United States Environmental Protection Agency Industrial Environmental Research Laboratory Cincinnati OH 45268 Research and Development EPA-600/S2-82-058 August 1982 Project Summary Environmental Considerations for Emerging Copper-Winning Processes H. Dolezal, M. Hayashi, G. Potter, and J. O. Burckle The weak SO2 emissions from primary copper have been and con- tinue to be the barrier to achieving SO2 emission limitations in smelter local- ities. The ambient air quality standards are obtained only through the SCS (supplementary control system), that is, by production curtailment in lieu of constant emission controls. This doc- ument, one of a series that addresses the weak SO2 emission problem, was undertaken to examine capabilities of several alternative smelting and hydro- metallurgical metal-winning technol- ogies for the production of copper. The investigation concentrated on the comparison of the degree of sulfur containment, energy consumption/ savings and costs of many newer, commercially employed pyrometallur- gical smelting processes in combina- tion with various types of final controls for sulfur containment. The emerging technologies for pyro- and hydrometal- lurgical processes are briefly discussed but are not analyzed in great detail owing to the lack of basic data in the open literature. This Project Summary was devel- oped by EPA's Industrial Environmen- tal Research Laboratory, Cincinnati, OH, to announce key findings of the research project that is fully docu- mented in a separate report of the same title (see Project Report ordering information at back). Introduction The objective of this study was to depict the potential of modern copper- winning processes, to contribute to the solution of the weak sulfur dioxide (S02 problem, and to identify potential attri- butes or barriers to employing these processes within the industry. The evaluation primarily emphasized air pollution potential, energy require- ments, and process economics. Thirteen processes were investigated in the first project phase (Table 1). As the study progressed, the main emphasis became the evaluation of the energy and economic aspects of the five most developed pyrometallurgical pro- cesses, specifically the electric furnace, Noranda process, Outokumpu and INCO flash furnace processes, and variations on the conventional reverberatory fur- nace practice for SOz control. This approach became necessary, as the information required for analysis of the emerging hydrometallurgical and pyro- metallurgical processes was not avail- able. It was found that none of the emerging hydrometallurgical processes have been developed to the extent that meaningful analyses could be per- formed. It was also found that some of the newer smelting methods such as the three-furnace, oxygen-enriched re- verberatory, converter smelting, top blown rotary converter, and DMA SOz processes have not yet been widely ------- Table 1. Processes Evaluated Phase I - Review Pyrometallurgical Processes Hydrometallurgical Processes Hecla-EIPaso Arbiter Cymet Duval "CLEAR" Mitsubishi Three-Furnace System Top Blown Rotary Converter (TBRC) Converter Smelting Oxygen Enriched Reverberatory Smelting Reverb Smelting with DMA SOz Process Electric Furnace Smelting Outokumpu Flash Furnace INCO Flash Furnace Noranda Furnace Phase II - In-Depth Evaluation Conventional reverberatory process (five scenarios)—(1) no SOz control. (2) with reverberatory gas vented up the stack and converter gas going to an acid plant, (3) with converter gas going to an acid plant and reverberatory gases going to a Bureau of Mines citrate process plant. (4) with both converter and reverberatory gases going to a Bureau of Mines citrate process plant, and (5) using a roaster with both roaster and converter gases going to an acid plant. Electric arc furnace smelting (two scenarios)—(1) SQz control by an acid plant, and (2) SOz control by a Bureau of Mines citrate process plant. Noranda process (three scenarios)—(1) SOz control by an acid plant, (2) SOz control by a Bureau of Mines citrate process plant, and (3) SOz control by direct reduction. Outokumpu flash smelting (two scenarios)—(1) using preheated air with SOz control by an acid plant, (2) using preheated air with SOz control by a Bureau of Mines citrate process plant. INCO flash smelting (two