Amax Incorporated

Allied Chemical Corporation

Dale K Huggins

Leo W Beckstead

Paul B Queneau

Robert F Hogsett

Eddie C Chou

John M Laferty, Jr

Mark H Berggren

Lowell R Anderson

Malcolm T Hepworth

Edward I Wiewiorowski

Francis J Smit

Robert C Ziegler

Fred J Gefri

John D Bruno

Ben W Wiegers

Kurt R Anast

Craig B Barlow

Lawrence F McHugh

Ammonium octamolybdate-alpha is formed by reacting powdered molybdenum trioxide with a solution of ammonium dimolybdate in water at the boiling temperature until thickening of the slurry occurs, after which the slurry is digested, filtered hot and the separated precipitate is dried.

Ammonium octamolybdate-alpha

Powdered coal is upgraded in utility and heat value by removal of ash and pyrite constituents by successively pressure caustic leaching the coal slurry at a temperature of at least about 175.degree. C., hydrochloric acid leaching the caustic leached coal to dissolve ash and pyrite residues not dissolved by the caustic, and pressure leaching the acid leached coal to remove alkali metals and chloride. Vanadium is also removed by the process.

Chemical leaching of coal to remove ash, alkali and vanadium

A process is provided for converting MoS.sub.2 to MoO.sub.2 wherein, MoS.sub.2 in particulate form is fed into a reactor while flowing MoO.sub.3 vapor therein to effect reaction thereof with MoS.sub.2 to form MoO.sub.2. The temperature in the reactor is maintained at a level sufficient to cause the reaction to go forward. A portion of the MoO.sub.2 is removed from the reactor as a product and the remainder is selectively oxidized at a temperature sufficient to generate gaseous MoO.sub.3 which is recycled to the reactor relative to the flow of MoS.sub.2 therein to convert the MoS.sub.2 to MoO.sub.2.

Process for the production of molybdenum dioxide

A process is provided for removing hexavalent selenium from an acidic sulfate solution containing at least one metal ion from the group consisting of nickel, cobalt and copper at ambient pressure and at a temperature not exceeding the boiling point of the solution. The solution is treated with an agent from the group consisting of a compound which will produce nascent hydrogen in the solution and finely divided metal from the group consisting of nickel, cobalt and copper resulting from in situ precipitation of the metal in the acid sulfate solution. Thus, following treatment with the compound, the hexavalent selenium is reduced to a form separable from the solution by solid-liquid separation.

Removal of hexavalent selenium from nickel, cobalt or copper sulfate

A hydrometallurgical process is provided for the recovery of molybdenum values from a molybdenum disulfide concentrate containing copper. The process comprises forming an aqueous slurry of finely divided molybdenum concentrate of carbonates and hydroxides of alkali metals, and pressure leaching the slurry in the presence of oxygen at an elevated temperature and pressure for a time sufficient to effect conversion of the contained molybdenum values to alkali metal molybdate and provide a residue containing copper oxide or basic copper carbonate from which copper is later recovered. The molybdenum values are recovered from solution by solvent extraction and the solvent thereafter stripped of the molybdenum as ammonium molybdenum using ammonium hydroxide. The molybdenum is recovered as crystals of ammonium molybdate by crystallization, e.g., by evaporating the stripping solution.

Process for recovering molybdenum and copper from sulfide concentrates

Vanadium and nickel values are selectively recovered from a petroleum coke residue by slurrying the coke in an aqueous solution of sodium carbonate providing an excess of the stoichiometric amount of sodium for formation of sodium vanadate and sodium sulfate, and then digesting the slurry at moderately elevated temperature in a pressurized autoclave under an oxygen overpressure supplying at least the stoichiometric amount of oxygen based on the vanadium and sulfur content of the slurry and advantageously sufficient additional oxygen to provide the thermal requirements of the digestion step by oxidation of carbon. In a continuous embodiment, the feed slurry temperature and feed solids content are adjusted according to a substantially inversely correlated relationship. The digestion temperature for a given total pressure and gas flow rate in the autoclave is adjusted to generate a pregnant liquor containing about 20 gpl to about 100 gpl of vanadate (V.sub.2 O.sub.5) from which at least about 50% of the input water has been converted to steam during the digestion. The vanadate liquor is separated from the digestion residue, which is then sequentially selectively leached for recovery therefrom of nickel and residual vanadium values.

Recovery of V.sub.2 O.sub.5 and nickel values from petroleum coke

A process for the soda ash digestion of scheelite concentrates is provided, the process comprising forming a slurry of a scheelite concentrate in an aqueous sodium carbonate solution and then digesting the slurry in an autoclave at an elevated temperature of at least about 180.degree. C. The concentration of the Na.sub.2 CO.sub.3 solution is substantially inversely correlated to the digestion temperature and substantially directly correlated to the Na.sub.2 CO.sub.3 /WO.sub.3 weight ratio such as to effect the selective dissolution of at least about 95% of the WO.sub.3 in the concentrate and provide a pregnant liquor containing WO.sub.3 while inhibiting substantial dissolution of gangue minerals.

Autoclave soda digestion of scheelite concentrates

A process for conditioning a tungsten concentrate containing tungsten as WO.sub.3, sulfur as sulfide, and calcite to fix at least a portion of the sulfur as calcium sulfate by reaction with the calcite, comprises providing a tungsten concentrate having a calcite content such that less than about 15 wt. % calcium sulfate based on the weight of the WO.sub.3 in the concentrate will be formed and heating the concentrate to a temperature of at least about 500.degree. C. in an oxidizing atmosphere to oxidize substantially all the sulfur in the concentrate to provide a conditioned concentrate having a calcium sulfate content less than about 15% based on the weight of the WO.sub.3, whereby the conditioned concentrate can be efficiently leached with alkali metal carbonates or hydroxides and the resulting alkali metal tungstate solution can be effectively treated to recover an ammonium tungstate solution.

