Deepsea Ventures, Inc.

Paul H Cardwell

William S Kane

Richard G Sandberg

Bruce E Barton

Harold H Schobert

Roger C Field

James A Olander

Hugh L McCutchen

This invention provides a two-stage leaching procedure for manganese nodules for obtaining directly from a second leaching stage a substantially pure stream of copper free of other metal values, the other metal values, including manganese, nickel and cobalt, having been previously extracted in an earlier leaching stage. Both leaching operations are carried out utilizing an ammoniacal aqueous solution on a reduced manganese nodule.

Simultaneous extraction of metal values other than copper from manganese

This invention provides a two-stage leaching procedure for manganese nodules for obtaining directly in one leaching stage the metal values other than manganese in one ammoniacal aqueous solution. The manganese nodules are reduced and then leached initially utilizing a solution of an ammonium salt, e.g., ammonium sulfate, to selectively leach out the manganese value, followed by a second stage leaching with an ammoniacal solution, to leach out the nickel, cobalt and copper values. The nickel, cobalt and copper values can then be individually separated from the second leach solution by liquid ion exchange extraction.

Extraction of metal values from manganese nodules

This invention provides a leaching procedure for manganese nodules for obtaining directly from a leaching stage all of the metal values, including manganese, utilizing an ammoniacal aqueous solution. The manganese nodules are reduced and then leached utilizing an ammoniated solution of an ammonium salt comprising at least about 150 grams per liter of ammonium ion and at least 0.83 Normal in the anion, other than hydroxyl. The resultant leach solution comprises the dissolved manganese, nickel, cobalt and copper values from the nodule ore, and can subsequently be treated, as by liquid ion exchange, to separate out the individual metal values.

Process for the simultaneous extraction of metal values from manganese

Ocean floor nodules are treated with halogenating agents to produce a pregnant leach solution which is subjected to selective solvent extraction to isolate metal values contained in the ore.

Method for separating metal constituents from ocean floor nodules

This invention provides a method for selectively extracting cobalt value from an aqueous ammoniacal solution containing dissolved nickel and cobalt. The solution is contacted, at a pH of at least about 8.5, with an organic solution of a hydrocarbon-substituted 8-hydroxyquinoline while maintaining the pH of the aqueous solution at least at about 8.5. by adding ammonia or ammonium hydroxide. There are also dissolved in the aqueous solution ammonium ion and halide ion. The cobalt value is selectively extracted into the organic solution which is then separated from the aqueous solution; the cobalt can be stripped from the organic solution.

Separation of cobalt from nickel in ammoniacal solutions using

This invention provides a method for treating manganese oxide ores in an aqueous medium, with hydrogen halide or sulfuric acid, and a hydrogen sulfide or a metal sulfide, e.g. an ore. A leach liquor containing the desirable metal halides is then separated from the solid, insoluble residue. Any iron value in either the manganese oxide ore or in any metal sulfide ore present is not dissolved or is converted to an insoluble iron oxide. Elemental sulfur is also obtained. The metal values in the leach liquor are recovered by crystallization of the manganese halide and liquid ion exchange extraction of the other metal values present.

Refining of manganese oxide ores

This invention provides a halidation process for obtaining a high purity manganese oxide from a manganiferous ore, while reclaiming a substantial portion of the hydrogen halide reagent. The process comprises halidating the ore with a hydrogen halide and leaching to form the corresponding halogen and an aqueous solution comprising dissolved manganese halide and ferric halide. The hydrogen halide can be in the gaseous state and/or dissolved in the aqueous leach solution. The manganese halide and the ferric halide are preferably individually separated from the leach solution by crystallization and by selective extraction, respectively. The crystallized manganese halide is reacted with water at a temperature of from about 400.degree. C to about 700.degree. C to yield the corresponding hydrogen halide, which is recycled, and manganese oxide. In one embodiment, a concentrated leach solution is formed at a temperature of at least about 90.degree. C using at least some gaseous hydrogen halide as the reagent, the solution having a concentration of manganese halide greater than the saturation concentration at ambient temperaures. The solution is then cooled to ambient and the manganese halide crystallized out. The ferric halide is then extracted from the solution. In a second embodiment, the ferric halide is first extracted from the leach solution and the manganese halide is then crystallized by evaporating the gaseous solution. If other nonferrous metal values are present, these can be removed by precipitation or cementation. Any remaining aqueous liquid is preferably recycled.