scenarios)—(1) using oxygen with SOz control by an acid plant, and (2) using oxygen with SOz control by direct reduction. used, and information was insufficient for analysis. Quantitative data on emis- sions and effluents in the published literature were inadequate to account for the distribution of minor elements in any of the processes. Therefore, the field of candidate processes quickly narrowed to the five, based upon the availability of detailed technical and economic data. A total of 14 scenarios were investigated for these five pro- cesses, which are in commercial use (see Table 1). Reverberatory smelting with no controls was the scenario used for the base case. Study Methodology All of the processes evaluated were similar, in that they were pyrometallur- gical operations that produced blister copper which was cast into anodes and electrorefined. To enable a direct com- parison of the various processes, each was assumed to produce 100,000 tons of electrorefined copper per year, start- ing from a hypothetical standard con- centrate, the composition of which is given in Table 2. This hypothetical concentrate is a composite based on feed materials used by smelters in the Western United States, excluding cus- tom smelters that treat complex ores. The basis of the hypothetical composi- tion is given in an Appendix to the report. Energy requirements for the produc- tion of a ton of copper by each of the processes evaluated were estimated Table 2. Chemical Composition of Standard Chalcopyrite Con- centrate (Dry Basis)* Constituent Composition, pet Cu 27.0 Fe 27.0 S 33.5 SiOz 9.0 CaO 0.5 Other^ 3.0 *Analysis of the standard concentrate was arrived at by averaging analyses of actual chalcopyrite concentrates used at a number of commercial smelters. ^"Other" includes oxygen, MgO, A/zOa, and minor elements. with the help of reports on energy use patterns prepared by Battelle Columbus Laboratories. Calculation methods equiv- alent to those used in the reports were used to make an itemized breakdown of total energy consumed in generating utilities and of the energy required for the raw materials. For raw materials, this included energy needed for mining and ore beneficiation, for smelting and refining of metals, for other raw mate- rials used as part of the production process, and for transportation to pro- cessing and refining plants. The material balance, energy require- ments, and cost estimate calculations were produced by a computer estima- ting program, developed by the Bureau of Mines under a separate program, which incorporated historic cost infor- mation from Bureau files. The costs reported for the evaluations performed in this project were updated to 1980. Flowsheets for each process evalu- ated were developed. A material balance for each scenario was then prepared. The material balance indicates constant values for the S02 content of smelter gases and represents the average flow for these fluctuating streams. Material balance flowsheets for the processes show how the major elements in the concentrates, fluxes, and prod- ucts are distributed. Included after all smelting operations are electrostatic dust precipitators in which an estimated 10 percent dilution of the gas occurs because of leakage. Whenever available, information concerning the minor ele- ments is given in the text. Cost estimates were prepared for modifications of the smelting processes ------- for the purpose of making relative comparisons of capital and operating costs. For this reason, some of the minor operations normally conducted in a smelter, such as recycle of dust and scrap, have been omitted to simplify the flowsheets and calculations. These esti- mates do not include any interest or other charges for invested capital or allowances for federal taxes and profit. Also included as part of the economic evaluation are estimates of the total energy requirements. Findings and Conclusions Estimated costs and energy require- ments were prepared for recovering copper from chalcopyrite concentrates by some 14 scenarios of 5 basic pro- cesses. The resulting estimates are presented in Tables 3 and 4. The evalu- ation shows that sulfur retentions greater than 90 percent are technically achievable and that the elimination of the weak SO2 stream by conversion to modern smelting furnaces combined with acid plant