OPIC CIPO (72) WADHAWAN, SATISH C., US 7) WADHAWAN, SATISH C., US (1) Int.CL.® BOID 11/04, CO1G 49/10, CO1B 9/02 (30) 1998/02/25 (60/075,936) US «zascay Demande-A pplication anan 2,318,823 (36) 1999/02/25 37) 1999/09/02 (4) EXTRACTION DU CHLORURE FERRIQUE AVEC UN SOLVANT (4) SOLVENT EXTRACTION OF FERRIC CHLORIDE (57) La présente invention conceme un procédé de Purification de solutions a base de chlorure ferrique contenant des impuretés, qui consiste a traiter tout abord Ia solution de chlorure ferrique (10) contenant des impuretés. avec un solvant organique (24), sélectionné a partir d'un alcool possédant entre environ 4 20 atomes de carbone, afin de dissoudre de maniére sélective le chlorure ferrique. Le solvant organique obtenu (26) est alors séparé du chlorure ferrique sélectivement dissout (30). et environ HH iste canada Industry Canada (37) A method of purifying ferrie chloride solutions with impurities having the following steps; first, the ferric chloride solution (10) containing impurities is treated with an organic solvent (24) selected from an alcohol having from about 4 to about 20 carbon atoms to selectively dissolve the ferric chloride, The resulting organic solvent (26) is then stripped from the selectively dissolved ferric chloride (30).’ CA 02318823 2000-07-27 PCT IAL, PROPERTY ORGANIZATION WORLD INTELLECTUAL, IZATION 6 INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (51) International Patent Classification 6 : BOLD 11/04, CO1B 9/02, CO1G 49/10 AL (11) International Publication Number: (43) International Publication Date: WO 99/43408 2 September 1999 (02.09.99) (QI) International Application Number: PCT/US99/04141, (22) International Filing Date: 25 February 1999 (25.02.99) (30) Priority Data: 60/075,936 25 February 1998 (25.02.98) US. (71)(72) Applicant and Inventor: ~_WADHAWAN, Satish, C. {IN/US}; 142 Phillips Place, Pitsburgh, PA 15217 (US). (14) Agent: LONG, Daniel, J 125 Ridgeview Drive, Etrs, PA 17319 (US). (81) Designated States: CA, IN, US, European patent (AT, BE, CH, CY, DE, DK, ES, Fl, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE). Published With international search report. (64) Title: SOLVENT EXTRACTION OF FERRIC CHLORIDE ‘SRP Souk - 1 16 ‘EMACTEN = 1 STREPAG = | Tomek = 1 (me sour oF ects) coo — F (57) Abstract ‘containing impurities is treated with an org: ‘A method of purifying feric chloride solutions with impurities having the following steps: first, the feric chloride solution (10) a solvent (24) selected from an alcohol having from about 4 to about 20 carbon atoms to Selectively dissolve the ferric chloride. The resulting organic solvent (26) is then stripped from the selectively dissolved fertie chloride (20),10 215 20 CA 02318823 2000-07-27 ‘Wo 99143408 PCT/US99/04141 SOLVENT EXTRACTION OF FERRIC CHLORIDE BACKGROUND OF THE INVENTION (1) Field of the Invention The present invention relates to the separation of chemicals and more particularly to processes for purifying ferrous or ferric chloride solutions. (2) Brief Description of Prior Developments The industrial use of pure the ultrapure iron chloride increases each year. The following processes are the major consumers: production of ferrites; production of pure iron powders; production of iron oxide elements; production of ultrapure alloys for the electronics industry; etching of copper plate or other copper materials; and synthesis of various compounds. There are three principal methods to Produce pure iron oxide. The first of these methods is the traditional means of obtaining salt by recrystallization to remove impurities, precipitation of iron hydroxide, followed by washing and calcination. Another method is the electrolytic production of metallic iron followed by conversion to the oxide. Still10 15 CA 02318823 2000-07-27 SETUS PEAS 24 Std hd another method is the purification of iron in the melt followed by burning of the iron powder. All of these methods involve multiple and labor intensive steps. Research into novel methods has been on going for many years. The production of iron and its purification via liquid-liquid extraction is relatively new and was recently introduced to the industry to obtain pure solutions of FeCl; and FeS0,. The traditional, industrial method used to obtain iron oxide was recrystallization, which has been replaced