CA1091935A - Process for recovering platinum group metals from ores also containing nickel, copper and iron - Google Patents

Abstract

PROCESS FOR RECOVERING PLATINUM GROUP METALS
FROM ORES ALSO CONTAINING NICKEL, COPPER AND IRON
Abstract of the Disclosure A process is described for the separation of platinum group metals (PGM) from ores also containing iron, nickel and copper as sulfides. The minerals in the ore are first concentrated by flotation and the ore concentrate is melted in an electric furnace to form a matte containing at least 95% of the precious metals. The matte is granulated while molten to granules of a mean size not greater than about 210 micrometers (µm) and then pressure leached with sulfuric acid and oxygen to separate the nickel, iron and copper as their respective sulfates, while recovering the PGM as a residue. Concentration of the leach residue by roasting and subsequent acid leaching yields a final PGM
product containing the major portion of the precious metals in the ore and substantially all (i.e., at least about 95%) of the precious metals in the ore concentrate and which contains less than 1% total nickel, iron and copper. The iron, nickel and copper in the leach solution can be sub-sequently recovered and/or discarded as, respectively, natrojarosite, nickel or copper metal or various compounds such as sulfides, hydroxides, or oxides, as appropriate to the specific application.

Description

~a~ 3 5 PROCESS FO~ R~COVERING PLATINUM GROUP METALS
1 F~OM ORES ALS9 CONTAINING NICKEL? COPPER AND IRON
Background of The Inventicn The invention herein relates to processes for recovering platinum group metals in concéntrated form from their ores. More particularly, it relates to a process for recovering a platinum group metal concentra~e from an ore containing, in addition to the platinum group metals, nickel, copper and iron.
Platinum group metals.(hereinafter sometimes LO referred to as "PGM") may be associated in ores and their concentrates with iron, copper and nickel sulfides. It has been known in the past to separate and refine these ores by conventional pyrometallurgical techniques, in which the various other materials (notably iron) are removed at inter-mediate steps in the process, leaving a PGM residue as the end product. A typical example is illustrated in U.S.
Patent No. 1,841,207. However, such processes generate large amounts of sulfurous gas emissions, notably S02 in combination with minor amounts of other sulfur oxides, and

2~ they have thus become environmentally unacceptable unless complex and expensive pollution control devices are incor-porated into the processes to control the sulfur emissions.
In U.S. Patent No. 3,293,027 a two-stage hydro-metallurgical process is shown where the principal aim is to recover nickel and cobalt from a ground metal matte containing 60X to 75% nickel,.lesser amounts of cobalt and copper, and small quantities of platinum.group metals, iron, sulfur, and especially arsenic. A preliminary hydrometallurgical treatment is used to separate the precious metals in a residue which also contains the bulk of the arsenic and iron, as well as some nickel and other non-ferrous metals.

~L~9~35 .
1 Fur~her treat~ent (such as cyanidation) is thus required to separate the precious metals from the iron and arsenic.
U.S. Patent No. 1,~96,807 illustrates collection of the platinum group metals in a high copper content matte and then further refinement to separate the precious metals from the copper. U.S. Patent No. 1,863,807 illustrates separation of a matte containing copper, lead, iron and precious metals from an ore also containing cobalt, nickel, arsenic and antimony. U.S. Patent No. 2,425,760 illustrates separation LO by controlled cooling of a molten matte of copper and nickel in the form of sulfides from a ~etal alloy containing the precious metals. U.S. Patent No. 2,777,764 illustrates a hydrometallurgical process for dissolving refractory ores and recovering precious metals therefrom by cyanidation.
U.S. Patent No. 2,829,967 discloses a process for separating platinum group metals from copper-iron-nickel sulfide ores by roasting the non-precious metals to oxides, chlorides or sulfates, leaching the salts to separate the iron and PGM, then chloride treating the solution to separate the iron and finally precipitating the PGM with a non-precious metal, such as copper or iron. U.S. Patent No. 1,634,497 discloses a process for two-stage roasting and leaching of copper-PGM
ores to separate the metals. U.S. Patent No. 3,767,760 discloses a process for acid leaching and aqua regia sepa-ration of PGM from copper ores. Other patents of i~terest illustrating separation processes haYing some relation to the present process for obtaining platinum group metals include U.S~ Patent Nos. 1,542,935; 1~983,274; 3,332,771;

3,576,620; 3,785,944; 3,793,430; 3,798,304; 39816,105; and 3~
3,879,272.