control are potentially the most effective method for S02 control and energy savings, while also being the most cost effective. The costs, in mid-1980 dollars, range from a low of 34.6 cents per pound for a conventional smelter with no S02 con- trols to 49.4 cents per pound for a conventional smelter using the USBM citrate process to treat both the rever- beratory and converter gases. If the conventional reverberatory smelter with no SOa controls is used as a standard for comparison, the various systems for controlling emissions will be found to increase capital investment"over a range of 30 to 34 percent and costs for producing copper over a range of 5 to 43 percent. The lowest cost smelter with SOz controls was an INCO flash opera- tion with an acid plant (36.4 cents per pound). When smelters with acid plants for SOz control are compared using a reverberatory smelter with an acid plant as a standard, the Noranda, Outokumpu, and INCO versions require about 30 percent less energy. Sulfur dioxide controls based on the USBM citrate process or on direct reduction will increase energy requirements by factors ranging from 1.5 to 2.0. Because of variations in local condi- tions, the effect of byproduct credits was not included in the computer program. The actual overall cost would depend on the availability of a market, either inter- nal or external, for the acid and/or sulfur produced. In most cases, where the use or sale of byproducts is possible, costs would be reduced by some inde- terminate amount that would depend on local conditions. It should be recognized, however, that in instances where little or no use or sale of byproducts is possible, costs would be increased owing to the cost of storage or disposal. In the cases where neutralization of sulfuric acid is necessary, the disposal cost could make a significant change in the economics of the process. In these evaluations no credits or penalties were applied for disposal of byproducts, so that all the processes could be compared on the same basis. However, a rough comparison of these effects was made based on assigned values of $20 per ton for sulfuric acid and $100 per ton for elemental sulfur. The effect of these byproduct values is shown in Table 5. As expected, byproduct values shift the unit production costs of copper to a lower range of 33 to 43.8 cents per pound, but they also have a leveling effect, in that costs for the Noranda smelter with an acid plant and the INCO and Outokumpu flash smelter with acid plants were in the lower end of the cost range (33.4 to 33.6 cents per pound). When a reverberatory smelter without pollution controls is used as a standard for comparison with alternative pro- cesses, the following conclusions are reached: • unit production costs in cents per pound of copper, without byprod- uct credit, will increase from 34.6 to a range of 36.4 to 49.4, with an INCO flash smelter in an acid plant giving the lowest increase, • estimates for byproduct credit shift unit production costs to a lower range of 33.0 to 43.8 cents, with INCO, Noranda, and Outokumpu flash smelters in acid plants giving cost in the lower end of the range, • sulfur retention increased from 2.4 percent to a range of 64.5 to 96.2 percent, with both an electric furnace in an acid plant and a reverberatory smelter treating re- verberatory and converter gases in a citrate plant giving the highest retention, and • energy requirements in million Btu per ton copper are 38.46 for the standard and range from 30.13 to 90.67, with both the Noranda and INCO smelters in acid plants using the least energy. ------- Table 3. Estimated Capital Cost, Operating Cost, and Energy Requirements* Process Noranda process Do. Do. Outokumpu flash Do. INCO flash Do. Electric smelting Do. Reverberatory Do. Do. Do. Do. Type of SOz Control Acid plant Citrate plant Direct reduction Acid plant Citrate plant Acid plant Direct reduction Acid plant Citrate plant None Converter gas to acid plant Converter gas to acid plant, reverberatory gas to citrate plant Converter and reverberatory gases to citrate plant Roaster and converter gases to acid plant Fixed Capital, Dollars 305,118.000 341,002,000 304.701.000 300,992.000 330,456.000 286,086.000 311,605,000 300,529,000 315,140,000 261,028,000 313,267,000 348,784,000 334,686,000 307,077,000 Working Capital, Dollars 