with extraction. A more effective method to achieve high-purity iron oxide is the combination of the extraction of iron from a chloride solution, followed by pyrohydrolysis of the pure FeCl; solution, which simultaneously produces iron oxide (Fe20s) and concentrated hydrochloric acid (HCl). The extraction of iron from acidic salt solution has been known for more than fifty years. The method is used in analytical chemistry as a means to purify various solutions from iron. With the introduction of new technology that utilizes pure iron oxide as a basic material, the liquid extraction of iron has received increased attention from industry. Tributylphosphate, (CiHs)sP0, (TBP), easily extracts FeCl; from solutions containing HCl. The higher the concentration of HCl, the steeper the equilibrium curve that10 15 CA 02318823 2000-07-27 ‘WO 99/43408 PCT/US99/04141 describes the partitioning of FeCl; between the organic and aqueous phases. The FeCl; is completely extracted from the aqueous phase if the concentration of HCl exceeds 50-60 g/l. Laboratory tests conducted in KSC, on continuously operating equipment, have demonstrated the feasibility of extracting Pure solutions of FeCls. However, in further testing at the pilot plant, using industrial FeCl; solutions, a problem arose with the use to tributylphosphate. The concentrations of Si and K exceeded the minimum allowable levels. In addition, P was also a major impurity, due to the use of TBP, which partially hydrolyzes when the concentration of HCl in the feedstock exceeds 90-100 g/l, which leads to large losses of TBP. In addition, salts of organic compounds, arising from the hydrolysis byproducts, completely contaminated the first attempts at extraction. The rate of layering of the emulsion was slow, due to the high viscosity of the organic phase and the small difference in specific gravity between the organic and aqueous phases, especially at the stages of raffinate removal and water in flow for re-extraction. Further experiments conducted completely corroborated the Previous results. In addition, TBP did not yield solutions as concentrated as those yielded by sending the feed directly to10 15 : CA 02318823 2000-07-27 WO 99/43408 PCT/US99/04141 the hydroprolysis equipment in the final analysis; TBP cannot be used for industrial production. Trioctylamine, (CeHi7)3N (TOA), after work-up with HCl, also easily extracts FeCl; at low Cl” concentrations in the equilibrated aqueous phase (70 or more g/l). TOA is usually used with a dilutent (kerosene), and problems are usually not encountered with separating the aqueous and organic phases. However, TOA also has certain disadvantage. low concentrations of FeCls. For example, low concentration re-extracts can lead to the co-extraction of other elements, i.e. Zn. For this reason, TOA is also not used in the industrial production of ultrapure iron oxide. Methylisobutylketone, C,HsCOCHs, (MBK) is also a good extractor of iron. However, it has a high vapor pressure and is extremely flammable. Its use in hot climates (such as India’s) is not possible. In addition, much liquid is lost during operations to evaporation and given the low concentration of FeCl; in re-extracts, extractions using MBK do not yield the desired economic returns. The above analysis shows that a new extractant is needed.10 15 CA 02318823 2000-07-27 ‘WO 99/43408 PCTUS99/04141 SUMMARY OF THE INVENTION The present invention comprises a process to purify ferrous or ferric chloride solutions with high amounts of impurities, especially impurities such as Ca, Na, Ma, V, Cr, Ni, and the like, that cannot be removed by conventional technologies using selective precipitation. The process developed is based on using a selective organic solvent that will selectively extract ferric chloride and leave the impurities in the raffinate. The process can be used for either ferrous or ferric chloride, since the ferrous chloride, if the solution contains any ferrous chloride, must be converted to the ferric chloride form by oxidizing with chloride. Also, in order to have a high degree of iron recovery, the iron in the raffinate is recovered by a subsequent extraction stage. Final recovery of ferric chloride from the organic solvent is achieved by stripping the solution with pure water. Since the ultimate aim is to produce