three minutes the condition of the light bulb is unchanged, repeat the phase inversion procedure, being particularly careful about the gradual restoration of the flow. Plants which are not equipped with phase inversion valves are designed to permit temporary interfuption of flow at the drawoff trough outlets of the respective preceding settlers. ‘This interruption is produced by manually sliding the plate(s) provided over the outlet, just as if they were gate valves. Occasionally while the plant is operating a mixer will shift phase spontaneously. The above procedure is also used to correct these randorn inversions. Vul-2 §IX PROVISIONS FOR "GUNK" REMOVAL, Although clarifiers, filters, or other means may be provided to remove suspended solide from the leach liquor before it enters the solvent extraction plant, they are never 100% effective. In addition, solids in the form of airborne dust also enter the mixer settlers. What happens to these solids? Some passes through the extraction stages with the aqueous phase and is carried away with the raffinate. The rest, remaining in the plant, obviously steadily increases in quantity. ~ The action of mixing distributes organic, aqueous, and solids in a [more or tessumifornrmixture-entering-the-settler—Those—noli the dispersed droplets are carried toward the interface as the droplets coalesce. Those in the continuous phase are subject to the drag of passing droplets approaching the interface. In both cases, if the i particle reaches the interface, no further forces act on it, other than pravity, and its vertical movement will cease. In other words, these solids with time-tend to concentrate at the interface. Other than phenomena connected with the relative wettability of the particle by the organic than the aqueous (which seem not to be of practical importance), solids at the interface block utilization of the interface area at that point for coalescence, effrctively reducing the settler size. In addition, the particle may provide a site for initiating bacterial growth of.slimes which extract nutriment from the kerosene in the organic, Such slimes further reduce the area available for coalescence. ‘As the effective horizontal surface is reduced, the thickness of the dispersion band increases, until eventually, if unchecked, dispersion material, rather than clear aqueous or clear organic, overflows the outlet weirs. This condition is called flooding. On some plants skimmer pipe is provided to permit intermittent removal of this interfacial gunk. -This is = Jong horizontal pipe installed permanently, or portable, located across the settler width several feet upstream of the organic overflow weir. It is equipped with suitable openings on the side facing the settler flow, and is suspended so that these openings receive flow only from the level of the interface. IX-1 I‘The suspending hangers are adjustable to permit matching the skimmer pipe to the interface. The electrical conductivity of the aqueous, and hon-conductivity of the organic is utilized to determine when the adjustment is correct, by means of an electrode probe mounted on the skimmer pipe, whose tip is at the same level as the centerline of the openings in the pipe. Clipping one lead of a bulb-and-battery circuit to the hanger support, and the other to the electrode probe, shows whether the skimmer pipe is too low (light on) or too high (light off). ‘Adjusting until the light just changes locates the skimmer properly. With the skimmer positioned, the outlet is connected by a suction hose to a portable pump, and fluid is pumped to a holding tank, at no more than the specified flow rate, from which it is fed to a centrifuge. The | ——organicand-aqueows-arereturned-to-the-cirew carded. IX-2 and_the-solids_ace_dis=ABSTRACT Cities Service Compony's Solvent Extraction-Electrowinning Plant at Miami, Arizona Cities Service's SXEW plant started operation in April 1976. The plant is novel in that the "Low-Profile" concep! was used for mixing, allowing construction of the mixer-settlers at ground level. Another unique feature is that the mixer-settlers do not hove covers, Stori-up problems were minimal, amounting mostly to learning about ond tuning up the operation. Design capacity was soon achieved and product quality was ovistanding from the initial production. Described are the features of the plant, the design and operating parameters, the product