16,613,000 21,185,000 20,979,000 16,639,000 21,320,000 16,426,000 22,049.000 18,211,000 22,027,000 15,679,000 18,250,000 21,204,000 22,768,000 17,918.000 Annual Operating Cost, Dollars 74,101,000 92,978,000 91,550,000 74.122,000 93,022,000 72,891,000 96.065,000 80,021,000 95.350.000 69,193,000 80,747,000 93,241,000 98,725,000 79,257,000 Energy Requirement, Million Btu/ton Cu 30.13 66.90 85.14 30.88 68.07 33.19 90.67 44.97 81.69 38.46 43.56 58.38 81.67 41.93 'Estimates are based on 1980 costs without allowance for escalation during construction period and do not include interest on invested capital, federal taxes, or prof it. Capacity basis is 100,000 tons per year of electrorefined copper. ------- Table 4. Summary of Processes Evaluated* Process Noranda process Do, Do. Outokumpu flash Do. INCO flash Do. Electric smelting Do. Reverberatory Do. Do. Do. Do. Type of SOz Control Acid plant Citrate plant Direct reduction Acid plant Citrate plant Acid plant Direct reduction Acid plant Citrate plant None Converter gas to acid plant Converter gas to acid plant. reverberatory gas to citrate plant Converter and reverberatory gas to citrate plant Roaster and converter gas to acid plant Total Sulfur Retention^ 437.8 437.5 398.0 364.6 364.3 367.2 333.8 368.3 357.3 9.1 246.9 368.3 367.8 292.5 Sulfur Recovered,^ pet 95.6 95.5 86.9 95.9 95.8 95.9 87.2 96.2 93.3 2.4 64.5 96.2 96.1 76.4 Byproduct Produced, tpd Sulfuric Acid 1.269.4 0 0 1,050.6 0 1,054.0 0 1.O43.2 0 0 690.8 690.8 0 823.0 Sulfur 0 410.5 375.2 0 339.8 0 311.6 0 337.1 0 0 114.1 337.O6 0 Estimated Overall Cost, cents/lb/Cu (No Byproduct Credit) 37.1 46.5. 45.8 37.1 46.5 36.4 48.0 40.0 47.7 34.6 40.4 46.6 49.4 39.6 * Estimates are based on 1980 costs without allowance for escalation during construction period and do not include interest on invested capital, federal taxes, or profit. Capacity basis is 100,000 tons per year electrorefined copper. ^TotaI sulfur retention includes sulfur in HtSO*, CaSO* slag, tailings, sulfur product, ------- Table 5. Estimated Effect of Byproduct Credit on Operating, Cost Process Noranda process Do. Do. Outokumpu flash Do. INCO flash Do. Electric smelting Do. Reverberatory Do. Do. Do. Do. Type of SOZ Control Acid plant Citrate plant Direct reduction Acid plant Citrate plant Acid plant Direct reduction Acid plant Citrate plant None Converter gas to acid plant Converter gas to acid plant, reverberatory gas to citrate plant Converter and reverberatory gas to citrate plant Roaster and converter gas to acid plant Annual Operating Cost. Dollars 74,101,000 92,978.000 91.550,000 74,122,000 93,022,000 72,891.000 96.065.000 80.021.000 95.350,000 69.193,000 80.747,000 93,241,000 98.725,000 79.257,000 Byproduct* Credit, Dollars 6,956.000 1 1.248,000 10,281,000 6.934.000 11.213,000 6,956,000 10.283,000 6.885.000 11,124,000 - 4,559,000 8,325,000 1 1, 123,OOO 5.432,000 Annual Operating Cost With Byproduct Credit, Dollars 67,145,000 81,730,000 81,259,000 67,188.000 81.809,000 65,935,000 85,782,000 73, 136,000 84,226,000 69, 193,000 76,188,000 84,916,000 87,602.000 73.825.000 Estimated Overall Cost, Cents/ Ib Cu No Credit 37.1 46.5 45.8 37.1 46.5 36.4 48.0 40.0 47.7 34.6 40.4 46.6 49.4 39.6 With Credit 33.6 40.9 40.6 33.6 40.9 33.0 42.9 36.6 42.1 34.6 38.1 42.5 43.8 36.9 Reduction In Cost Cents 3.5 5.6 5.2 3.5 5.6 3.4 5.1 3.4 5.6 0 2.3 4.1 5.6 2.7 Percent 9.4 12.0 11.4 9.4 12.0 9.3 10.6 8.5 11.7 0 5.7 8.8 11.3 6.8 *Based on $20.00 per ton for HzSO* and $100.00per ton for elemental sulfur for a production basis of 100.000 tons per year o) electrorefined copper. H. Dolezal, M. Hayashi, and G. Potter are with the U.S. Bureau of Mines, Salt Lake City Research Center. Salt Lake City, UT; the EPA author J. O. Burckle (also the EPA Project Officer, see below) is with the Industrial Environmental Research Laboratory, Cincinnati, OH 45268. The complete report, entitled "Environmental Considerations for Emerging Copper-Winning Processes," (Order No. PB 82-227-794; Cost: $12.OO. subject to change) will be available only from: National Technical Information Service 5285 Port Royal Road Springfield, VA 22161 Telephone: 703-487-4650 The EPA Project Officer can be contacted at: Industrial Environmental Research Laboratory U.S. Environmental Protection Agency Cincinnati. 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