high-purity iron oxide in a spray roaster plant, it is also essential to produce a relatively high concentration of ferric chloride in the purified solution. To achieve about 30-35% ferric chloride in the final solution, the impure liquor is concentrated to about 50% ferric chloride by evaporation. Depending upon the final requirement, two to three stages of solvent extraction and two to three stages of evaporation may be used. Each solvent extraction10 15 CA 02318823 2000-07-27 ‘Wo 99/43408 PCT/US99/04141 stage may contain as much as fifteen or more cells, consisting of as much as nine cells for extraction and six cells for stripping. . Also, due to very high amounts of impurities, it may be advantageous to introduce an intermediate washing with the water stage. In such a case, each solvent stage will have extraction, washing, and stripping In order to economize the steam consumption, the multiple effect evaporators may be used. BRIEF DESCRIPTION OF THE DRAWINGS Other objects, features and advantages of the present invention will become apparent upon reference to the following description of the preferred embodiments and to the drawing, wherein corresponding reference characters indicate corresponding parts in the drawing and wherein: FIG. 1 is a schematic illustration of a preferred embodiment of the process of the present invention; FIG. 2 is a schematic illustration of an alternate preferred embodiment of the processes of the present invention; and FIG. 3 is a schematic illustration of the leach liquor processing unit employed in the process of the invention.10 15 CA 02318823 2000-07-27 ‘wo 99/43408 PCT/US99/04141 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Referring to FIG. 1, there is an initial feed solution of FeCl; provided in line 10 to an evaporation apparatus 12. Condensate from this evaporation apparatus is transported in line 14; the stripping apparatus 16; pure water is added to the condensate in line 18. Ferric chloride solution is transported from the evaporation apparatus 12 in line 20 to an extraction apparatus 22. Organic solvent that is preferably N-octanol is introduced to the extraction apparatus 22 in line 24. The solution is removed from the extraction apparatus 20 in line 26 to the stripping apparatus 16. Solvent is removed from stripping apparatus 16 in line 28 and a pure solution of ferric chloride is removed in liquor line 30. Raffinate is removed from extraction apparatus 22 in line 32 to line 34 and then introduced to evaporation apparatus 36. Condensate is removed from evaporation apparatus 36 in condensate line 38, which connects to strip solution line 40 and strip solution line 42. A feed line 44 connects the evaporation apparatus 36 to an extraction apparatus 46, and organic solvent is introduced to the extraction apparatus 46 through an organic solvent line 48. Line 50 removes solution from the extraction apparatus to a stripping apparatus 52, and there is an off-line 54 from this stripping apparatus as well as a liquor line 56 that connects to the initial feed line 10. A raffinate line 58 connects the10 15 CA 02318823 2000-07-27 WO 99/43408 PCT/US99/04141 extraction apparatus 46 to another extraction apparatus 60, which also is provided with solvent through organic solvent line 62. Line 64 connects extraction apparatus 60 with stripping apparatus 66 that has an off-line 68 and liquor line 34. Raffinate is removed from the extraction apparatus 60 as waste solution in raffinate line 70. Referring to FIG. 2, in an alternate embodiment ferric chloride is introduced in feed line 72 to evaporation apparatus 74. Condensate is then removed from this evaporation apparatus 74 in condensate line 76 to extractor apparatus 78. There is an organic input line 80 for this extractor apparatus 78 as well as an extractor output line 82, which connects to a washer apparatus 64. A washer output line 86 connects to a stripper apparatus 88 that is outputted to line 80. Condensate is introduced to stripper apparatus 88 in condensate lines 75 and 90, and solution is removed from the stripper apparatus in output line 92 that connects to an evaporator feed line 94 and a liquor output line 96. Line 94 connects to an evaporator 98, which is outputted in line 100 to line 89. Evaporator 98 is also connected to washer apparatus 84 by line 