quality, the minor start-up problems, and the test programs for fine-tuning of the operation. LL PDR LCCities Service Company's Solvent Extraction-Electrowinning Plant at Miami, Arizona Cities Service Company's Miami solvent extraction-electrowinning plant started operation in April 1976, replacing @ copper precipitation plant in an existing leaching operation. The in-situ leaching is to recover the copper remaining after underground mining stopped in 1959. The solvent extraction plant was built with two trains each handling 1500 g.p.m. of pregnant leach solution in three extraction and two stripping stages. The mixers are the "low profile" design which resulted in substentis! savings‘of construction ‘costs by allowing the mixer settlers fo be built at ground level, The low profile concept is based on recognition that plug flow prevails in ‘he mixer section. The mix tonk is primarily for residence time, which can be obtained as well by horizontal flow in the channel as by vertical flow in the tank. There were other design features of the plant which resulted in low capital costs. that the mixer settlers are not covered. Another factor was One of these feature: the decision to use @ high current density in the tank house. The plant start-up was exceptionally smooth for a new plant. There were some minor leaks which were not detected until acid solutions and organic diluent were put into the pipelines and mixer-setilers. Some of the mixing impeller set screws were not 316 stainless steel as specified, and had to be replaced. The most serious start-up problem was with the rectifier transformers in the tank house. Because of inadequate cooling, the tronsformers overheated and failed. This coused o delay for repairs, ond resulted in a chemical imbalance in the circuit because copper was being extracted in solvent extraction but was not béing removed in electrowinning.tl taal teh eel tl tft Pl Some of the plant operating parameters had to be changed from the original design parameters because of a higher grade feed than originally predicted. This wos not @ serious problem since solvent extraction was designed for a fixed flow, not a fixed grade, The most serious continuing problem in solvent extraction is "gunk", the sludge Jayer which builds up at the interface in the settler. Several methods to remove the gunk have been tried with little success to date. In electrowinning, the main problem is corrosion due to acid mist. Some changes have been made to improve ventilation and reduce the problem of acid mist. There hos been substantial test work fo optimize the mixing in the low-profile design. Initially, the stripping portion of the circuit was not producing a good stripper organic because the emulsion was breaking in the mixing chonnel. This required more mixing energy in stripping to solve the problem. Most of the work has deolt with the ing channel, the liquid depth to the number and location of auxiliary mixers in the impeller, and the mixer speed. Daily copper profiles were taken to monitor the results of these changes. The results to date have been encouraging and future work should yield even better results.CITIES SERVICE COMPANY'S SOLVENT EXTRACTION-ELECTROWINNING PLANT At Miami, Arizona By C. L. Pfalzgraff and A. D. Kennedy ‘The Miami solvent extraction-electrowinning plant was built to replace a copper precipitation plant iti an existing leaching operation. The idea for changing to SX-EW was introduced 4n 1973 when alternative copper recovery systems were being studied for a proposed dump leaching operation associated with the new mine and conctntrator at Cities Service Pinto Valley Operations After looking at the possibilities, it was decided that solvent extraction- electrowinning was economically feasible for copper recovery at the Miami leaching operation. » HISTORY The Miami orebody was mined by top slicing and block caving from 1910 to 1959, Mining was stopped when ore from the underground draw points no longer contained enough copper for profitable operation. However, the subsidence material above the draw points and the edjoining pillars contained copper values sufficient to encourage efforts to recover it by in-situ leaching. Actually small scale leaching had been started above some worked out areas in 1941; these efforts vere intensified in 1961 after mining had stopped, and the entire subsidence area of about 140 acres was