3~ L~ 5 1 Also of pertinence is "The Initial Development of Processes for the Direc~ Leaching of Iron-Nickel-Copper Mattes Containing Platinum-Group Me~als and For the Produc tion of Ferronickel," by J. P. Martin et al. Report No.
1720, National Institute for Metallurgy, Johannesburg, South Africa (March 7, 1975). This report describes a process in which P6M are partially separated from an ore containing copper, iron and nickel by a series of steps involving smelting, granulation and acid leaching with dilute sulfuric acid. In this process sulfides are formed, including hydrogen sulfide, and the PGM are not fully separated but rather are retained in a major copper sulfide component.
Objects of the Invention It is an object of th~s ~nvention to provide a hydrometallurgical technique for separating platinum group metals from ores also containing nickel, copper and iron in an environmentally acceptable manner.
It is also an object of this invention to provide a process for separating platinum group metals from ores containing nickel, copper and iron, wherein the platinum group metals are separated first, thus minimizing the pro-cessing needed to recover the precious metals and giving the producer an option as to further treating of the residue containing the remaining metals.
It is further an object of this invention to provide a process which can be economically utilized on PGM
ore deposits which are for any reason mined at a relatively low production rate.
Brief Summary of the Invention The invention herein is a process for the separa~
tion of a platinum group metal concentrate from ores con ~ 9~L~D;~S

1 taining PGM, nickel, copper and iron. ThP process comprises first concentrating the ore by flotation to form a concen-trate and then subjecting the concentrate to electric furnace melting to form a low grade matte; granulation of the matte to form granules; leaching the metals from the matte granules under pressure in the presence of sulfuric acid, ox~gen and water, filtering the leached materials to obl;ain a filtrate containing dissolved salts of nickel, iron and copper and a filter cake containing the precious metals, sulfation roasting the filter cakei and subsequently acid leaching metals from the roasted filter cake and filtering the leached materials at least once more to further concentrate the P~M, and finally drying the filter cake from the last of the subse-~uent filtrations to produce a PGM concentrate containing at least 25% platinum group metals and less than 1% copper, nickel and iron.
In a further embodiment of the invention, the filtrate is thereafter treated with sodium ion under appro-priate conditions in the sulfate ion containing solution to percipitate the iron in the form of natrojarosite. The filtrate may then be further treated with sodium acid sul~ide to produce copper sulfide which is removed by filtration, and the filtrate may therea~ter be treated ~ith lime to produce nickel hydroxide as a precipitate. Alternatively, after na~rojarosite precipitation the filtrate may be neutralized to precipitate the copper and nickel as their hydroxides or treated under pressure with hydrogen sulfide to produce mixed copper and nickel sulfides. The copper and niGkel compounds may be recovered and the natrojarosite discarded, since the latter is merely a synthetically ~I~?~L~3 S

