Asarco LLC

Smelter Control Research Association, Inc.

William H Wetherill

James M Henderson

Walter F Johnson

Adrian E Albrethsen

Max L Hollander

Ivor E Campbell

An ammonia-based double-alkali process for removing sulfur oxides from stack gases. In this process, usually continuous, stack gases are contacted with an aqueous wash liquid containing ammonium sulfite as a sulfur oxide reactive compound to form a spent absorbent liquor containing bisulfite, sulfite and sulfate salts of ammonia. A portion of the reactive compound is regenerated by reacting the spent scrubbing liquor with a source of calcium ions, usually limestone. During the regeneration, calcium sulfite solids are precipitated as a by-product, any gypsum solids precipitation during the process being tolerated for a time insufficient to degrade substantially process performance. The resultant calcium solids are separated from the regenerated liquor which is returned for further contact with the stack gases, a portion of these solids being recycled to the regeneration stage. The process is preferably regulated by monitoring and controlling of the calcium concentration of the regenerated liquor, upset conditions being corrected by the addition of make-up ammonia during regeneration of the liquor.

Ammonia double-alkali process for removing sulfur oxides from stack gases

SO.sub.2 is removed from a SO.sub.2 -containing gas mixture utilizing an aromatic amine as absorbent, followed by scrubbing the SO.sub.2 -depleted, aromatic amine-enriched effluent gas with sulfurous acid-and ammonium sulfate-containing aqueous solution to remove substantially all of the gaseous aromatic amine from the gas. The effluent gas is discharged ultimately to the atmosphere without any additional scrubbing of the gas, after its discharge from the sulfurous acid scrubbing zone, with sulfuric acid solution or any other acid solution or any acid.

Recovery of sulfur dioxide from gas mixtures

Ammonia is added to combined aqueous scrubbing solutions containing an organic base-sulfuric acid reaction product, preferably an aromatic amine-sulfuric acid reaction product, an organic base-sulfurous acid reaction product, preferably an aromatic amine-sulfurous acid reaction product, and water in one or more separating zones located exteriorly of an absorption tower. The combined aqueous scrubbing solutions are obtained from sulfurous acid and sulfuric acid solution scrubbing sections of the absorption tower wherein an organic base, preferably an aromatic amine, is utilized as absorbent in a lower absorber section of the tower to remove SO.sub.2 from a SO.sub.2 -containing gas mixture, followed by scrubbing the SO.sub.2 -depleted, aromatic amine-enriched gas from the absorber section first with sulfurous acid solution in the sulfurous acid scrubbing section of the tower to remove most of the gaseous aromatic amine therefrom and then with dilute sulfuric acid solution in the sulfuric acid scrubbing section of the tower, to remove a major portion of the residual gaseous aromatic amine from the gas. Liquid sulfuric acid solution containing a relatively high concentration of aromatic amine-sulfuric acid reaction product is withdrawn from the lowermost tray in a preferred tray-equipped tower scrubbing section, and a major portion, i.e. more than 50%, of this withdrawn sulfuric solution is passed back to and introduced preferably onto the fourth or third tray from the top of the tray-equipped scrubbing section. Liquid sulfuric acid solution containing a relatively low concentration of aromatic amine-sulfuric acid reaction product is also withdrawn from preferably the second tray or third tray from the top of this section when the introduction of the returned acid solution is onto respectively the third tray or fourth tray from the top of the section, and such withdrawn acid solution having the relatively low concentration of aromatic amine-sulfuric acid reaction product is returned and introduced onto the top tray of this sulfuric acid scrubbing section. The sulfur dioxide is stripped from the pregnant aromatic amine absorbent from the absorbing section in the stripping section of a stripping tower. The ammonia treatment of the combined aqueous scrubbing solutions in the external separating zone results in release of the aromatic amine from the aromatic amine-sulfuric acid reaction product by reaction of the ammonia with the aromatic amine-sulfuric acid reaction product and also in the formation of ammonium sulfate. Aqueous liquid solution containing the ammonium sulfate and aromatic aminesulfurous acid reaction product is withdrawn from a lower layer thereof, which is beneath an upper layer of released aromatic amine, in the separating zone and passed to the regenerator section of a stripping tower. Aromatic amine vapor and SO.sub.2 gas are liberated in the regenerator section and a considerable quantity of steam is generated therein. Aqueous solution containing ammonium sulfate is withdrawn from the lower portion of the regenerator section and, after bleeding off only a small portion of this aqueous solution, is passed, after cooling, into the upper portion of the sulfurous acid scrubbing section of the absorption tower and introduced therein. SO.sub.2 gas, obtained in the process, is supplied into the lower portion of this sulfurous acid scrubbing section and is dissolved in water of the introduced aqueous ammonium sulfate solution to form sulfurous acid. In another embodiment, the effluent gas from the sulfuric acid scrubbing section of the tower is scrubbed in alkali metal carbonate scrubbing section of the tower with a liquid alkali metal carbonate solution, e.g. a dilute aqueous sodium carbonate solution.

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 INVENTION

Process for the recovery of antimony values from ores containing

SO.sub.2 is removed from a SO.sub.2 - containing gas mixture utilizing an aromatic amine as absorbent, followed by scrubbing the SO.sub.2 - depleted, aromatic amine - enriched gas with sulfurous acid solution to remove most of the gaseous aromatic amine therefrom and then with dilute sulfuric acid solution to remove substantially all of the small amount of residual gaseous aromatic amine from the gas. The aqueous scrubbing solutions containing aromatic amine sulfite and aromatic amine sulfate from the respective sulfurous acid and sulfuric acid scrubbing zones are combined and ammonia is added thereto, resulting in release of the aromatic amine and in the formation of ammonium sulfate. Aqueous solution containing the ammonium sulfate is introduced into the upper portion of the sulfurous acid scrubbing section.

Growing community of inventors

Staten Island, NY, United States of America

William H Wetherill