brought under leach by 19634, The solution grade was over 2 gpl to start, but dropped to less then 1 gpl over a period of years. . In 1973-74 a core drilling program in the mine subsidence area was under- taken to prove the leaching ore reserves necessary to justify the SX-EW project. In addition, feasibility studies were made by Cities Service and outside engincer- ing firms, and General Mills Chemicals Company conducted laboratory studies toPage 2 determine 1f solvent extraction could be applied to the Miani leaching operation. The result df these studies was the decision to build the Miami SX-EN plant. PLANT CONCEPTS _AND_DESIGN As with all new plants, one objective for design was to build the best possible plant at minimum capital expense. This can be done by limiting the facilities to be built and by incorporating new technology vhere appropriate. Both concepts were used for the Miami plant. ee Hirt step_token-to-keep-coste-down-was—to-minimize—the-nunber—of ixer=— settler stages in solvent extraction. Evaluation of test work by General Mills Chemical Company showed the optimum economic configuration to be three extraction and two stripping stages. The plant was built with two trains of this configur- ation, each handling half the feed. Using new technology to reduce capital costs introduces a certain amount of risk, In this instance, the Holnes & Narver "low-profile" mixer” was considered technically feasible and would result in a substantial savings by eliminating the support structure for the settlers as well as most catwalks, platforms, and handrails. The low-profile concept is based on recognition that plug flow prevails in the mixer section, This means that after the initial mixing, the remainder of the mixer residence time is for organic~aqueous contact and that contact time can be achieved by horizontal flow in a channel as well as by vertical flow in a tank. One benefit of doing this 1s that there is less pumping function required of the Pumping mixer which means less power input. While this power savings is not economically significant, the lover pumping energy input should result in lover entrainment losses, or additional low-shear mixing energy can be added downstrean with no increase in entrainment losses”.Page 3 The mixer-settler units were built partly on cut and partly on fill. In order to minimize the chance of acid and organic leaks and spills, the mixer- settlers were built of concrete and lined with stainless steel. The stainless Steel liner gave the greatest protection against costly spills.at no extra cost over other liner materials considered. Figure I is a diagrammatic representation wf-onetraia of the SX plant. Mixing times were set at three minutes in each stage except the S-1's which were set at six minutes because of the greater copper transfer requirement in those mixers. The additional mixing time was achieved by doubling the length of the low-profile mixing channel. Each mixer section had one primary pumping mixer and a smaller secondary mixer for additional mixing energy input. The one exception to this was one E-3 which had three variable speed secondaty mixer for test work. A third step to decrease capital costs was a decision to omit roofs on the mixer-settlers. No technical reasons could be found to require the roofs, and tevestigation showed there should be little or no harmful effect from: exposure to the weather. “There was an added benefit to leaving the roofs off, which is that all areas of the mixers and settlers are open for visual inspection. In the tankhouse, the primary consideration vas to produce a high quality cathode at the lovest cost. By using a high current density for electrovinning, the size of the tankhouse could be decreased, resulting in a lower capital investment. With careful control, there should be no deterioration of cathode quality at the design current density of 21.2 amps per square foot. The major significant contaminant in electrowon cathodes is lead from the anodes. In order to control this, the anodes selected were calcium-lead and cobalt was added to the electrolyte at a concentration of 40 ppm before electro- winning was started. This coubination resulted in very good quality cathodes from the start, eliminating the problem of what to do with off grade cathodesPage 4 produced during start-up. PLANT CONSTRUCTION AND START-UP ‘the Mian SX-EW project wes divided into ‘seven phases which were” 1, Planning . Preliminary Engineering 3. Review 4. Detail Engineering 5. Detail Engineering/Construction Overlap 6. Construction t 7. Startzup In order to establish a time frame, certain milestones are listed below: I September 1974 - Complete preliminary engineering and budget study ' November 1974 Start detail engineering May 1975 = Start construction February 1976 Start plant checkout March 1976 ~, Fill circuit with organic, electrolyte and leach solution April 29, 1976 First cathode production July 1976 = Full production achieved As Cities Service had no prior experience on this type of plant, special consideration was given to ensure satisfactory startup and operation. First, a detailed startup and operating matual was prepared. This served as a useful learning tool as well as a guide for startup and early operation. Second, supervisory personnel visited operating SX-EW plants in Arizona (Cyprus Bagdad, Cyprus Johnson, and Ranchers Bluebird) in order to learn oper ating procedures and to better understand operating problems. Third, classtoom sessions were held for supervisory personnel’ to explain the fundamentals of solvent extraction and electrowinning. Also at theset Poge 5 sessions, there was discussion on unique features in the Miami plant and a trading of ideas and observations from the visits to operating plants. This program prepared our people to start the plont when it was completed and was instrumental in achieving an unusually smooth startup. Nevertheless, a few minor problens did arise. There are always the little leaks which cannot be detected until a plant is placed under operating conditions. In the Miami plant, these leaks were detected when acid solutions and organic diluent were put into the pipelines and mixer-settlers. Thése facilities had been water, vacuum end dye tested and no leaks Found, but operating conditions quickly pointed them out Another problem was that some of the stripper impellors fell off the shafts soon after the acid strength was built up in the electrolyte. It was found that not all of the impeller set screws were 316 stainless steel as specified; these screws had to be replaced. Amother situation which arose during -startup dealt with the mixer design As originally conceived, the emulsion would move down the channel by overflowin and underflowing successive transverse baffles”. It vas soon found that there was not enough freeboard to accomodate both the rise in head from the baffles and the mixing turbulance, gone emulsion slopped over the sides of the mixing Compartment. To prevent envision from siopping over, every other baffle was removed. This was a minor job, but it still leaves unanswered the question of how the mixers would perform as originally designed. The most serious problem encountered during startup was with the rectifier transformers in the tankhouse. There vas no practical method to test this equipment unt At vas ready to be used under actual operating conditions and of course, this was the part of the plant which failed to work properly when needed. The problem was inadequate cooling, which coused the transformers to 8 corrected overheat and fail. Mork by field crews and vendor representativ:te eet deeded mde) Page 6 the problem but not before it led to other complications. Solvent extraction vas already in operation. When the rectifier transformers failed, there wos en imbalance because copper was being extracted but was not being removed in the tankhouse.. .Some copper was extracted in the old cementation plant and some solution was bypassed, but these actions were not sufficient to prevent the copper concentration in the electrolyte from rising to the saturation point and precipitating copper sulfate in settlers, pipelines, and tanks. Some time vas lost in redissolving copper sulfate in the smaller lines and reestablishing normal flows. : After the problem with the rectifier transformers was solved, the plant was restarted and soon reached full production. A problem associated with gaining experience in the plant was when the iron concentration in the electrolyte got too high. This was the result of two mistakes: The ‘L1X64N concentration in the organic was too high, which in- creased iron transfer to the electrolyte and the iron bleed was not operated to maintain a safe level of iron in the electrolyte. The most serious effect of the high dron