Abstract:
A process for recovering at least one precious metal from an ore containing carbonaceous material is disclosed. The process involves the use of promoting amounts of certain metal redox couples and/or metal components, in particular, certain metal complexes with ligands. 
     Preferred metal compositions comprise at least one of (1) redox cyclable vanadium (5+) ligand complex, (2) redox cyclable iron (3+) ligand complex, and (3) redox cyclable manganese (3+) ligand complex. In the process, the use of at least one regenerable component capable of maintaining the complexed metal in the desired oxidation state provides for integrated process synergy.

Description:
RELATED APPLICATIONS 
     This application is a continuation-in-part of co-pending application Ser. No. 751,793 filed Aug. 29, 1991, now abandoned which is a continuation-in-part of co-pending application Ser. No. 627,896 filed Dec. 13, 1990 now abandoned which application is a continuation of application Ser. No. 213,884 filed Jun. 30, 1988 now abandoned which application is a continuation-in-part of application Ser. No. 005,140 filed Jan. 20, 1987, now U.S. Pat. No. 4,765,827 and application Ser. No. 025,069, filed Mar. 12, 1987, now U.S. Pat. No. 4,801,329. Each of these applications and patents are hereby incorporated in their entirety herein by reference. 
    
    
     BACKGROUND OF THE INVENTION 
     This invention relates to a process for recovering at least one metal, e.g., gold, silver, the platinum group metals and the like, from an ore containing carbonaceous material and the metal to be recovered. In particular, the invention relates to a process which involves processing a metal-containing ore so as to facilitate the recovery of the metal from the ore. 
     Carbonaceous ores, i.e., ores which contain elemental carbon (e.g., graphite) and/or organic compounds, often contain valuable metals, such as gold, silver, the platinum group metals and the like. Once characteristic of such ores which has made them difficult and expensive to process is that the presence of carbon and organic compounds inhibits metal recovery using conventional, e.g., cyanide, processing. In other words, the presence of organic material in such carbonaceous ores tends to interfere with metal extraction, e.g., by cyanidation. For example, a substantial amount of carbonaceous ore is not amenable to conventional cyanidation techniques because of the presence of carbon (which often acts like activated carbon), and relatively long chained organic hydrocarbon-type compounds containing sulfur, nitrogen, carboxylic acid groups and the like. 
     There is a growing world-wide interest in metal recovery from carbonaceous ores. Thus, in spite of the substantial work which has been done to provide for such metal recovery, a need currently exists to provide for a process for metal recovery from carbonaceous ores. 
     SUMMARY OF THE INVENTION 
     A process for recovering at least one metal from an ore containing the metal and at least one of certain carbonaceous material has been discovered. 
     In one broad aspect, the present process involves contacting at least one ore containing at least one metal to be recovered and carbonaceous material with at least one added metal component in an amount effective to at least promote the oxidation of the carbonaceous material. The contacting occurs at conditions effective to (1) chemically oxidize at least a portion of the carbonaceous material, and (2) at least partially liberate the metal to be recovered from the ore. By liberation is meant that the gold is more susceptible to recovery, for example by cyanidation, than without pretreatment. The first metal is then recovered from the ore. 
     In one embodiment, the contacting occurs in the presence of an additional oxidant, more preferably a gaseous source of oxygen, e.g., air, enriched/diluted air, oxygen and the like. 
     In one embodiment, the redox couple or added metal component is preferably selected from at least one of the following: (A) at least one iron component, preferably an iron complexing agent, in which iron is present in an amount in the 3+ oxidation state effective to promote the oxidation of the the carbonaceous material; (B) at least one vanadium component in which vanadium is present in an amount in the 5+ oxidation state effective to promote the oxidation of the carbonaceous material; (C) at least one copper component in which copper is present in an amount in the 2+ oxidation state effective to promote oxidation of the carbonaceous material; (D) at least one cobalt component in which cobalt is present in an amount in the 2+ oxidation state effective to at least promote the oxidation of the carbonaceous material; (E) at least one manganese component in which manganese is present in an amount in the 3+ and/or 4+ oxidation state effective to at least promote the oxidation the carbonaceous material; and mixtures thereof. The ore or ores preferably contain precious metals, such as gold, silver, the platinum group metals and the like, which can be recovered using the process of this invention. The various embodiments of this invention can be practiced singly or in any combination of embodiments, with selection and optimization generally being a function of the ore type and desired metal value recovered. 
