Process for the recovery of antimony values from ores containing sulfo- antimony compounds of copper, and arsenic

摘要

Tetrahedrite ore concentrate, sodium sulfide added as such or formed in situ, calcium values preferably supplied as lime, and a reducing agent, e.g. coke, are smelted for a period sufficient to convert a major portion or substantially all of the antimony to a water-soluble sodium compound of antimony and sulfur and a major portion or substantially all of the arsenic also contained in the concentrate to a water-insoluble calcium compound of arsenic and oxygen. The sodium sulfide is incorporated into the charge for the smelting in an amount sufficient to convert at least a major portion of the antimony into the water-soluble sodium compound of antimony and sulfur; and the lime is incorporated into the smelting charge in amount sufficient to convert at least a major portion of the arsenic into the water-insoluble calcium compound of arsenic and oxygen. A soda matte obtained from the smelting and containing the soluble sodium compound of antimony and sulfur and the insoluble calcium compound of arsenic and oxygen as well as a water- insoluble sulfur compound of copper is leached with an aqueous liquid, ordinarily water, to dissolve substantially only the soluble sodium compound of antimony and sulfur. The aqueous leach solution containing the soluble sodium compound of antimony and sulfur is separated from an insoluble leach residue containing the insoluble calcium compound of arsenic and oxygen and the insoluble sulfur compound of copper. BACKGROUND OF THE INVENTIONPP1. Statement of the InventionPPThis invention relates to the recovery of antimony values and more particularly to a process for the recovery of antimony values from ores or ore concentrates containing sulfo-antimony compounds of copper.PP2. Description of the Prior Art PPOres containing sulfo-antimony compounds of copper, such as tetrahedrite ore or ore concentrate, frequently contain arsenic as an impurity due to the arsenic substituting for some of the antimony in the tetrahedrite. The presence of the arsenic is undesirable as the chemistry of the arsenic follows generally that of the antimony, and consequently the arsenic reports in excessive amounts in the antimony upon recovery of the antimony from the tetrahedrite. Inasmuch as the specifications for market grade antimony call for, by weight, 0.05% maximum arsenic in one grade of antimony and 0.10% maximum arsenic in another grade thereof, and the arsenic usually reports in the antimony in amounts appreciably in excess of 0.10% by weight, the presence of the excessive amount of arsenic in the antimony is undesirable and disadvantageous from a commercial standpoint.PPU.S. Pat. No. 1,654,527 discloses the production of metallic antimony and alloys containing antimony and alkali metal arsenates from antimony-and arsenic-containing ores. Antimony trioxide is mixed with a stoichiometric amount of arsenic trioxide and heated in the presence of an alkali metal compound such as sodium carbonate or sodium hydroxide to obtain metallic antimony and an alkali metal arsenate in two separate layers. The alkali metal arsenate is recovered by leaching and crystallization. U.S. Pat. No. 1,523,980 discloses the removal of arsenic present in antimonial metals or antimonial lead by stirring the molten metal or alloy with caustic soda or soda ash to remove the arsenic without affecting the antimony. U.S. Pat. No. 1,097,897 discloses the extraction of antimony from its sulfide ores by melting the ore with sodium sulfate, carbon, iron sulfide and sodium carbonate to form the sulfo salt and oxide of antimony, removing the slag formed during the melting operation, smelting the sulfo salt and oxide of antimony with iron and carbon to form Sb, and recovering the iron sulfide and sodium sulfide from the slag formed during the reduction process by leaching to dissolve the sodium sulfide in the leaching water. U.S. Pat. No. 1,104,810 discloses the recovery of arsenic and antimony from ores by mixing the finely divided ore with sulfur and sodium sulfide or calcium sulfide. The quantity of sodium sulfide or calcium sulfide added to the ore is calculated to assure that the arsenic and antimony are converted into double sulfides with the sodium or calcium which are water-soluble, and can therefore be extracted by leaching in water. The resulting mixture is heated at a low temperature in a furnace and then leached. U.S. Pat. No. 3,709,680 discloses the removal of arsenic from a sulfo-ore concentrate such as, for example, tetrahedrite by leaching the sulfo-ore concentrate with an alkali metal sulfide solution which dissolves the arsenic to form an arsenic pregnant solution and an insoluble residue, separating the undissolved residue therefrom, acidifying the arsenic pregnant solution to precipitate arsenic and other mineral values as insoluble salts and to form an arsenic barren solution, and treating the arsenic barren solution to regenerate sulfur and sodium values for recycle to the process. U.S. Pat. No. 2,348,360 discloses recovery of antimony from ore also containing arsenic and copper without forming semi-metallic sulfides of calcium. Sulfur and sodium carbonate is mixed with the ore, the mixture is heated rapidly and excess sulfur vaporized, and the residue is then leached with water. Both the antimony and arsenic are rendered water-soluble. The leach solution is filered and H.sub.2 S gas then contacted with the solution to precipitate antimony pentasulfide, which is recovered by