concentration was that, combined with high temperatures, it attacked the eathodes, suspension loops and caused cathodes to drop in the electrowinning cells. i Even with these problems, it was considered a very smooth startup for a new plant, PLANT OPERATION : There were changes in leaching operation between the time the plant was Segigned and the time the plant was built. These changes included using the exploratory drill holes in the subsidence area to inject part of the leach solution, and increasing the acid concentration of the Jeach solution. The result wes a higher grade feed to solvent extraction than originally predicted. This was nota problem since solvent extraction was designed to handle a fixed \Page 7 flow, not a fixed grade, The situation was easily handled by increasing the LIN64N in the organic and increasing the current density in the tankhouse to correspond to the increase in copper. ‘A comparison'of design’and operating parameters is shown in Table 1.” All of the changes, except the O/A ratio, were made because of the higher feed grade. The O/A ratio was determined by how to most easily run the plant and maintain the proper continuous phase in each mixer. While results have been good, there is still room for improvement. The Ee eramery_in_soluent_extraction hes been shout ABO, but seish tmprawed mixing, a recovery of 93-94% should not be unrealistic. The cathode quality has been very’good from the start. Analyses of indi- vidual cathodes on Septeuber 7, 1976 and December 21, 1976 are shown in Table 2. These analyses are typical of the cathodes produced in the Miami. tankhouse. Another item of interest is the loss of organic. In the first few months there was a relatively high loss of the diluent, probably because of evaporation. There has also been some relatively small but unknown loss of organic to. the ground because of spills. , Total organic addition from startup to Decenber 31, 1976 was equivalent to 108 ppm organic loss, with the losses having an spparent LIX concentration of 4% versus 6% actually in use. These losses include all spills, evaporation, and entrainment. Starting in August 1976, we have added make-up on the assumption of 50 ppm losses and have not been able to measure any change in our plant inventory. The information gathered during 1977 should give a much clearer picture ‘since it will be continuous operation with less chance of interruptions or organic spills. The very nature of solvent extraction and electrowinning presents certsin problems. In solvent extraction, the most serious, continuing problem 4s "gunk", the sludge layer that builds up at the interface in the settler. If gunk is not 1 removed, it will eventually move with the organic from oné mixer-settler to thePage 8 next, carrying entrained aqueous. This can have a serious effect on the chemical balance of the circuit if the transfer of aqueous is significant. 1m the Miamf plant, the gunk collects primarily in the E-1's and the S-1's, and these are the settlers where most of the work has been done to renov it. Two methods’ have been used; one using a slotted collector pipe at the inte face connected to a pump to transfer it to a holding tank for further processiny ‘end the second using a screen basket attached to a crane to dip the gunk from the settlers, Neither of these methods is entirely satisfactory; the first requires very close attention to keep gunk, rather than organic or aqueous, going to the collector pipe, and the second method stirs up the gunk and causes it to move from one mixer-settler to another. After the gunk is removed from the circuit, it must be treated to recover the organic it contains. One common practice Js to centrifuge the gunk to separate the solids and aqueous from the organic. This hasbeen tried in the Miami plant, but to date a satisfactory Separation has not been made betwen the solids and the organic. One problem from not having settler roofs is wind, which causes a wave action on the organic surface and stirs up the gunk at the interface. Usually this 4s not serious, but it can increase the movement of gunk enough to affect Tecovery by carrying electrolyte from stripping to extraction. There 4s some organic carried into the tankhouse with the electrolyte. This has been a decreasing problem since startup, but one which has had an interesting impact on plant operation. The pregnant electrolyte first passes