     The benefits resulting from the process of this invention, e.g., improved rate of oxidation including solubilization and/or conversion to a different form, i.e., solids, such as insoluble jarrosite, sulfates, arsenates and the like, improved rate of oxidation of the carbonaceous material and/or yield/recovery of desired metal as a function of time, are substantial. Without wishing to limit the invention to any specific theory of operation, it is believed that many of such benefits result from the promoting effect of one or more of the above metal redox couples and/or metal components in the process of this invention. The promoting effect of the presently useful redox couples and metal components allows the process to be effective, e.g., from the standpoint of improved recovery of desired metal as a function of time, on a wide variety of difficult to process ores. 
     Improved yields or recoveries of metal are often achieved under less severe conditions by practicing the present process, especially when compared to recovering metal from the carbonaceous ore without utilizing the process of this invention. The present process is relatively easy to operate and control. Relatively low concentrations of promoters are used and relatively mild operating conditions may be employed. With regard to carbonaceous ores, operating and capital costs are often reduced relative to previous chlorination/oxidation procedures which require substantial amounts of chemicals and/or expensive metallurgy to combat corrosion problems. Thus, the present invention can provide a cost effective approach to metal recovery from carbonaceous ores. 
     DETAILED DESCRIPTION OF THE INVENTION 
     The present process provides substantial advantages. For example, the use of at least one of certain promoting metal redox couples and promoting metal components, such as one or more iron components, vanadium components, copper components, cobalt components and manganese components (with or without complexing agents), provides for improved contacting, e.g., to increase the rate of carbonaceous material oxidation and ultimately to improve the yield of metal or metals recovered. The improved rate of carbonaceous material oxidation also results in significant process and cost economies. In addition, effective metal recoveries can be achieved utilizing low grade (heretofore difficult to process) carbonaceous ores. Further, the present process does not require the addition of sulfur dioxide or hydrogen sulfide to maintain or culture any bacteria. 
     The process of the present invention is useful for metal recovery from carbonaceous ores, as defined herein. A large number of ore bodies and large amounts of carbonaceous ores are susceptible to be treated in accordance with the present process. Examples of such ores include: oxidized and carbonaceous ores from various locations in north central and northeastern Nevada, such as the Carlin ore, the Cortez ore and the Witwatersrand ore; ores from the Prestea and Ashanti gold fields in Ghana; the Natalkinsk and Bakyrichik ores from the Soviet Union; various Canadian ores such as the gold ore from the McIntyre Mine, located near Schamacher, Ontario; and the like ores. The carbonaceous ores may include oxidized ore material, possibly even a major amount of oxidized ore material. Also, the carbonaceous ores may contain metal pyrites. The carbonaceous ore which contains metal pyrites may be processed for pyrite removal by physical and/or chemical means to reduce the pyrite content of the ore prior to the contacting step of the present invention or be processed along with the carbonaceous portion of the ore. For example, subjecting the ore to various procedures such as grinding, particle size fractionation, flotation and the like can reduce the amount of metal pyrites in the ore. 
     The present process employs at least one of certain metal redox couples and/or metal components. Such metal components may include alkali and/or alkaline earth metals provided that they also contain one or more additional metals which are effective in the present invention. Such metal redox couples and/or metal components are present during the contacting step in an amount effective to at least promote the oxidation of the carbonaceous material in the ore. Thus, such metal redox couples and/or components are present in an amount effective to promote such oxidation and/or to oxidize the carbonaceous material in the ore. 