filtration. U.S. Pat. No. 2,230,972 discloses the recovery of antimony from ores also containing tin by roasting the ore in the presence of a carbonaceous reducing agent, an alkali metal compound such as soda ash, and sulfur. Sodium sulfide is utilizable in place of the soda ash and sulfur. The antimony and tin are converted into soluble polysulfides which are recovered from the ore by water leaching. The antimony may be recovered by electrowinning. U.S. Pat. No. 2,116,891 discloses the removal of antimony, arsenic, copper, zinc, etc. from non-ferrous metal scraps, by covering the molten metal scrap with a layer of caustic alkali such as sodium hydroxide, whereby the sodium and antimony unite to form intermetallic compounds. If arsenic is present in the metal scrap, the sodium-antimony compound will also include the analogous sodium-arsenic compound, such compounds having a lower specific gravity than the molten metal from which they separate and rise to the surface to form a layer of pasty or mushy consistency which is periodically skimmed off.PPOBJECTS OF THE INVENTION PPOne object of the invention is to provide a new and improved process for the recovery of antimony values from ore and ore concentrates containing sulfo-antimony compounds of copper and also containing arsenic, for example tetrahedrite.PPAnother object of the invention is to provide a new and improved process for the treatment of ore and ore concentrates containing sulfo-antimony salts of copper and also containing arsenic, for example tetrahedrite, to separate undesirable arsenic from the antimony and to separate and concentrate the antimony and copper values in a form from which these values can be readily recovered.PPA further object is to provide a new and improved process for the treatment of ore and ore concentrates containing sulfo-antimony salts of copper and also containing arsenic and silver, for example tetrahedrite, to separate arsenic from the antimony and to separate and concentrate the antimony, copper and silver values in forms from which these values can be readily recovered.PP An additional object of this invention is to provide a new and improved process for the recovery of antimony values from ore and ore concentrates containing sulfo-antimony compounds of copper, and also containing arsenic, for example, tetrahedrite, which yields high purity antimony metal containing less than 0.01% arsenic.P PAdditional objects and advantages will be readily apparent as the invention is hereinafter described in detail.PPBRIEF SUMMARY OF THE INVENTIONPPThe aforementioned objects are attained by the process of this invention which comprises:PPa. smelting a charge containing a material, e.g. an ore or ore concentrate, containing the sulfo-antimony compound or compounds of copper, and arsenic, e.g. tetrahedrite, sodium sulfide, calcium values supplied as lime and/or calcium carbonate, and a reducing agent, usually a carbonaceous solid reducing agent, e.g. coke, for a period sufficient to convert at least a major portion of the antimony to a water-soluble alkali metal compound of antimony and sulfur and at least a major portion of the arsenic to a water-insoluble calcium compound of arsenic and oxygen;PP b. the sodium sulfide being incorporated in the smelting charge in an amount sufficient to convert a major portion, all or substantially all of the antimony into the water-soluble sodium compound of antimony and sulfur, and the calcium values being supplied to the smelting charge in an amount sufficient to convert a major portion, all or substantially all of the arsenic into the water-insoluble calcium compound of arsenic and oxygen;PPc. leaching an alkaline matte obtained from the smelting of (a) and containing the water-soluble alkali metal compound of antimony and sulfur, the water-insoluble calcium compound of arsenic and oxygen and a water-insoluble sulfur compound of copper with an aqueous liquid, ordinarily water, to dissolve the soluble alkali metal compound of antimony and sulfur therein to the substantial exclusion of the calcium compound of arsenic and oxygen and sulfur compound of copper; andPP d. separating an aqueous liquid leach solution containing the soluble alkali metal compound of antimony and sulfur from an insoluble solid leach residue containing the insoluble calcium compound of arsenic and oxygen and the insoluble sulfur compound of copper.PPIt is critical for good results, that sodium salts, e.g. sodium sulfide or sodium sulfate, be utilized for the smelting inasmuch as the potassium salts, e.g. potassium sulfide or potassium sulfate, were found to be very inferior. With utilization of the sodium salts in the smelting, over 90% extraction of antimony from tetrahedrite was achieved. However, with the substitution of the potassium salts for the sodium salts, despite using over twice as much of the potassium, the antimony extraction was considerably less. The striking superiority of the sodium salts over the potassium salts for use in the smelting for the recovery of the antimony was unexpected.P PThe sodium sulfide is incorporated in the smelting charge usually in an amount which is sufficient to provide in the solution obtained by leaching the matte produced by the smelting an atomic ratio of S.sup.= to Sb within the atomic ratio range of about 2.0:1 to about 3. 5:1 respectively. The calcium values are supplied to the smelting charge usually in an amount which is sufficient to provide in the resulting alkaline matte an atomic ratio of Ca to As within the atomic ratio range of about 1.3:1 to about 9.5:1 respectively.