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Treatment of Copper Smelting and Refining Wastes

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Treatment of Copper Smelting and Refining Wastes RI 9522 REPORT OF INVESTIGATIONSI1994 ~y Treatment of Copper Smelting SftOK.¥E FUiSiAAoH 09iTER and Refining Wastes ~ rAAY 3 1995 us BUREA!.} OF MINES By D. K. Steele, K. S. Gritton, !.315~"YAve. SPOf<AH!, WA SIIiJ!07 and S. B. Odekirk UNITED STATES DEPARTMENT OF THE INTERIOR BUREAU OF MINES i 1_ i I I 'I U.S. Department of the Interior Mission Statement As the Nation's principal conservation agency, the Department of the Interior has responsibility for most of our nationally-owned public lands and natural resources. This includes fostering sound use of our land and water resources; protecting our fish, wildlife, and biological diversity; preserving the environmental and cultural values of our national parks and historical places; and providing for the enjoyment of life through outdoor recreation. The Department assesses our energy and mineral resources and works to ensure that their development is in the best interests of all our people by encouraging stewardship and citizen participa­ tion in their care. The Department also has a major responsibility for American Indian reservation communities and for people who live in island territories under U.S. administration. Cover: A copper waste dump. Report of Investigations 9522 Treatment of Copper Smelting and Refining Wastes By D. K. Steele, K. S. Gritton, and S. B. Odekirk UNITED STATES DEPARTMENT OF THE INTERIOR Bruce Babbitt, Secretary BUREAU OF MINES " :1 ! " International Standard Serial Number ISSN 1066-5552 CONTENTS Page Abstract. .. • . .. .. 1 Introduction . • . 2 Leach studies .................................................................•..... 3 Waste characteri7..ation .............................................................. 3 Leaching of bath-smelter flue dust ..................................................... 3 Sulfuric acid leach ............................................•...............•.. 3 Bleed electrolyte leach ............................................................ 4 Leaching of flash-smelter flue dust ...................................................'. ,. 4 Acid leach ........... 4 Water leach in conjunction with weak-acid-bleed leach .................................... 5 Characterization of leach residues . 5 Acid leach residues .............................................................. 5 Water-weak-acid leach residues ..................................................... 5 Postleach process flowsheet options . 6 Processing of flue dust leach residue . 6 Processing of leach solutions . • • • • . 6 Overview..... ..................................................... ......... ... 6 Copper recovery as sulfate, arsenic removal using S02 reduction-precipitation ................... 6 Precipitation of arsenic as calcium-iron arsenate ... :..................................... 6 Arsenic removal by solvent extraction ................................................. 7 Copper recovery by cementation on powdered iron .................•.............•....•.. 7 Neutralization of weak-acid-bleed leach fIltrate for bismuth removal. • . • . • 8 Characterization of bismuth-rich gypsum . • . 8 Sulfide precipitation of arsenic and copper ..........................................',.. 8 Vitrification of sulfides ..................................•.....•..........•.........• 8 Vitrification of contaminated arsenic sulfides . • . • . • . • . •.. : . 11 Sulfide precipitation from synthetic acid-plant-blowdown solution . •. 11 Leaching of copper smelter slag ............................•............................ 12 Summary and conclusions .. • • . • • . • . • . • . 12 References . .. • . 13 ILLUSTRATIONS 1. Bismuth precipitation under oxidized conditions .......................................... 9 2. Bismuth precipitation under reduced conditions ...............................•.......... 9 3. Hydrogen-sulfide-induced precipitation of copper and arsenic at 60 °C . 10 TABLES 1. Compositions of solid copper-processing wastes used in treatment studies ....................... 3 2. Compositions of liquid copper-processing wastes used in treatment studies ...................... 3 3. Comparison of metals leached from flue dust D using various leaching solutions .................. 4 4. Metal leached using reagent-grade acid and weak-acid-bleed solutions. 4 5. Effects of chloride and fluoride concentration on solubility of bismuth when leaching flash-smelter flue dust ......................................................................... 5 6. Composition of flash-flue-dust leach fIltrates . .. .. 5 7. Weight percent metal extracted from flash-smelter flue dust using water and simulated weak-acid-bleed solution with varying amounts of hydrochloric acid in weak-acid-bleed solution .................. 