     The presently useful metal redox couples and metal components are preferably selected from the group consisting of iron components, copper components, cobalt components, vanadium components, manganese 3+ and/or 4+ components and mixtures thereof. More preferably, the metal redox couples and metal components are selected from the group consisting of iron components in which iron is present in an amount in the 3+ oxidation state in an amount effective to at least promote the oxidation of the ore&#39;s carbonaceous material; copper components in which copper is present in an amount in the 2+ oxidation state effective to at least promote the oxidation of the ore&#39;s carbonaceous material; cobalt components in which cobalt is present in an amount in the 2+ oxidation state effective to at least promote the oxidation of the ore&#39;s carbonaceous material; vanadium components in which in which vanadium is present in the 3+, 4+ or 5+, preferably 5+, oxidation states in an amount effective to at least promote the oxidation of the ore&#39;s carbonaceous material; manganese components in which manganese is present in the 3+ and/or 4+ oxidation state of the ore&#39;s carbonaceous material, and mixtures thereof. Any suitable metal component may be employed provided that such component is capable of at least promoting the oxidation, noted above. Particularly useful vanadium 5+ components are vanadium pentoxide, and the soluble vanadates and oxyanion derivatives thereof, and complexes of vanadium 5+ with ligands. 
     The copper +2 components are particularly effective when present in combination with an amount of ferric ion. In this embodiment, the copper +2 component acts to enhance the overall oxidation of the carbonaceous material. If one or more vanadium and/or copper components are present in the contacting, the vanadium 5+ and/or copper 2+ concentration is preferably at least about 10 ppm., more preferably about 50 ppm. to about 1.0% and still more preferably about 100 ppm. to about 0.1% or to about 0.5%, by weight of the aqueous composition present during the contacting, calculated as elemental vanadium and/or copper. 
     When vanadium 5+ and/or copper 2+ components are employed, the reducible manganese component is preferably capable of oxidizing and maintaining an effective amount of vanadium/copper component to the vanadium 5+ and/or copper 2+ oxidation states at the contacting conditions. 
     In one embodiment, the iron, copper and cobalt, vanadium and manganese components are soluble and are preferably selected from iron complexes with ligands, copper complexes with ligands, cobalt complexes with ligands, vanadium components with ligands, manganese components with ligands, and mixtures thereof. Such complexes preferably include at least a portion, more preferably a major portion and still more preferably substantially all, of the metal in the preferred oxidation state, noted above. 
     Examples of iron complexes useful in the present invention include iron complexes with polyfunctional amines, for example, ethylenediamine, propylene diamine, ethanol amine, glycine and asparagine and salts thereof; phosphoric acids and phosphoric acid salts, for example, ethane-1-hydroxy-1, 1-diphosphonic acid; pyridine and substituted, chelating pyridine derivatives, for example, phenanthroline, 0-phenthroline, 2, 2&#39;-bipyridyl, glyoxime and salicylaldehyde derivatives; aquo; and CN--. Among the particularly preferred iron complexing agents for use in the present invention are those selected from the group consisting of substituted, chelating derivatives of pyridine, aquo, CN-- and mixtures thereof. 
     Examples of copper complexes useful in the present invention are copper, in particular copper 2+, complexes with pyridine, 1, 10-phenanthroline, imidazole, substituted, non-chelating derivatives thereof and mixtures thereof. These derivatives include substituents such as hydroxy, carboxyl, amino, alkyl and aryl groups. 
     Cobalt, in particular cobalt 2+, complexes of chelating Schiff&#39;s bases are preferred. These ligands include, for example, ligands utilizing 1, 2 diamines, 1, 3-diamines, substituted 1, 2 dionemonoximes, substituted 1, 3-dionemonoximes, substituted salicylaldehydes and mixtures thereof, such as bis (salicylaldehyde) ethylenediamine and bis (2, 3-butandione- monoxime) ethylenediimine. Examples of vanadium and manganese complexes involving oxyonions are sulfate, nitrate, and carboxylates, e.g., acetates. 
     As will be recognized by those skilled in the art, the stability of the complexes formed will often be affected by the pH of the aqueous composition employed in the present contacting step. Some stability of the complex or complexes may have to be sacrificed because of the pH of the aqueous composition during the contacting, which pH may be preferred for various processing reasons. This reduced complex stability has surprisingly been found not to have an undue adverse effect on oxidation. The particular pH employed can also affect the salt form of the complexing agent employed, and such complexing salts are complexing agents within the scope of this invention. 
     The presently useful metal complexes are preferably not fully complexed, with, for example, partial metal/ligand complexes, i.e., not fully complexed, at a ratio of ligand to metal which substantially reduces the redox cycling activity of the ligand complexes. This feature, i.e., active redox cycling complexes, apparently facilitates the ability of the metal species to rapidly cycle between oxidation states and/or to promote the desired oxidation. With vanadium complexes, the mole ratio of vanadium to ligand is more preferably about 1 to about 3, still more preferably to about 2, with iron complexes the mole ratio of iron to ligand is more preferably about 1 to about 3, more preferably to about 2, and with manganese complexes the mole ratio of manganese to ligand is more preferably about 1 to about 2.0, still more preferably to about 1.5. 