102. For solutions that have a medium range of multiple impurities, it is essential to use one or more washing steps. The number of washing steps would depend upon the nature of the solution and the extent of impurities. Raffinate line 104 comes off the10 15 CA 02318823 2000-07-27 ‘Wo 99743408 PCT/US99/04141 extraction apparatus 78 to connect to line 106 for introduction of solution to another evaporator 108 from which condensate is removed in line 110, Organic solvent is introduced in lines 111 and 112 to extractor apparatus 114 from which solvent is removed in line 116 to washer apparatus 118. Solvent is removed from the washer apparatus 118 in line 120 to a stripper apparatus 122, which is connected to solvent line 112. A condensate line 124 also brings condensate from line 110 to stripper apparatus 122, and a stripper output line 126 to remove solution from the stripper 122. Line 128 removes solution from washer apparatus 118 and is connected with stripper output line 126 to flow into recirculation line 130 which is connected to feed line 72. Washer apparatus 84 is connected by line 132 to washer apparatus 118. Extraction apparatus 114 is connected by raffinate line 134 to recirculation line 136 and to waste solution line 138. Referring to FIG, 3, leach liquor feed line 140 is connected to a leach liquor filter 142. The leach liquor filter output line 144 is connected to leach liquor preheater 146 that is heated by steam provided in steam header 148. Condensate is removed from the preheater 146 in condensate return line 150 and line 152 connects evaporated liquor to chlorination column 154. Chlorine is provided to the chlorination column 154 in chlorine line 156. Chlorinated liquor is removed to a storage tank in line 158 and evaporated material is removed in line 160 to a10 15, CA 02318823 2000-07-27 WO 99/43408 PCT/US99/04141 chlorination scrubber 162. Line 164 recirculates material from the chlorination scrubber 162 to the leach liquor filter output line 144. Chlorination scrubber output line 166 removes liquor to an ilmenite liquor storage tank (not shown). It was discovered that waste acid derived form the pickling of stainless steel contains a very high amount of nickel and chromium (1-38). It seems that solutions can be purified even without the washing step and a revised flow sheet was developed or indicated in FIG. 3. In such a scheme, two independent stages of Mixer-Settler, without the washing stage was selected. N-octanol does not extract iron from aqueous solutions below 270-300, g/l FeCls. This means FeCl cannot be completely extracted. with N-octanol, but above this concentration, it can be used. N-octanol extracts FeCl; efficiently in the 280-850 g/l concentration range, while impurities are weakly extracted. The equilibrium extraction curve (the dependence of the concentration of FeCl; in the organic solvent on the concentration in the aqueous phase) is practically a straight line. Here the Y-axis is expressed as the solution density, which can easily be converted to concentrations, knowing the corresponding concentration of HCl. However, the given information is sufficient to evaluate the extraction. The extraction proceeded well; taking into account the decrease in the volume flow of the water phase, the extraction of V into the 1010 15 20 CA 02318823 2000-07-27 Wo 9943408 PCT/US99/04141 organic phase reaches 70-73%. Depending on the concentration of FeCl; in the feed and water phase, the concentration of FeCl: in the organic phase can reach 180 g/l. At high concentrations of HCl, the extraction proceeds easily; the final concentration of FeCl; is 250-260 g/1 (if the organic phase is not already saturated with iron). If the HCl concentration is low, the raffinate reaches a density of 1,230-1,240 g/l, which corresponds to a FeCl; of 280-300 g/l. -In working with certain solutions (high HCl concentrations, the necessary concentration of the raffinate was 1,165 g/l (830 g/l for the opposing organic phase), which was practically without FeCl;. The re-extraction of the water results in a liquor with a concentration of 400 g/l FeCl; and higher. During the re-extraction of the condensate containing HCl, the concentration of FeCl) and the presence of acid in the water phase, which was in equilibrium with the organic phase, limits the FeCl; in the organic phase, lowering the efficiency of the re-extraction process. The work with N-octanol has demonstrated the following: 1.A sufficiently high-purity of liquor (only traces of impurities). 