1 produced version of a co~mon mineral occurring in nature and is chemically stable and environmentally acceptable.
Briet Descrietion of the Drawirigs FIG. 1 illustrates schematicaliy the process of this invention for obtaining the PGM concentrate.
FIG. 2 is a schematic flow diagram illustrating recovery of the PGM concentrate and, in addition, one embodi-ment of the present process for further tre~ting and separation of the iron, copper and nickel components.
FIG. 3 illustra~es schematically another embodiment of that part of the present process in which the nickel and copper components are recovered.
FIG. 4 illustrates schematically a third embodiment of that part of the present process in which the nickel and copper components are recovered.
- Detailed_Description and Preferred Embodiments The initial ore 2 from a mine (which in a typical instance contains approximately 0.05% to 0.2% copper, 0.10 to 0.25% nickel and approximately 0.15 to 1.0 ounce of precious metals per ton) is passed to a flotation concen-tration process 4. This is a conventional flotation con-centration system wherein the major portion of the gangue is removed leaving a concentrate 5 which comprises approximately 1% to 5% of the original ore. (All percentages stated herein are percentages by weight.~
This mill concPntrate is fed into an electric furnace 10 either in its initial partiGulated form or it may be pelletized in pelleti~ing unit 6 and fed as pellets. In either case it is combined with flux 8 (typically limestone and hematite) to form the furnace charge. Also included in the electric furnace may be recycles of processed dust and s l reverts. In the electric furnace slag resistance melting causes the entire charge to melt and separate to form a lower layer of sulfidic matte and an upper l~yer of slag containing the silica, magnesium and alumina in the con-centrate. Slag is formed at about four times the rate of matte formation, and may be tapped continuously or inter-mittently as required and granulated, as by high pressure water sprays, for discard.
The matte is periodically tapped through line ll and granulated in unit 13 to form a finely divided material for further processing. By "finely divided'l is meant that the mean particle size of the matte granules is not greater than 210 ~m (65 mesh, Tyler Sieve Series). It is preferred to obtain matte having this particle size by mechanically striking a stream of molten matte with a rotating impeller and simultaneously quenching the matte droplets thus formed with a high pressure water spray. The granulation step renders the mat~e more amenable to the subsequent leaching process when the latter is carried out in the preferred temperature range of 100C to 140C (~12F to 284F). In particular, the degree of separation subsequently obtained between the PGM into the residue and the base metals into the solution is substantially enhanced when compared, for instance, to a matte which is coarsely granulate~ to a mean size of only 600 to 700 ~m.
A small amount of sulfur dioxide is formed by the combustion of sulfur distilling from the melting concentrate.
This sulfur9 however, amounts to only about 10% to 2S% of - the sulfur in the entire furnace feed. Since no more than about 25~ of the sulfur entering the process is expelled in a gaseous form, the application of any of a number of con-1~9~Lg35 1 ventional sul,`ur oxide recovery systems, such as lime scrubbers, will effect adequate emission abatement.
FIG. 2 illustrates a typical manner of handling the furnace dust and sulfur oxides. The off gases con-taining fine dust are removed through line 12 and sent to electrostatic precipitator 14. The precipitated dust is removed through line 16 and is returned to the furnace directly through line 17 or it may be fed to pelletizing unit 6 through line 19. The S02 and any other sulfurous 1~ gases may be passed through line 18 to lime scrubber 20 where they are contacted with lime 22 and reacted to Form calcium sulfate and sulfite, which may be discarded as indicated at 24. The slag separated from the matte in the electric furnace may be discarded as indicated at 26 and/or recycled as indicated at 28.
To obtain a matte size which is best suited for subsequent processing steps the granulated matte is now preferably further comminuted by grinding in a ball mill to a particle si~e range of at least 50% minus 400 mesh (37 ym), and preferably at least 60% minus 400 mesh (37 ~m).
The electric furnace matte now passed to the pressure leaching unit 36 through line 15 contains virtually all of the copper, nickel, platinum group metals and over 70% of the iron and 75% of the sulfur in the original ore, and will generally comprise 1ess than 1% of the original ore weight. The pressure leaching process serves to dissolve as much of the copper, nickel and iron as possible by oxidation in the presence of the sulfur in the matte to form copper, nickel and iron sulfates. The reactiQn is carried on in the presence of water 30, sulfuric acid 32 and oxygen 34 in a pressure vessel 36. Sulfuric acid addition will be in l amounts of about 0.8 to 2.0 lb acid per lb of matte feed, preferably 1.2 to 1.6 lb acid per lb of matte feed. Suf-ficient oxygen is added to maintain a total pressure of 40 to 155 psia (2.7 to 10.5 atm), preferably 70 to 125 psia (4.8 to 8.5 atm) in the pressure vessel (or autoclave).