     Any suitable ligand system may be employed. The ligands are preferably derived from the group consisting of compounds containing acetylacetonate functionality, carboxylic acid functionality (more preferably containing up to about 15 carbon atoms per molecule), poly, more preferably three, carboxylic acid functionalities, substituted carboxylic acid functionality (more preferably containing up to about 15 carbon atoms per molecule) poly, more preferably three, substituted carboxylic acid functionalities, group and mixtures thereof. Particularly useful ligand systems are derived from the group consisting of compounds containing acetylacetonate functionality, citric acid functionality, tartaric acid functionality, nitrilotriacetic acid functionality, and mixtures thereof and their partial salts particularly, sodium, potassium and ammonium partial salts, and partial esters and substituted derivatives thereof. Particularly preferred species are citric acid, tartaric acid and nitrilotriacetic acid and their partial salts and esters thereof as illustrated above. 
     The specific amount of the metal redox couple or metal component, e.g., metal complex, employed may vary over a wide range and depends, for example, on the carbonaceous ore and/or the metal redox couple/metal component employed, and on the degree of oxidation desired. 
     In certain embodiments, preferred concentrations of the metal complex are in the range of about 150 to 10,000 ppm, more preferably about 200 to about 1,000 ppm., or to about 5000 ppm, by weight based upon the aqueous composition employed in the contacting, calculated as elemental metal. It is generally convenient to provide the metal complex in combination with, preferably in solution in, the aqueous composition used in the contacting step. 
     The metal complex can be added to the contacting step and/or can be formed in situ prior to or in the course of the contacting. 
     The present contacting preferably takes place in the presence of an aqueous liquid medium or composition. The metal redox couples or metal components, which are preferably soluble in the aqueous medium, may be added to the aqueous medium prior to the contacting. Any suitable, aqueous medium can be employed in the present process. The pH of the aqueous medium may be acidic, neutral or basic depending, for example, on the composition of the ore or ores being treated, the specific metal redox couple or metal component being employed, and the presence or absence of other components or entities during the contacting. Preferably, the pH of the aqueous composition is in the range of about 1 or less to about 13, e.g., about 10,  or more. The pH of the aqueous medium may be adjusted or maintained, e.g., during the contacting step, for example, by adding acid and/or base. 
     In certain embodiments, the pH of the aqueous composition may be in the range of about 0.1, preferably about 0.5, to about 5, or in the range of about 1.5 to about 4.5, or about 3.0 and lower. In other embodiments, the pH of the aqueous composition may be in the range of about 1 or 1.5 to about 3.0 or about 1 or 1.5 to about 2.5. 
     In still other embodiments, the contacting preferably occurs at a slightly acidic pH, i.e., a pH no lower than about 6, or at an alkaline pH. If a vanadium complex is present, the contacting is more preferably conducted at a pH in the range of about 6 to about 13, while if an iron complex is present, the pH is more preferably about 6.5 to about 9.5. For manganese complex the pH is preferably about 7.5 to about 10.5. These more preferred pH ranges are particularly useful when it is desired to maintain the metal redox couple or metal component substantially soluble, e.g., in the aqueous medium, at the contacting conditions. 
     The aqueous medium comprises water, preferably a major amount of water. The medium is preferably substantially free of ions and other entities which have a substantial detrimental effect on the present process. Any suitable acid and/or base or combination of acids and/or bases may be included in, or added to, the medium to provide the desired pH. For example, hydrogen halides, preferably hydrogen chloride, sulfurous acid, sulfuric acid, metal salts which decompose (in the aqueous medium) to form such acids, alkali metal hydroxides, alkaline earth metal hydroxides, ammonium hydroxide, metal salts which decompose (in the aqueous medium) to form such bases, their corresponding carbonates, preferably sodium carbonate, mixtures thereof and the like may be employed. The quantity and composition of the aqueous medium may be selected in accordance with the requirements of any given ore to be treated and as may be found advantageous for any given mode applying the present process in practice. In carrying out the present process, one or more wetting agents and/or sulfur dispersion agents can be included in, e.g., added to, the aqueous composition (in addition to the metal redox couples or metal components) to further enhance rates and/or yields. Examples of such agents include hydrocarbon sulfonates, lignosulfonates, alkyl substituted succinic anhydrides, alcohol ethoxylates and the like. 