Halidation of manganiferous ore to obtain metal values and recovery and

This invention provides a process for obtaining the nonferrous metal values from a manganese oxide ore, by reacting the ore with an aluminum halide or a ferric halide at a temperature of at least about 50.degree. C and preferably, at least about 130.degree. C. The manganese oxide ore can be treated with or without reduction. If reduction of the manganese oxide ore is desired, it can be accomplished prior to, or simultaneously with, the reaction with the aluminum halide or ferric halide. The resulting nonferrous metal halides can be separated from the reacted ore residue by conventional methods such as leaching or evaporation.

Halidation of nonferrous metal values in manganese oxide ores

This invention provides a process for separating the halide of cobalt, and optionally nickel, from a pregnant aqueous solution, the aqueous solution also containing a manganese halide. The process comprises initially extracting the cobalt halide and a portion of any manganese halide which is present into an organic extract. The nickel halide is then separately extracted from the solution. The manganese halide is preliminarily preferentially stripped from the organic extract containing cobalt and manganese utilizing an aqueous solution comprising halide ions. The cobalt halide in the extract can then be stripped into an aqueous solution together with the remaining manganese to form a strip solution. The manganese is then preferentially extracted from the strip solution, leaving a manganese-free, substantially pure cobalt solution. Any nickel can be selectively extracted from the manganese remaining in the pregnant solution.

Separation of nickel and cobalt and manganese in solution

A process is provided to produce pure elemental metal; such as manganese, by reacting a halide of the elemental metal with aluminum. The halide of the elemental metal is present as a molten pool wherein the temperature at the bottom of the pool is sufficient to maintain the elemental metal molten and the temperature at the top of the pool is below the boiling point of the metal halide in the pool. Aluminum halide is removed as a vapor overhead and a layer of molten metal collects at the bottom of the pool of molten halide.

Reduction method for producing manganese metal

Ocean floor nodules are treated with aqueous hydrogen halide to produce a pregnant leach solution which is subjected to selective solvent extraction to isolate metal values contained in the ore.

This invention provides a process for obtaining substantially pure manganese metal by the reduction of a manganese oxide or a manganese halide by reaction with a subhalide of a transport metal. The transport metal can be aluminum, silicon, or titanium. In preferred embodiments of this procedure, a continuous closed cycle process is carried out wherein the transport metal value is reconverted to its subhalide and recycled for reaction with additional manganese compound.

Reduction to manganese metal using metal transporting compounds

This invention provides a process for separating metal values from an anhydrous mixture of metal halides in a fluid state, i.e. vapor or liquid; the separation is made by contacting a fluid mixture containing a halide of at least one less-noble metal selected from the group consisting of iron and manganese, and a halide of at least one more-noble metal selected from the group consisting of copper, cobalt and nickel, with an elemental metal. This procedure is especially effective in the refining of ocean floor nodule ores.

Direct recovery of metals from fluid anhydrous metal halides derived

This invention provides a process for selectively removing metal values from ocean floor nodule ore by a two-stage procedure. In the first stage, the ore is leached with an aqueous solution of sulfuric acid or a hydrogen halide to preferentially remove nickel and copper. In the second stage, the ore is leached with a reducing agent to preferentially remove cobalt and manganese. The two leach solutions can then be further treated to separate the individual metal values, e.g., by liquid ion exchange procedures.

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Zanoni, VA, United States of America

Paul H Cardwell