5 8. Composition of typical leach solutions produced at defmed optimal conditions, dust sample D ........ 6 9. Test conditions for selective precipitation of arsenic from acidic leach solutions ................... 7 10. Cementation of copper after arsenic removal ............................................ 8 --------- ii TABLES-Continued Page ~ I 11. Concentrations of metals in TCLP leachates obtained from bismuth-rich precipitates .............. 8 12. Compositions of vitrified products produced using various mixtures of arsenic-trisulfide and elemental sulfur ....................................................................... 10 13. Weight-loss and TCLP data for contaminated arsenic sulfides ............................... 11 14. Hazardous elements leached from AS2S3 glass with 1.5 pct contamination ....................... 11 15. Composition of synthetic acid-plant blowdown .......................................... 12 16. Composition of typical sulfides precipitated from synthetic acid-plant-blowdown solutions ........... 12 17. Results of slag-leaching tests ....................................................... 12 il 'I UNIT OF MEASURE ABBREVIATIONS USED IN THIS REPORT giL gram per liter pet percent h hour t metric ton mg/L milligram per liter tr oz/st troy ounce per short ton min minute V volt , :I mL milliliter wt pct weight percent mV millivolt °C degree Celsius oz/t ounce per ton TREATMENT OF COPPER SMELTING AND REFINING WASTES By D. K. Steele,1 K. S. Gritton,2 and S. B. Odekirk3 ABSTRACT The domestic primary copper industry generates in excess of 600 million t of mining and mineral­ processing waste annually. Most of the waste poses negligible environmental threat, but a small fraction, because of toxic or corrosive characteristics, may be subject to regulation under Subtitle C of the Resource Conservation and Recovery Act (RCRA) or other pertinent regulations. Among the wastes generated by various copper producers are flue dusts, slags, refmery-bleed solutions, and. acid-plant wastes. The U.S. Bureau of Mines (USBM) has researched methods to mitigate the environmental .. threat posed by copper-processing wastes while recovering valuable metals ffom these materials. Acid~ leach processing of flue dusts has been demonstrated feasible along with sulfide treatment of liquid refinery wastes and acid-plant-bleed and gas-cleaning solutions to precipitate dissolved metals. In, addition, the feasibility of removing copper and molybdenum from slag, as well as stabili7.ation of precipitated sulfide wastes by vitrification, have been investigated. lChemical engineer. 2supervisory chemical engineer. 3PhysiCllI science technician•. Salt Lake City Research Center, U.S. Bureau of Mines, Salt Lake City, UT. 2 INTRODUCTION Processins of sulfide ores often results in the concen­ which pose less risk to the environment and provide a tration of en.vironmentally sensitive, or other deleterious, dense, stable, and more easily handled form for the waste. contaminants into various waste streams. Arsenic, cadmi­ The U.S. Bureau of Mines has researched the processing um, lead, and other metals may be concentrated in flue of arsenic-containing waste materials to remove the arsenic dusts, water-treatment slu4ges, .. and furnace liners, as well and recover metal values (~7). Pressurized chloride­ as refmery and acid-pljplt soluUpns. While these waste oxygen leaching of arsenic-bearing wastes was investigated streams may contain,signifi~t amounts of valuable met­ by Smyres and coworkers (5), although a sulfuric-acid als, recovery is cODlPUcAtedbltthe presence of objection­ leach may offer some advantages since sulfide-mineral able materials which are. diffic,ult to separate from the processors generally produce the acid as a byproduct, thus valuable components.. The. recovery of metal values from providing a cheap reagent. The acidic bleed streams from waste materials can mitigflte opcrationalcQ.sts. associated electrolytic metal refmeries, or the bleed solution from with waste disposal and could. also provide opportunities. to sulfuric-acid plants, could also provide acid for leaching. reduce the environmental risks and liabilities. posed by the Since these acid-bearing solutions must be removed to storage or disposal of the untreated substances. control impurities in the refming and acid-production proc­ While the reprocessing of low-volume wastes may not esses,coprocessing of flue dust with such solutions may have been economically attractive in the past, waste­ provide treatment options for the utilization and disposal management. regulations promulgated as a result of the of both wastes. Resource Conservation and Recovery Act (RCRA) require The USBM has also investigated the leaching and re­ mineral processors to recycle or properly treat potentially covery of metals
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