     The amount of metal redox couples or metal components employed may vary widely provided that such amount is effective to function as described herein. Such metal redox couples or metal components are preferably present during said contacting in an amount less than about 2%, more preferably in the range of about 10 ppm. to about 1% by weight, calculated as elemental metal, based on the amount of ore present and/or liquid present during contacting such as a solution used in an agitated leach or during a vat or heap leach. One of the substantial advantages of the present process is that large amounts of metal redox couples or metal components are not required although adjustments can be made depending on the deleterious carbon concentration in the ore. Thus, in order to reduce costs still further while achieving benefits of the present invention, low concentrations of such materials are preferably selected The mole ratio of complexing agent to metal ion that is used to form the promoter component may be in the range of about 0.01to 5, for example about 0.5 to about 2.0. Preferred concentrations of metal redox couples or metal components are in the range of about 20 to 10,000 ppm, more preferably about 50 to about 1,000 ppm. or to about 5,000 ppm by weight, based upon the aqueous composition, calculated as elemental metal. 
     The present contacting is preferably conducted in the presence of at least one oxidant other than the metal redox couple or metal component or the reducible manganese The oxidant is present in an amount effective to do at least one of the following: maintain or form the metal redox couple or metal component, produce or regenerate at least a portion of the metal redox couple or metal component, and/or oxidize at least a portion of the carbonaceous material in the ore. The oxidant or oxidants may be present during the contacting step and/or during a separate step to form and/or regenerate the metal redox couple or metal component. Any suitable oxidant capable of performing one or more of the above-noted functions may be employed. The oxidant is preferably selected from the group consisting of molecular oxygen (e.g. in the form of air, dilute or enriched air, or other mixtures with nitrogen or carbon dioxide), singlet oxygen, ozone, inorganic oxidant components containing oxygen and at least one second metal and mixtures thereof. More preferably, the oxidant is selected from the group consisting of molecular oxygen, oxidant components containing oxygen and at least second metal and mixtures thereof. Still more preferably, the oxidant is selected from the group consisting oxygen, oxidant components containing oxygen and at least one second metal and mixtures thereof. One particularly preferred system involves an oxidant component containing oxygen and at least one second metal, and molecular oxygen in an amount effective to maintain the oxidant component in the desired oxidized state and/or to oxidize at least a portion of the carbonaceous material in the ore. Care should be exercised to avoid large excesses of the oxidant to as to minimize reactions that could solubilize deleterious elements, i.e., arsenic, etc. The amount of oxidant employed is preferably in the range of about 10 to about 200%, preferably about 80% to about 140% of that needed to oxidize the carbonaceous ore to allow for improved liberation of the metal to be recovered in the present process. 
     The reducible second metal oxidants useful in the present invention may be chosen from a wide variety of materials. The second metal or metals are preferably not the same as the metal or metals to be recovered from the ore or ores. Preferably, the second metal is a metal which forms reducible metal oxides which are reduced during the conduct of the process of this invention. Many of the transition metals have this property. Typical examples of metals which have this property include minerals and other compounds which are generally solids under the condition of the process, such as, manganese, tin, lead, bismuth, germanium, antimony, indium and certain of the rare earth metals and minerals, e.g., cerium, praseodyminium and terbium and mixtures of rare earth minerals which typically have varying ratios of lanthanum, cerium, etc. Such reducible second metal components are preferably capable of becoming at least partially reduced at the present contacting conditions to form a reduced second metal component. 
     The present contacting results in at least a portion of the reducible second metal component being chemically reduced to form a reduced second metal component. This reducible/reduced second metal component can exit the contacting zone and be separated from the ore or ores, in particular the contacted ore or ores, i.e., partial to substantial separation. This component can be used on a once-through basis, or may be regenerated to reducible second metal component, in situ or externally and recycled to the contacting zone. In the case of a once-through basis, it is preferred to minimize the amount of reduced second metal component exiting with the ore or ores. Such regeneration can be done by electrochemically (preferably external) oxidizing the reduced second metal component or oxidizing the reduced second metal component with molecular oxygen, in situ or external, preferably promoted for purposes of enhanced yield and rate, at ambient and/or elevated temperatures to convert the reduced second metal component to a reducible second metal component. 