2. No problems with evaporation; the rate of striation of the emulsion is good. 3. N-octanol is not volatile at the process temperatures. uw10 15 CA 02318823 2000-07-27 Wo 99/43408 PCT/US99/04141 4. Phase mixing is not significant. 5.A “third phase” is observed only in the first three (counting the number of extractions of the water phase) stages of the extraction. 6. At high FeCl; and HCl concentrations in the water phase and temperatures of 20 - 30°C, the solution partially crystallizes; this can be avoided in practice if the the feed is held at 40-45° C before pumping. 7. A washing of the organic phase with a non-volatile liquor is effective. The waste solution from synthetic rutile production (after chlorinaton) could be characterized as “impure” with a high HCl concentration. Here, it was not possible to directly achieve a high-purity liquor, that is, without washing. The washing required a 580 g/l FeCl; liquor. That concentration corresponds to the equilibrium concentration of FeCl; in the water phase in the first stage of extraction. The washing must not be done with a lower concentration of FeCls, since a significant portion of FeCl; will enter the water phase and the concentration in the organic phase will fall and the liquor will be lower in FeCl; than permissible. In the experiments, the liquor was washed two times. Practically, the industrial process should include three washings. The washings should be returned to the extraction 1210 15 CA 02318823 2000-07-27 Wo 99/43408 PCT/US99/04141 process. The re-extraction with highly acidic condensates is not desirable. If in the process of evaporation it is possible to achieve a condensate lower in HCl concentration and use it in the re-extraction, this would be the better solution to use. The raffinate, after the first stage of the extraction, is again evaporated. Raffinate-2 is added to the first raffinate to achieve the required extraction of FeCl;. The organic phase, after the second phase after the second extraction, will contain many more impurities than after the first extraction, and must be washed more carefully. In fact, the possible extraction processes are defined by which extraction stage the solutions are sent back to after the first and second washings. Raffinate-1 is mixed with the recycled and amalgamated solutions after washing and is sent to the evaporator a second time. The condensate is used for the re-extraction. The evaporated solution undergoes seven stages of extraction until the organic phase saturates at 162.5 g/l FeCl. Then it undergoes two washings of three stages each. The first stage is the amalgamated solution after I and III washings; the second stage is the final washing with fresh solution. The re- extract-2 is likewise put through five stages with the condensate. The re-extract-2 should reach the same quality as the re-extract-1. Raffinate-2 is divided into two parts; the 1310 15 CA 02318823 2000-07-27 ‘Wo 99143408 PCT/US99/04141 majority goes into the recycled solution to undergo another extraction of FeCl3, while some is discarded as waste. The major difficulty in developing the technology is the jarge concentration of impurities in the solution entering the second extraction. The impurities are nearly half of the FeCl; concentration. It is difficult to achieve an ultrapure product from that, while simultaneously minimizing washing. Similar purification of ferrous chloride solution, using the above solvent extraction process can be achieved by first chlorinating ferrous chloride to ferric chloride solution. The exhaust gases are scrubbed with the impure ferrous chloride solution. The exhaust gases are scrubbed with impure ferrous chloride solution to achieve acceptable chlorine emissions. A system consisting of solvent extraction with/without chlorination and spray roaster acid regeneration is used to Produce high-purity Iron oxide. The system is designed and Coordinated so that excess condensate water is used as make-up water for the absorber to produce regenerated acid. This will eliminate any wastewater stream and produce 18% or 32% HCl, to Produce high concentration acid (above 26% HCl). While the present invention has been described in connection with the preferred embodiments of the various figures, it is to be understood that other similar embodiments 14‘CX 02318823 2000-07-27 ‘WO 99143408 PCT/US99/04141 may be used or modifications and additions may be made to the described embodiment for performing the same function of the present invention without deviating therefrom. Therefore, the present invention should not be limited to any single embodiment, but rather construed in breadth and scope in accordance with the recitation of the appended claims. 