through the starter cells where the combination of higher temperature and oxygen bubbles generated at the anode brings the organic to the surface. At this point, the organic can be skimmed from the electrolyte before it goes to the commercial cells. In February 1977, the emulsion in the S-1 mixers was changed from organic continuous to aqueous continuous to determine the effect of higher aqueous re- I cycle and the continuous phase on copper transfer. When this change was uade,there vas a noticeable decrease in the amount of organic entrainment going to the tankhouse. This finding 4s contrary to the iden that organic continuous mixing 4s necessary to produce 9 clean aqueous discharge at the weir. In this instance, “there was both an increase in copper transfer, due to the highes recycle, and a decrease in organic entrainment in the electrolyte. ‘The most serious problem in the tankhouse has been corrosion due to the acid mist. Deiisting balls are used on the commercial cells and removeable Repairs and changes on the tankhouse have been necessary because of concentra= “fons of acid mist, especially around the ventilating fans. Another change hes been to remove the solid floor around the cells and replace it with fiberglass Brating to improve airflow at the tops of the electrovinning cells. TEST WORK After the startup problems have been solved, there ig some fine tuning necessary in a new plant to achieve the desired efficiency. This is especially ‘rue in a plant using new technology as is the case vith low-profile mixing in the Miami plant. eg hor perion of operation ar veepaces et 4 that the extraction Portion of the plant was doing’a very good job with the Stripped organic which was being produced. However, the stripping nection ves not doing its Job well enough to give the desired overall results. The Problem was insufficient mbcing to maintain an emulsion throughout the mixing compartments. In order to Sorrect this situation, {t was necessary to move auxiliary mixers from extraction Bes Miter ctacting thictpren me cee that some routine pro— cedure to measure progress would be needed. For that reason, a sampling Procedure was established to obtain a complete copper Profile of each train svery day. The reason for taking @ complete profile was that all parts of the Plant are interconnected and a change in one mixer affects’ the performance of \Page 10 other mixers. While working with the auxiliary mixers, several important parameters became readily apparent. These were: 1. Number of mixers in the mixing. channel, 2. Location of mixers in the mixing channel, 3. Liquid depth to the impellors, and 4. Mixer speed. Items 3 atid 4 were mainly limiting conditions. Locating the impellor higher in the channel and running at faster speed produced better mixing_but also caused vortexing and splashing. The controlling factors vere the limiting speed for the mixer gear boxes and the minimum impellor liquid cover to prevent vortexing and splashing. Figure 2 shows the effect of changing the number of auxiliary mixers in one of the S-2 mixers. In this case, the S-1 was doing such » good job of stripping the organic that there was little change observed in the results from the S-2 when comparing data while running one or two auxiliary mixers in the channel. Figure 3 shows the effect of mixer location in the channel. In the first case (solid line) there were auxiliary mixers in the Nos. 2 and 3 compartments, and in the second case (dotted line), there were auxiliary mixers in the Nos. 3 and 5 compartments of: the’ S-1. The second case shows much better copper transfer in the S-1, which resulted in lower stripped organic from the S-2. This was a good comparison of intense mixing near the feed end of the mixing channel (first case) and more uniform mixing throughout the length of the channel (second case). Later, a third auxiliary mixer was added to the S-1 which further improved stripping.Page 11 In order to demonstrate the progress made in stripping, figure 4 shows typical. stripping isotherms from plant data in August and December 1976, Figure 5 shows the stripping isotherm for March 1977 at different operating conditions. Two observations can be made from these. graphs: As work pro- Bressed, tore of the stripping was being done in the S-1, and better mixing has resulted dn a lower copper content in the stripped organic. The improved stripping did show