     Manganese is a more preferred second metal. In one embodiment, the reducible manganese component includes manganese in the 4+ oxidation state. One particularly useful reducible manganese component is manganese (manganic) dioxide and its pyrolusite, manganite, birnessite and manganese-bearing minerals from the spinel group. Silver, manganese-containing ores in which at least a portion of the silver is locked by the manganese-bearing minerals are particularly useful in combination with ores containing carbonaceous material, as described herein. A second preferred embodiment is redox active manganese +3 where the manganese is complexed as above and is capable of reoxidizing one of the other metal complexes and/or metal components set forth above, such as vanadium under the process condition of pH, for example, at pH&#39;s greater than about 7. It is contemplated that the first and second reducible manganese components can be the same or different or mixtures thereof. In the above embodiment, it is preferred to have present molecular oxygen during processing. The latter system provides substantially soluble components for recovery of metal. 
     The amount of oxidant employed in the present invention is chosen to facilitate the desired functioning of the present contacting step. Without limiting the invention to any specific theory or mechanism of operation, it may be postulated that when oxidant is employed such oxidant acts in conjunction with the metal redox couple or metal component to oxidize at least a portion of the carbonaceous material in the ore and &#34;liberate&#34; the metal to be recovered from the ore. Although the metal redox couple or metal component may take an active part in the oxidation and liberation functioning, when oxidant is employed, such metal redox couple or metal component preferably acts as a catalyst and may be, and preferably is, used more than once in the present contacting step, e.g., is recycled to the present contacting step or is employed to contact more than one increment of the ore or ores. 
     The amount of oxidant employed preferably acts to facilitate the desired oxidation of at least a portion of the carbonaceous material and liberation of metal to be recovered from the ore. The specific amount of oxidant employed varies depending on many factors, for example, the specific ore or ores being treated, the specific metal redox couple, metal component and oxidant being employed, and the specific degree of oxidation and metal liberation desired. If a reducible second metal oxidant is used, it preferably is used in an amount in the range of about 0.1% or less to about 10% or more to about 150% by weight of the metal sulfide or deleterious carbon content of carbonaceous ore. Preferably, the amount of second metal component employed in the present contacting step should be sufficient to provide the oxidation/metal liberation to the desired degree. More preferably, the amount of second metal component employed should be about 40% to about 250%, more preferably about 80% to 120%, of that required to achieve the desired degree of metal and/or sulfide and/or carbon oxidation. Substantial excesses of second metal component should be avoided since such excesses may result in materials separation and handling problems, and may result in reduced recovery of the desired metal or metals. 
     Although one or more of the oxidants may be utilized in a separate oxidation or regeneration step, it is preferred that such oxidants, and in particular reducible second metal components, be present and effective during the contacting step of the present invention. 
     The contacting of the present invention takes place at a temperature and pressure and for a time sufficient to obtain the desired results. A combination of temperature and pressure effective to maintain water (the aqueous medium) in the liquid state is preferred. In one embodiment, temperatures of about 20° to about 140° C. with temperatures in the range of about 20° C. to about 110° C. and in particular between about 25° C. to about 80° C. being especially useful. Contacting pressure may be in the range of about atmospheric to about 500 psia or more. Pressures in the range of atmospherio to about 100 psia have been found to provide satisfactory results. 
     Contacting times vary widely depending, for example, on the mode in which the contacting is performed. Such contacting time may range from minutes to weeks or even months. For example, if the contacting occurs in a stirred tank with the ore or ores present in a slurry with the aqueous medium and the metal redox couple or metal component, the contacting time preferably is in the range of about 0.1hours to about 60 hours, more preferably about 1 hour to about 24 hours. On the other hand, if the contacting takes place with the ore or ores placed in a heap with the aqueous medium and metal redox couple or metal component being made to flow through the heap, the contacting time is preferably in the range of about 1 day to about 6 months, more preferably about 7 days to about 60 days. 