Process for conditioning tungsten concentrates

A process for extracting tungsten values from an aqueous phase into an organic phase, comprises

Solvent extraction of tungsten from aqueous tungstate solutions

A continuous process with feedback control is disclosed for the soda ash digestion of tungsten concentrates in which a slurry of the concentrate in an aqueous sodium carbonate solution is digested in an autoclave at a temperature of at least about 180.degree. C. to provide a pregnant solution of WO.sub.3. High dissolution efficiency is maintained during digestion by continuously monitoring the pregnant solution which includes determining the specific gravity and the Na.sub.2 CO.sub.3 concentration of the pregnant liquor from which feedback signals are produced which are used to control the amount of Na.sub.2 CO.sub.3 and H.sub.2 O fed to the slurry in accordance with the digestion conditions predetermined to provide the desired dissolution efficiency.

Autoclave soda digestion of scheelite concentrates with feedback control

A process for the soda ash digestion of refractory tungsten concentrates is provided, the process comprising forming a slurry of the concentrate in an aqueous solution to which sodium carbonate is added in stages while digesting the slurry in an autoclave at a selected elevated temperature of at least about 180.degree. C. to control the concentration of the sodium carbonate during digestion to provide high extraction yields of the contained WO.sub.3. The total amount of the Na.sub.2 CO.sub.3 added stage-wise to complete the digestion is substantially inversely correlated to the digestion temperature and substantially directly correlated to the Na.sub.2 CO.sub.3 /WO.sub.3 weight ratio such as to effect dissolution of at least about 97%, and generally at least about 98%, of the WO.sub.3 in the concentrate and provide a pregnant liquor containing WO.sub.3, the stage-wise addition of the sodium carbonate being such as to inhibit the dissolution of gangue minerals, such as silica, contained in the concentrate.

Autoclave soda digestion of refractory scheelite concentrates

A process for the soda digestion of mixed wolframite and scheelite concentrates is provided, the process comprising forming a slurry of the mixed wolframite and scheelite concentrates in an aqueous sodium carbonate solution and then digesting the slurry in an autoclave at a temperature of at least about 180.degree. C. During digestion a predetermined amount of sodium hydroxide is added calculated stoichiometrically to react with NaHCO.sub.3 formed as a result of the hydrolysis of FeCO.sub.3 or FeCO.sub.3 and MnCO.sub.3 produced during the digestion of the wolframite and convert it to Na.sub.2 CO.sub.3. The concentration of the Na.sub.2 CO.sub.3 solution is substantially inversely correlated to the digestion temperature and substantially directly correlated to the Na.sub.2 CO.sub.3 /WO.sub.3 weight ratio ranging from about 0.9 to 2 such as to effect dissolution of at least about 95% of the WO.sub.3 in the concentrate and provide a pregnant liquor containing said WO.sub.3.

Combined autoclave soda digestion of wolframite and scheelite

A calcium tungstate concentrate is produced by slurrying an aqueous sodium tungstate liquor with calcium carbonate at about 130.degree. C. to about 200.degree. C. while providing sufficient carbon dioxide overpressure to convert sodium carbonate in the slurry to sodium bicarbonate, wherein the conversion of sodium tungstate to solid calcium tungstate in the slurry is promoted. The carbon dioxide is then stripped from the slurry, causing the sodium bicarbonate to convert to sodium carbonate, and a calcium tungstate concentrate is filtered from the slurry. The invention is useful in upgrading impure calcium tungstate concentrates.

Autoclave tungstate upgrading of scheelite concentrates

Basic sodium tungstate leach liquor is treated to reduce the concentration dissolved therein of silica, phosphorus and fluorine impurities in a process which comprises providing a small but effective amount of magnesium in the liquor to maximize removal of silica and phosphorus from solution in the liquor while maintaining the liquor temperature between about 60.degree. C. and about 100.degree. C. and the liquor pH between about 9 and about 11, filtering the liquor, adjusting the liquor pH to between about 6 and about 8 and the liquor temperature to between about 20.degree. C. and about 60.degree. C., and then providing a small but effective amount of aluminum hydroxide in the filtered liquor to maximize removal of fluorine from solution in the liquor while maintaining the liquor temperature between about 20.degree. C. and about 60.degree. C. and the liquor pH between about 6 and about 8.

Treatment of sodium tungstate leach liquor containing dissolved silica,

A process is disclosed for recovering tungsten and molybdenum values from tungsten concentrates containing molybdenum in an amount at least about one-twentieth of the amount of contained WO.sub.3. The concentrate, generally a wolframite concentrate, is subjected to dissolution in hot NaOH solution to provide a pregnant liquor or solution containing tungsten and molybdenum values. The solution, after purification, is treated with a sulfide precipitation agent to precipitate MoS.sub.3 and some WS.sub.3 using a stoichiometric excess of a sulfide precipitating agent to produce a filtrate containing tungsten substantially free of molybdenum. The sulfide precipitate is dissolved in dilute NaOH solution and again precipitated using a stoichiometric deficient amount of the sulfide precipitating agent to produce a precipitate of MoS.sub.3 low in tungsten. The foregoing sulfide precipitation steps may be reversed.

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Golden, CO, United States of America

Dale K Huggins