up in extraction by decreasing the copper content of the reffinate, In extraction, the improvement has not been nearly ‘as dramatic as in Ty pring —igure6-shows—the-ef fect of adding an mux ITary WIKeE Eo Che ET ~ There is significant improvement in the copper transfer in E-1, but this is not carried through the E-2 and E-3 mixers, In fact, the decrease in copper in the raffinate is just about equal to the decrease in copper in the feed for the data periods before and after putting the mixer in the E-L. Figure 7 shows that an auxiliary mixer in E-2'has just ebout the same effect as im E-1. The changes here are smaller because there Se less copper transfer in E-2 than in E-1, The slope of the operating line is different for the two data periods because of a change’in the 0/A ratio. Figure, 8 shows plant extraction data for August and Decenber 1976 and figure 9 shows the same data for Pocembez-I076 and March 1977. Nearly all of the improvement in extraction is due to improvement in stripping since mixers were being removed from extraction. As the stripped organic improved, ex- traction started to work on a more favorable portion of the curve. Further Auprovement in mixing, to take full advantage of the stripped organic, should improve extraction. Further work is avaiting delivery of additional auxiliary mixers. The Miami SX-EW plant has performed very well for a new facility. The low-profile mixing concept docs‘work and results should improve as more in-Page 12 formation is gathered about mixing optimization. REFERENCES 1, Fletcher, J. B-, In-Place Leaching - Miami Mine, 1969. 2. Paige, P. M., Selected Equipment Modifications, Solvent Extraction and Electrovinning, Presented to the Annual, Hydronetallurgical Neeting, Canadian Institute of Mining and Metallurgy, October 7, 1975. 3. Bennett, W. A., and Kontny, V. L., The Cities Service SX-EW Project Story, Presented to the Arizona Conference of the American Institute of Mining Engineers, December 6, 1976. ACKNOWLEDGMENTS The author wishes to acknowledge the cooperation of Cities Service Company's management in presenting this paper.’ Individuals participating in or rendering advicé on the technical aspects of the studies include: Wayne Jensen and Brant Sudderth of General Mills Chemicals, Inc., P. M. Paige of Holmes and Narver, Inc., and N. B. Gillespie and B. M. Frazier of Cities Service Company.Page 13 TABLE 1 Operating Parameters; Miami SX-EW Plant Actual Design? Ist Quarter 1977 Pregnant Leach Solution Flow 3000 gpm 3000 gpm cB inant Leach Solutson-Grode— 95 gp T.05 gpl cu Electrolyte Advance : 125 gpm 140 gpm : O/A Ratio d:l 1.1-1.2:1 Settler Area 1.85 gpm/sq.ft. 2.0 Bpm/sq.ft. L1X64N Concentratio# 4.5% 6.0-6.5% tathode Production 30,600 Ibs./day 33,000-34,000 abs. /a Flectroviining Currént Density 21.2 amps/eq.ft. 25-30 amps/sq.ft.rage 44 TABLE 2 Cathode Analysis Sept. 7, 1976 Dec. 21, 1976 tome mol ea met mel et Sample Sample cuz 99.98 99.98 Pb Ppa ae fle3 Fe Ppa 2.8 3.2 Ni ppm LS 1.3 Sb ppm 1.6 1.3 As ppm <1. <1 Se ppm <10 <10 Te ppm <1 “1 Bi ppm <0.1 20.1 Sa Ppa <2 <2 Au ppia <1 é1 Ag ppm <1 41 9, ppm 105 95 s ppm cee a1WOM INVIERS TSI050 00 3.00 Cain Organic (4/1) \ 7 T T 1 A Se soo | 1 £ wool. + Z 3 1 AUXILIARY saIKER IN 52 soo + ——— zauxiiany mxensinsa ! 1 1 L 1 ° 020 040 060 80 100 320 | Cvin Organi f/1) FIGURE 2 STRIPPING s00 soo L 3 ok : | L Soreness CompantMentTs2 &3 soo ustiany manxens tn 1 Convantwents 3.85 1 L \ L 1 ° 020 000 129a ed a Cuin Aqueous (9/1) sol wef ef ef oe met oe eet ef oot oe met —— — EARLIER fauGusT 1976) LATER [DECEMBER 1976) 0.60 0.20 1.00 Cu in Organic (9/1) FIGURE 4 STRIPPINGvty Guin Aqueous 1 L L 040 0.60 020 Guin Orjanie (9/1) FIGURE 5 STRIPPING — MARCH 1977 120A auxsdny en ie v NO AUXILIARY MIXER INE 1.20 / 4 O 1.00 B 020 6 0.60 a0 0.20 1 L 1 L 1 ° 020 040, 60 20 1.00 120 Cuin Aqueous (9/1) FIGURE 6 a1.60 r — — — auxiuiany siixen iv es onty AUXILIARY MIXERS IN E-2 AND ES T T Guin Organic (gt) i i: 1 1 040 0.60 ozo 1.09 1.20 Cuin Aqueous (9/1) FIGURE 7T T EARLIER (AUGUST 1976) — — — tater (occempen 1976) ic (9/1) Wu in, Organi t ‘060 Cuin Aqueous (9/1) FIGURE ® ozo 1.00T T i T T EARLIER (AUGUST 1976) A — — — tater (oecemsen 1976) ZA nie (ft) in, Orga 1 1 1 060 080 1.00 Cuin Aqueous (9/1) FIGURF &1.60 140 azo T T T T MARCH 197 Cuin Orgonie f 100 | oo | a0 | 020 |- 1 1 1 1 1 “020 00 0.60 080 1.00) Cu in Aqueous (9/1) FIGURE 9 even action \ aAReH wT 4.20