15,CA 02318823 2000-07-27 ‘Wo 99743408 PCT/US99/04141 What is claimed is: 1.A method of purifying ferric chloride solutions with impurities comprising the steps of: (a) treating said ferric chloride solution with impurities with an organic solvent selected from an alcohol having from about 4 to about 20 carbon atoms to selectively dissolve the ferric chloride; and (b) then stripping the organic solvent from the selectively dissolved ferric chloride. 2. The method of claim 1 wherein the organic solvent is a normal alcohol. 3. The method of claim 2 wherein the organic solvent has from about 6 to about 10 carbon atoms. 4. The method of claim 3 wherein the organic solvent is N- octanol. 5. The method of claim 4 wherein in step (a) the ferric chloride solution is partially evaporated before addition of the solvent. 16CA 02318823 2000-07-27 PCTS EMS 2) Se? th 6. The method of claim 5 wherein in step (a) raffinate is removed after addition of the solvent. 7, The method of claim 6 wherein in step (a) after removal of raffinate, solution is added to the raffinate after which said solution and raffinate is further evaporated. 8. The method of claim 7 wherein steps (a) and (b) are successively repeated a plurality of times. 9. The method of claim 1 wherein the impurities are selected from a group consisting of Ca, Na, Ma, V, Cr and Ni. 10.A method of purifying a ferric chloride solution with impurities comprising the steps of: (a) introducing said ferric chloride solution with impurities to an evaporation apparatus and partially evaporating said ferric chloride solution with impurities to produce a condensate and remaining unevaporated ferric chloride solution with impurities; (b) removing said unevaporated ferric chloride solution with impurities remaining after step (a) to an 7cca 02318823 2000-07-27 : 99/8 a 9'7 SEP 1989, extraction apparatus and adding to said extraction apparatus, an organic solvent which is an alcohol having from 4 to 20 carbon atoms such that said organic solvent extracts the impurities from the ferric chloride solution; (c) removing the ferric chloride solution and organic solvent with extracted impurities produced in step (b) from the extraction apparatus to a stripping apparatus; (d) removing the condensate produced in step (a) to the stripping apparatus; and (e) in the stripping apparatus, stripping the organic solvent with impurities from the ferric chloride solution and then separately removing said ferric chloride solution and the organic solvent with extracted impurities from the stripping apparatus. 11.The method of claim 10 wherein in step (d) water is added to the condensate before said condensate is removed to the stripping apparatus. 18 a Sennen SHEETCA 02318823 2000-07-27 POTUS 99/0414 27 SEP 1999. 12.The method of claim 10 wherein after step (g) of the ferric chloride solution removed from the stripping apparatus has further impurities, and comprising the further steps of: {£) introducing said ferric chloride solution with impurities removed from the stripping apparatus on step (g) to a second evaporation apparatus and partially evaporating said ferric chloride solution with impurities to produce a condensate and remaining unevaporated ferric chloride solution with impurities; (g) removing said unevaporated ferric chloride solution with impurities remaining after step (f) to a second extraction apparatus and adding to said second extraction apparatus, an organic solvent which is an alcohol having from 4 to 20 carbon atoms such that said organic solvent extracts the impurities from the ferric chloride solution; (h) removing the ferric chloride solution and organic solvent with extracted impurities produced in step (g) from the second extraction apparatus to a second stripping apparatus; 19 aiMEN SHEETCA 02318823 2000-07-27 Pens 72/ Ad (i) removing the condensate produced in step (f) to the second stripping apparatus; and (3) in the second stripping apparatus, stripping the organic solvent with impurities from the ferric chloride solution and then separately removing said ferric chloride solution and the organic solvent with extracted impurities from the second stripping apparatus. 