Reaction temperature is maintained at approximately 100C to 140C (210F to 285F), preferably 110C to 130C (230~ to ~65F) and typical residence time is approximately 2 to 6 hours, preferably 3 to 4 hours. The extent of the reaction is limited to dissolution of about 94% to 98% (preferably 95% to 97%) of the weight of the matte. Beyond this point it has been found that the platinum group metals, particu-larly palladium and rhodium, begin to dissolve more markedly.
The pressure leached residue is transferred through line 38 to ~iltration unit 40, which may be a conven-tional plate and frame pressure filter or other device suitable for the filtration of hot liquors. The solid residue containing approximately 1% to 8% PGM is retained as a cake on the filter while the acidic solution containing 2~ the dissolved iron, nickel and copper sulfates is removed as a filtrate liquid through line 42. The specific percentage of PGM will depend in part on the elemental sulfur content of the residue, with more PGM content where there is less elemental sulfur content.
The filter cake is now subjec~ed to a refinement process to upgrade the PGM content at the expense of any remaining copper, nickel, iron and sulfur, since the latter metals should generally be reduced to less than 1% total in the PGM concentrate in order to assure that the latter will normally be acceptable to a PGM refinery. Elemental sulfur is first removed by volatilization in an inert atmosphere, 1 by dissolution in an organic solvent, or by hot filtration, as indicated at 43.
The filter cake is then subjec~ed to roasting in unit 44 in a controlled atmosphere of oxygen at about 450C
to 525C (840F to 975F), preferably about 500C (930F), to convert the sulfides to copper, nickel and iron sulfates respectively. The amount of sulfur not taken up by the con-trolled oxidation passes off as sulfur dioxide and may be collected in an appropriate sulfate emission control system such as the lime scrubber previously described. The sulfated materials are then acid leached in unit 4& with dilute H2S04 and the acid leached material is filtered in unit 48. For best results the concentration of the acid should not exceed about 750 gm/l (7.7 molar). The filter cake is dried in unit 50.
In order to maximize the recovery of precious metals, the filtrate is passed through line 51 to a cemen-tation step to recover any dissolved platinum group metals in unit 52. Such concentration may be achieved by the addition of cementiny agents to the PGM solution while it is being agitated in a stirred vessel. Typical cementing agents which may be used include metals such as iron sponge, iron powder and nickel powder, preferably iron powder, and in some cases organic compounds such as hydrazine. The filtrate containing the cemented precious me~als is then filtered a second time in unit 54 and the solids returned to the precious metal recovery system as indicated at 56.
These solids are blended with the solids of the drier 50 and the entire material collected as platinum group metal concen-trate 58. If desired, all or part of the entire series of concentration steps of sulfation roasting, acid leaching, ~q~ L~3~
1 filtration, cementat;on and drying may be repeated several times It is especially advantageous to repeat the acid leaching and filtration steps at least once. The recovered PGM concentrate, which typically comprisés less than 0.01 weight percent of the original ore, nonetheless contains more than 80% of the paladium and platinum in the original ore. The concentrate itself contains on the order o-f 2S% to 80% precious metals and less than 1% total iron, nickel and copper, depending on the exact treatment characteristics of the original ore.
Iron recovery in the form of a jarosite is illus-trated in FIG. 2. The two quantities of filtrate from filtration units 40 and 54 are passed respectively through lines 42 and 60 to be mixed and blended with sodium ion 62 in unit 64 in the presence of sulfate ion. Commonly the filtrate itself contains sufficient sulfate ion for the - jarosite formation reaction, so the sodium ion may be in the form of any soluble ionizable sodium compound which does not impart a detrimental anion to the system (i.e., an anion which causes undesirable reactions with other components of the system or which is difficult to separate or handle subsequently). Sodium carbonate has been used successfully as the source of sodium ion. It is also possible to use sodium sulfate as the source of sodium ion where the filtr~te is low in sul~ate ion or where the presence of excess su1fate ion is not objectionable. The sodium ion, sulfate ion and iron react to form a sodium-iron double sul~ate known as nat~-ojarosite. This is precip;tated in unit 66 in the presence o~ calcium carbonate 68 in the form o~ pulverized ~0 limestone or lime (preferably limestone). The limestone is added continuously to maintain a pH in the range of 1.1 to 1 1-6 (preferably 1.4 to 1~ for a period of 2 to 5 hours (preferably about 3 to 4 hours) at a temperature of 85C to 95C (185F to 205F). The natrojarosite is then filtered in unit 70, which comprises a top fed horizontal belt filter, washed and removed for discard. The liquids from the lime treating unit 66 and the filtration unit 70 may be collected and passed through line 72 for further treating to separate copper and nickel. Many details of natrojarosite formation and separation are illustrated in U.S. Patents Nos. 3,434,798;