     The present process may be conducted on a batch or continuous basis. The present contacting step may be conducted on a pad, with the ore or ores to be treated situated in a heap; or in a vat, tank or other suitable arrangement. The primary criterion for the contacting step is that the desired carbonaceous material oxidation and metal liberation take place. Preferably, the metal-containing carbonaceous ore and the oxidant and the metal redox couple or metal component are brought together to form an intimate admixture generally with the aqueous composition. The ore or ores are preferably subjected to particle size reduction, e.g., by crushing, grinding, milling and the like, prior to contacting to render the ore or ores more easily and/or effectively processed in the present contacting step. Air or other gaseous oxidant may be dispersed through, or otherwise contacted with, this admixture during the contacting step to achieve the desired result. Amounts of acid and/or base and/or ferric ion can be added to the initial admixture and/or may be added during the contacting to provide the desired pH and ferric ion concentration. 
     The pH of the aqueous liquid medium may be adjusted or maintained during the contacting step, for example, by adding one or more basic components to the aqueous liquid medium. Any suitable basic component or combination of such components may be included in, or added to, this medium to provide the desired basicity. For example, basic alkali metal and alkaline earth metal components, e.g., hydroxides, silicates, carbonates and bicarbonates, mixtures thereof and the like may be employed. Because of cost, availability and performance considerations, calcium hydroxide, sodium hydroxide, sodium carbonate, and mixtures thereof are preferred. 
     If bacteria are employed, it is preferred that this intimate admixture also include the bacteria. If bacteria are utilized, the aqueous composition preferably includes one or more nutrients useful by the bacteria. One or more of these nutrients may be included with one or more of the ores, sulfide material, reducible manganese-containing material, intimate admixture and aqueous composition. 
     The solid ore/material remaining after the contacting step may be subjected to any suitable metal recovery processing step or steps for the recovery of the metal, e.g., silver, gold, the platinum group metals and the like. For example, this solid ore/material may be neutralized with any suitable acidic or basic material, such as sulfuric acid, carbonates, bicarbonates white lime or milk of lime, and then subjected to a conventional sodium cyanide extraction, followed by activated carbon treatment and zinc dust precipitation. Alternately, the solid ore/material after contacting can be neutralized and subjected to an ammonium thiosulfate or an acid thiourea extraction followed by zinc dust precipitation. Still further, the solid ore/material after contacting can be subjected to a brine extraction followed by ion exchange to recover the desired metal or metals. The conditions at which these various recovery processing steps take place are conventional and well known in the art, and therefore are not described in detail here. However, it is important to note that conducting the metal recovery processing on the ore/material after the contacting of the present invention provides improved metal recovery performance relative to conducting the same metal recovery processing without this contacting. 
     In a further embodiment of this invention the contacting step and metal, e.g., silver, gold, platinum group metals and the like, recovery step can be practiced at the same time in the same processing system, i.e., agitated, vat or heap. The pH of both systems should be similar to avoid any deleterious side reactions e.g., destruction of the cyanide solution or thiourea. For example, the metal redox couples and metal components which are effective at higher pH&#39;s, e.g., about 7 to about 13, can be used in the presence of cyanide leaching solution to provide both liberation and recovery of metals in the same system. Particularly preferred metal complexes are the soluble redox active complexes of vanadium, iron, manganese and mixtures thereof, in particular those complexes wherein the ligands are derived from compounds having polycarboxylic acid functionalities and substituted polycarboxylic acid functionalities and the preferred ranges, substituents and species as set forth above. 
     One processing arrangement which provides outstanding results involves the agglomeration of, for example, the metal-containing carbonaceous are and reducible second metal component. The ore, ores and/or materials are preferably subjected to crushing, grinding, or the like processing to reduce particle size to that desired optimum metallurgical liberation, generally a maximum particle diameter of about 1/2 inch or less. The solid particles are mixed with sufficient aqueous liquid and if desired, promoter and bacteria. This intimate admixture is formed into agglomerates by conventional processing, such as agglomeration, extruding, pilling, tableting and the like. 