13. The method of claim 12 wherein the ferric chloride solution removed from the second stripping apparatus is added to the ferric chloride solution prior to the introduction of ferric chloride solution with impurities to the evaporator in step (a). 14.The method of claim 11 wherein after step (j) the ferric chloride solution removed from the second stripping apparatus has further impurities, and comprising the further steps of: (x) introducing said ferric chloride solution with impurities from the second stripping apparatus to a third evaporation apparatus and partially evaporating said ferric chloride solution with 20 AREINEN CHETimpurities wen 29/604 fle! to produce a condensate and remaining ferric chloride solution with impurities; (1) removing said impurities extraction extraction an alcohol ferric chloride solution with remaining after step (k) to a third apparatus and adding to said third apparatus, an organic solvent which is having from 4 to 20 carbon atoms such that said organic solvent extracts the impurities from the ferric chloride solution; (m) removing the ferric chloride solution and organic solvent produced in step (1) from the third stripping apparatus with extracted impurities to a third stripping apparatus; (n) removing the condensate producec in step (k) and adding said condensate to the third stripping apparatus; and (o) in the third stripping apparatus, stripping the organic solvent with impurities from the ferric chloride solution and then separately removing said ferric chloride solution and the organicCA 02318823 2000-07-27 PCTUS 04141 BEMIS 27 Se? SEP Pt 99 solvent with extracted impurities from the third stripping apparatus. 15. The method of claim 14 wherein raffinate is removed from the third extraction apparatus as waste solution. 16.The method of claim 15 wherein the ferric chloride solution is removed from the third stripping apparatus and is introduced to the second evaporation apparatus. 17.The method of claim 10 wherein the organic solvent is a normal alcohol. 18.The method of claim 17 wherein the organic solvent has from about 6 to about 10 carbon atoms. 19.The method of claim 18 wherein the organic solvent is N- octanol. 20.The method of claim 1 wherein the impurities are selected from a group consisting of Ca, Na, Ma, V, Cr and Ni. 21.A method of purifying a ferric chloride solution with impurities comprising the steps of:CA 02318823 2000-07-27 wAUS 97/28 bed (a) introducing said ferric chloride solution with impurities to an evaporation apparatus and partially evaporating said ferric chloride solution with impurities to produce a condensate and remaining unevaporated ferric chloride solution with impurities; (b) removing said unevaporated ferric chloride solution with impurities remaining after step (a) to an extraction apparatus and adding to said extractor, an organic solvent which is an alcohol having from 4 to 20 carbon atoms such that said organic solvent extracts the impurities from the ferric chloride solution; (c) removing the ferric chloride solution and organic solvent with extracted impurities produced in step (b) from the extraction apparatus to a washing apparatus for washing to remove extracted impurities; (d) removing the washed ferric chloride solution and organic solvent washed in step (c) to a stripping apparatus;wes 7/08 tebe! (e) removing the condensate formed in step (a) to the stripping apparatus; and (£) in the stripping apparatus, stripping the organic solvent from the ferric chloride solution and then separately removing said ferric chloride solution and the organic solvent from the stripping apparatus and recirculating the organic solvent to the evaporation apparatus. 