3,~34,947; 3,493,365; 3,684,490 and 3,691,038. The natrojarosite, being a mineral occurring in nature, may be safely discarded with a minimum of environmental impact.
The filtrate liquid, now largely free of iron, may as noted be further treated to recover the copper and/or nickel values in any of the alternative processes shown in FIGS. 2, 3 and 4. In the embodiment shown in FIG. 2, the fi7trate is passed to thickening unit 74 where it is con-tacted with a reactive sulfide 76 (preferably sodium acid sulfide or hydrogen sulfide) under conventional conditions.
This causes the copper sulfate to precipitate as copper sulfide which is removed by filtration in unit 78. This precipitate is composed of about 55% copper and less than 4%
nickel. It thus contains approximately 70% to 75% of the original copper and only about 2% to 3% of the original nickel from the ore. While thus not a pure copper sulfide, it is sufficiently concentrated in copper to be acceptable as a feed to a copper smelter.
The remaining liquid, no~ containing principally nickel, is passed through line 80 to precipitation unit 82 where it is precipitated in the presence of lime 84 under conventional conditions. ~he precipitate is then thickenecl , 1 in unit 8~, f~ltered in unit 86 and dried in unit 88 and recovered in the form of nickel hydroxide. The nickel hydroxide precipitate contains approximately 10 to 15%
nickel and less than 0.1% copper. It thus contains approxi-mately 6~% of the original nickel content of the ore and less than 1% of the original copper content, calcium sulfate being the principal diluent. As with the copper sulfide precipitate, the nickel hydroxide precipitate is sufficiently concentrated in nickel to be acceptable as feed to a nickel refinery or smelter. The remaining filtrate liquid can be recycled through line 90 back to the original pressure leaching operation and/or other parts of the process as dilution and/or wash water to maximize recovery of all metal.
More preferably, however, as shown in FIG. 3, the filtrate liquid in line 72 may be treated to precipitate the contained copper and nickel as a mixed sulfide. In this method the filtrate from jarosite precipitation is diluted in the ratio of 2-3 parts of recycled tail liquor to one part of filtrate. After increasing the pH of the diluted solution to about 3.5 with lime 92 in unit 94, the resultant solution is treated in autoclave 96 in the presence of hydrogen sulfide gas 98 at a pressure of about 115 psia ~7.8 atm) and about 130C (265F) to precipitate the metals as mixed sulfides containing substantially all of the contained metals (including a small amount o~ residual iron) and normally analyzing 21% to 23% copper, 32% to 36% nickel, less than 1% iron, and 30% to 32% sulfur. This precipitate is removed from the vessel 96, thickened in unit 100, and 0 passed to filtration unit 102 (preferably a plate-and-frame filter). The filter cake, after washing, is suitable for 1 sale while the filtrates may be recycled as at 104 to the original oxygen pressure leaching operation and/or to other parts of the operation for re-use and maximum recovery of metals.
, In a further alternative method (shown in FIG. 4) for removing the copper and nickel as hydroxides from the solution in stream 72, the whole stream is contacted in unit 105 with lime 106 to raise the pH to 8 to 9 at a temperature of between 50C to 70C (120F to 16QF), preferably about 60C ~140F). All of the copper, nickel and residual iron, and substantially all of the calcium, are contained in a low grade precipitate normally analyzing 4% to 5% copper, 12% to 14% nickel, 1% to 2% iron and 18% to 20% calcium. As with the previous two alternative methods, the precipitate is thickened in un1t 108 and then removed from the solution by a use of a suitable filtration device 110, the filtrates being recycled to the process as at 112.
A principal advantage of any of these process embodiments is that they yield a copper and nickel product suitable for further treatment. This is done at a low cost, with simple equipment as is suitable for small operations and without the introduction of soluble cations such as ammonium ion which introduce an expensive waste disposal problem into the process.
Although the three previously cited techniques for copper and nickel removal are the preferred ~echniques for a small operation, it would also be possible to recover copper and nickel from the solutions, after iron removal, as metals or oxides with a high degree of purity by such techniques as cementation, solvent extraction purification, electrowinning and other conventional techniques of copper and nickel 1 hydrometallurgy. However, such methods require a considerable capital investment in process equipment and are only economically justified where the production of by-product copper and nickel is high enough.