     The agglomerates are placed on a pad, to form a heap which is built up by addition of agglomerates, preferably over a period of time in the range of about 15 days to about 60 days. During the time the heap is being built up, and preferably for a period of time ranging up to about 3 months, more preferably about 2 months to about 3 months after the last agglomerates are added to the heap, an aqueous composition containing the metal redox couple and/or component and preferably adjusted for pH, ferric ion and/or the presence of air, is made to flow through the heap, e.g., from the top to the bottom of the heap. If bacteria are used, the aqueous composition includes one or more nutrients for the bacteria. After contacting the heap, the aqueous composition is collected and processed for disposal; or processed for manganese, second metal and/or metal redox couple and/or metal component metal recovery, regeneration and/or recycling to the heap. This contacting provides another important benefit in that at least a portion of the &#34;cyanacides,&#34; such as copper, which may be present in the ore and/or metal sulfide-containing material is removed and/or deactivated. Such &#34;cyanacides&#34; cause substantial increases in cyanide consumption if present in cyanide extraction processing. Therefore, removing and/or deactivating cyanacides in the present contacting step provides for more effective metals recovery by cyanide extraction. 
     After the heap-aqueous composition contacting has proceeded to the desired extent, an aqueous basic (e.g., white lime, milk of lime or the like basic components) composition is contacted with the heap to neutralize the heap if a pH below 7 was used. After this neutralization, the agglomerates may be placed on a second heap, which is preferably larger than the heap previously described. 
     In addition, the neutralized agglomerates may be broken apart and reagglomerated prior to being placed on the second heap to provide for any incidental neutralization and/or to expose the treated ore for subsequent cyanidation. This can be done using conventional means, such as subjecting the agglomerates to grinding, milling or the like processing, and then forming the second agglomerates by agglomeration, extruding, tableting, pilling, pelletizing or the like processing. 
     In any event, if a second, preferably larger, heap is formed on a pad, or if one heap is used, then a dilute aqueous cyanide, preferably sodium cyanide, solution is made to contact the heap. Typically, this cyanide contacting is performed in the presence of air. Preferably, the cyanide solution is percolated through the heap. The cyanide solution, after being contacted with the heap, contains the metal or metals to be recovered. This solution is collected and sent to conventional further processing for recovery of the metal or metals. 
     Both heaps are preferably maintained at ambient conditions e.g., of temperature and pressure. Also, both heaps may be built up and worked (contacted) with the aqueous composition and the cyanide solution for as long as the economics of the particular application involved remain favorable. 
     When an agitated leach in vessels is used for the process, contact times may vary depending, for example, on the specific ore or ores being contacted, the other components present during the contacting and the degree of metal recovery desired. Contact times in the range of about 5 minutes or less to about 48 hours or more may be used. Preferably, the contact time is in the range of about 4 hours to about 36 hours, more preferably about 8 hours to about 24 hours. During this time, agitation can be advantageously employed to enhance contacting. Known mechanical mixers can be employed. 
    
    
     The following non-limiting examples illustrate certain of the advantages of the present invention. 
     EXAMPLE I 
     A quantity of a high carbonaceous ore was selected for bench scale testing. The experiment employed 1000 grams of ore (75% minus 65 mesh) which produced 33 weight percent solids of an aqueous fraction. The system was agitated with air sparging and suspended in a water bath maintained at 50° C. The conditions and results of this experiment is summarized as follows: 
     Conditions: The aqueous fraction included 0.5% by weight of vanadium, as vanadium citrate (1.74 mole citrate, per mole vanadium); and 10 grams of manganese dioxide. Twenty-four hours stirring with air was used. The ore was analyzed as containing large quantities of carbonaceous material and had a gold content of 0.051 ounces per ton. The gold recovery by conventional cyanidation after 72 hours based on Head vs Tail Analysis was 57.8%. 
     Results: The ore after processing was subjected to cyanidation in the same manner as the untreated ore and a gold recovery of 80% was achieved. 
     These results show the outstanding effectiveness of a combination of metal, particularly vanadium complexed with ligands and an oxygen transfer agent such as manganese dioxide for the recovery of gold from a highly carbonaceous ore. These examples also show the cyclic redox activity of the metal/ligand catalysts is effective to provide for substrate oxidation and a process which produces enhanced gold recovery. 
     While the present invention has been described with respect to various specific examples and embodiments, it is to be understood that the present invention is not limited thereto and that it can be variously practiced within the scope of the following claims.