22.The method of claim 21 wherein in step (f) there are additional impurities with the ferric chloride solution recovered from the stripper apparatus, comprising the further steps of: (g) introducing said ferric chloride solution with impurities recovered from the stripper apparatus to a second evaporation apparatus and partially evaporating said ferric chloride solution with impurities to produce a condensate and remaining unevaporated ferric chloride solution with impurities; (h) removing said unevaporated ferric chloride solution with impurities remaining after step (g) to a 4A 02318823 2000-07-27 second extraction apparatus, and adding to said second extraction apparatus an organic solvent which is an alcohol having from 4 to 20 carbon atoms such that said organic solvent extracts the impurities from the ferric chloride solution; (i) removing the ferric chloride solution and organic G) (k) qa) solvent with extracted impurities produced in step (h) from the second extraction apparatus to a second washing apparatus for washing to remove extracted impurities; removing the washed ferric chloride solution and organic solvent washed in step (i) to a second stripping apparatus; removing the condensate formed in step (g) to the second stripping apparatus; and in the second stripping apparatus, stripping the organic solvent from the ferric chloride solution and then separately removing said ferric chloride solution and the organic solvent from the stripping apparatus and recirculating the organic solvent to the evaporation apparatus. 25 alaexinen SHEETCA 02318823 2000-07-27 BCTIUS 99/04141 zi SEP 1999 23.The method of claim 21 wherein raffinate is removed form the extraction apparatus. 24.The method of claim 21 wherein the ferric chloride solution is removed from the stripping apparatus and a portion of said solution is reintroduced to said washing apparatus. 25,The method of claim 24 wherein a portion of said ferric chloride solution is removed from the stripping apparatus is evaporated and reintroduced to said stripping apparatus. 26.The method of claim 21 wherein the organic solvent is a normal alcohol. 27.The method of claim 26 wherein the organic solvent has from about 6 to about 10 carbon atoms. 28.The method of claim 27 wherein the organic solvent is N- octanol. 29.The method of claim 21 wherein the impurities are selected from a group consisting of Ca, Na, Ma, V, Cr and Ni. ao rem NED SHEETCA 02318823 2000-07-27 - S 99/04 i AI 27 SEP 1999 30.The method of treating a ferric chloride leach liquor solution with impurities comprising the steps of: (a) filtering said ferric chloride leach liquor solution; (b) heating said ferric chloride leach liquor solution; introducing the heated and filtered ferric chloride leach liquor solution in a chlorination column; (c) introducing the ferric chloride treated in the chlorination column to a chlorination scrubber; (d) recovering the liquor from the chlorination scrubber. 31. The method of claim 21 wherein liquor from the chlorination column is removed to a storage unit. AUcainen QueerPCT/US99/04141 CA 02318823 2000-07-27 WO 99/43408 1/3 SS ~ = - _ i= yonon (wounos aiswa) = 3IYNLLIVa J 01 29 . i ~ NOUV a TD ia c= amigas a|_ NUO R= ara 7 ¥9 N i ~ NOUNIOS dls 99 i SIVNIY 08 yon 9S re I~ ONIddILS ke tl - NOWOVULXS |.__- _ a Il ~ SINVO4O Hl ~ NOUMOS tals n—fi-au ly as [ Il = NOL¥OdvAa ————a ag : A _ ap " il ~ 3U¥SN30NOD ) = awa 7 (194 40 NOlMIOS 34nd) 1 - YondH t nr 80 UaYM 3nd | - 9NIgdldLS wen { - NOWOVYLG INvONO gi 92 on 1- Gad i a a O1 1924 NOILATOS 0334 TILINI =e a oy I- “Y= IVSN30N0D SUBSTITUTE SHEET (RULE 26)PCT/US99/04141 CA 02318823 2000-07-27 ‘Wo 99/43408 2/3 s ___NOWNTOS 3IS¥A Oy old cn rr = ye : ms ei 2-3VNLIY __ | ESV ONVOHO ‘ ad <}--4 EB} po ~----4 eat ego | ~~ {2a} - - T 7 rT | Gay ol a FO ot ou nl SIVSNONOD la MW 7-A3 yoy TOKO tt eh | z-aavswaanoa Noluntos - TA] ~“Tyonor ONS WOH NOUMTOS—Y)—gor- len 0 1 a : 8 n _ 158i INVONO aan 2-yonon Ea tah 1 7 ~~ flask - a =H fx = ~~~ oman rat--}} 08 1g , 5 : v8 ol o6~ | =T1VSN3ONO0 1A ¥Os NOUMOS 0-032 ~ a Y a tu ¥L ‘SUBSTITUTE SHEET (RULE 26)CA 02318823 2000-07-27 PCT/US99/04141 WO 99/43408 3/3 YNVL 3OVYOLS YONDN, Q3IVNIOTHD OL YNVL JOVYOLS YONOM IUINIAT! OL NAM100 NOILWNINOTHD EOL INOIHD << ~~ 3 Y38NYIS as NOILYNIYOTHD Log UaLVIHUd yonOr HOV3 cr —— | =) spams > me vad yonon HOVE) q yonon Hova1 Ort U30V3H_AVIIS SUBSTITUTE SHEET (RULE 26)‘SRP SOUTON = 1 a6 wee ek T[unon Sain Frc) cape — 1 f ¥ r 7 a g a § sm sun = a seeme 1} s ‘a STON = a