Claims (27)

WHAT IS CLAIMED IS:

1. A process for the separation of a platinum group metal concentrate from an ore containing iron, nickel and copper in addition to said platinum group metals, which process comprises:
(a) concentrating said ore by flotation to form a concentrate;
(b) subjecting said ore concentrate to electric furnace melting to form a low grade matte;
(c) granulating said matte to form granules;
(d) leaching metals from said granules in the presence of sulfuric acid, oxygen and water;
(e) filtering the leached metals to obtain a filtrate predominately containing dissolved salts of said iron, nickel and copper and a filter cake predominately containing said platinum group metals;
(f) sulfation roasting said filter cake;
(g) acid leaching copper, nickel and iron metals from the roasted filter cake; and (h) filtering and recovering a solid platinum group metal concentrate from said roasted and leached filter cake.

2. The process of Claim 1 wherein said granulation of step (c) comprises mechanically striking a molten stream of said matte with a rotating impeller and simultaneously quenching the granules with a high pressure water spray.

3. The process of Claim 1 wherein said granules are of sizes such that at least 50% are less than 37 µm.

4. The process of Claim 2 further including mechanically grinding said matte granules to a particle size such that at least 50% are less than 37 µm.

5. The process of Claim 4 wherein at least 60 of the mechanically ground particles are less than 37 µm.

6. The process of Claim 1 wherein said sulfation roasting, acid leaching and filtration of steps (f), (g) and (h) are repeated at least once.

7. The process of Claim 1 wherein said leaching of step (d) is conducted at a temperature of 100°C to 140°C.

8. The process of Claim 7 wherein said leaching is conducted at a temperature of 110°C to 130°C.

9. The process of Claim 1 wherein said leaching of step (d) is conducted with a sulfuric acid concentration of 0.8 to 2.0 pounds of acid per pound of said granules.

10. The process of Claim 9 wherein said leaching is conducted with a sulfuric acid concentration of 1.2 to 1.6 pounds of acid per pound of said granules.

11. The process of Claim 1 wherein said leaching of step (d) is conducted with sufficient oxygen to maintain a reaction pressure of 40 to 155 psia.

12. The process of Claim 11 wherein said leaching is conducted with sufficient oxygen to maintain a reaction pressure of 70 to 125 psia.

13. The process of Claim 1 wherein said leaching of step (d) is conducted for a period of 2 to 6 hours.

14. The process of Claim 13 wherein said leaching is conducted for a period of 3 to 4 hours.

15. The process of Claim 1 wherein said roasting of step (f) is conducted in an oxygen atmosphere at a temper-ature of 450°C to 525°C.

16. The process of Claim 1 further comprising:
(i) passing filtrate from step (h) through concentration with a cementing agent and then filtering the cemented materials prior to recovery of the platinum group metal concentrate.

17. The process of Claim 16 wherein said cementing agent is iron powder.

18. The process of Claim 1 further comprising:
(i) contacting the filtrate of step (e) with sodium ion and sulfate ion in a solution to convert the iron in said filtrate to natrojarosite and precipitating and sepa-rating said natrojarosite from said solution.

19. The process of Claim 18 wherein said conver-sion of iron to natrojarosite is conducted at a solution pH
in the range of 1.1 to 1.6.

20. The process of Claim 19 wherein said solution pH is in the range of 1.4 to 1.6.

21. The process of Claim 18 wherein said conver-sion of iron to natrojarosite is conducted for a reaction time of 2 to 5 hours.

22. The process of Claim 21 wherein said conver-sion of iron to natrojarosite is conducted for a reaction time of 3 to 4 hours.

23. The process of Claim 18 wherein said conver-sion of iron to natrojarosite is conducted at a temperature of 85°C to 95°C.

24. The process of Claim 18 further comprising:
(j) contacting said solution from which said natrojarosite has been separated with a reactive sulfide to form copper sulfide and precipitating, separating and recovering said copper sulfide.

25. The process of Claim 24 further comprising:
(k) contacting the solution from which said copper sulfide has been separated with lime to form nickel hydroxide and precipitating, separating and recovering said nickel hydroxide.

26. The process of Claim 18 further comprising:
(j) contacting said solution from which said natrojarosite has been separated with hydrogen sulfide while maintaining said solution at a pH of about 3.5, a temperature of about 130°C and an H2S pressure of about 115 psia to form a mixture of sulfides of nickel and copper and thereafter precipitating, separating and recovering said mixed sulfides.

27. The process of Claim 18 further comprising:
(j) raising the pH of said solution from which said natrojarosite has been separated to a pH in the range of 8 to 9 by contacting said solution with lime to form copper and nickel hydroxides and thereafter precipitating, separa-ting and recovering said hydroxides.