Production of copper via looping oxidation process

Abstract

Copper is produced by a looping oxidizing process wherein oxidation of copper sulfide concentrate to molten blister copper by conversion with copper oxides (and optionally oxygen from air) in a one step, molten bath operation to produce molten blister copper, iron oxide slag, and rich SO.sub.2 off gas. The blister copper is treated in an anode furnace to reduce the iron content and oxidize residual sulfur, and prepare it for either electrolysis or reoxidation.

Claims

1. A method for production of copper comprising: (a) providing (1) a copper sulfide concentrate product of mining or mineral refining comprising copper and iron metal including sulfides thereof and (2) one or more copper oxides, to a molten bath wherein they react with each other for smelting desulfurization, (b) wherein the copper oxides are provided to the molten bath in stoichiometric or in excess of up to about 20 wt % of stoichiometric ratios, (c) agitating the molten bath, (d) thereby oxidizing the sulfide concentrate in a one step to produce: (1) molten blister copper, (2) iron oxide-containing slag, and (3) highly concentrated SO.sub.2 off gas, (e) removing at least a portion of said molten blister copper from step (c) and contacting it with oxygen to produce copper oxide, (f) recirculating the copper oxide produced in step (e) to the molten bath of step (a), (g) removing at least a portion of the molten blister copper produced in step (d) for further refining or processing.

2. The method of claim 1, wherein the iron oxide-containing slag is further treated with carbon in the form of coal, natural gas, coke or a combination thereof to produce copper metal.

3. The method of claim 1, wherein the concentrated SO.sub.2 off gas is provided to one or more of plants selected from the group consisting of a handling plant for sulfuric acid production, a gypsum production plant, and a sulfur dioxide liquefaction plant.

4. The method of claim 3 wherein energy is produced and captured by the further step of producing sulfuric acid from the rich SO.sub.2 off gas from the smelting furnace.

5. The method of claim 4, wherein reoxidation of copper to copper oxides produces energy.

6. The method of claim 1 wherein the copper oxides provided in step (a) is CuO, Cu.sub.2O or a combination thereof.

7. The method of claim 6, wherein the stoichiometry of the reaction in the smelting furnace, in which the copper feed is converted to metallic copper, a slag, and an SO.sub.2 off gas is defined as the amount of CuO required to completely (1) convert the copper contained in the feed to metallic copper, (2) oxidize any iron in the feed to FeO and/or Fe.sub.2O.sub.3, which report to the slag, and (3) oxidize any sulfur in the feed to SO.sub.2 and substantially maintained in providing the sulfide and oxide.

8. The method of claim 6, wherein a flux material is provided and the copper concentrate, flux and the one or more copper oxides are fed into the molten slag where they react before separating to molten slag and blister copper.

9. The method of claim 1, wherein the temperature of the smelting furnace, wherein the oxidation of the copper concentrate is performed, is 1100-1400° C.

10. The method of claim 1 wherein a chemically inert gas is injected into the molten bath.

11. The method of claim 10, wherein the chemically inert gas is N.sub.2.

12. The method of claim 10, wherein the furnace for the oxidation of the copper concentrate is an electric furnace with tuyères to blow the chemically inert gas into the molten bath.

13. The method of claim 1, wherein the content of SO.sub.2 produced is 20-100 wt %.

14. The method of claim 1, wherein the sulfur content in the molten copper is reduced to below 1%, and the oxygen content in the molten copper is reduced to below 0.6 wt %.

15. The method of claim 14, wherein the sulfur content in the molten copper is reduced to below 0.9%, and the iron content in the molten copper is reduced to below 0.002 wt %.

16. The method of claim 1, wherein the residual copper content in the treated bath is below 0.5 wt % and the total copper recovery from the bath exceeds 92%.

17. The method of claim 1, wherein copper is reoxidized with air to produce the required amount of copper oxide for use in the smelting-desulfurization step.

18. The method of claim 17, wherein at least 80 wt % CuO relative to capacity of the copper to be reoxidized is produced.

19. The method of claim 1, wherein molten copper is atomized to molten droplets and reoxidized in a vertical, flash or downer furnace.

20. The method of claim 1 wherein the blister copper is further oxidized in a reoxidation furnace to produce copper oxide(s).

21. The method of claim 1 wherein the one or more copper oxides are provided from one or more external sources selected from the group consisting of pigments, spent catalysts, battery components, sulfates, carbonates, hydroxides and one or more of the minerals such as malachite, azurite, cuprite, chrysocolla, blue vitriol, antlerite, brochantite.

22. A method for production of copper comprising the steps of: (a) feeding copper sulfide concentrate, CuO, and gaseous oxygen or air into a molten bath of a furnace, wherein the total of the CuO and the gaseous oxygen, combined, are fed in stoichiometric ratio or in slight excess of up to about 20 wt % of stoichiometric ratios; wherein the content of the total CuO is 96.6-100 wt % and content of the gaseous oxygen is 3.4 to 0 wt %, (b) agitating the molten bath operation to produce (1) molten blister copper, (2) iron oxide slag, and (3) highly concentrated SO.sub.2 off gas, (c) treating the blister copper to reduce the iron content and oxidize residual sulfur, and prepare it for either electrolysis or reoxidation.

23. The method of claim 22, wherein the iron oxide slag is treated in a slag treatment furnace by carbon in the form of coal, natural gas, coke or a combination thereof reduction and wherein the molten blister copper is provided to an anode furnace.

24. The method of claim 23, wherein the slag is treated to recover copper.

25. The method of claim 24, wherein the furnace used to treat the slag is an electric furnace.

26. The method of claim 24, wherein the residual copper content in the treated slag is reduced below 0.5 wt % and the total copper recovery from the slag exceeds 92 wt %.

27. The method of claim 22, wherein the method for feeding the copper concentrate, flux and CuO is such that both materials are fed into the molten slag where they react before separating to molten slag and blister copper.

28. The method of claim 22, wherein the temperature of the smelting furnace wherein the oxidation of the copper concentrate is performed is 1100-1400° C.

29. The method of claim 22, wherein the air is injected into the molten slag formed during the oxidation of the copper concentrate to promote chemical reaction.

30. The method of claim 22, wherein a chemically inert gas is injected into the molten slag formed during the oxidation of the copper concentrate to promote chemical reaction.

31. The method of claim 30, wherein the chemically inert gas is N.sub.2.

32. The method of claim 30, wherein the furnace for the oxidation of the copper concentrate is an electric furnace with tuyères to blow the chemically inert gas into the molten slag.

33. The method of claim 22, wherein the sulfur content in the molten copper is reduced to below 1%, the iron content in the molten copper is reduced to below 0.3% and the oxygen content in the molten copper is below 0.6 wt %.

34. The method of claim 22, wherein the sulfur content in the molten copper is reduced to below 0.9% and the iron content in the molten copper is reduced to below 0.002 wt %.

35. The method of claim 22, wherein copper is reoxidized with air to produce the required amount of CuO for use in the smelting-desulfurization step.

36. The method of claim 35, wherein at least 80 wt % CuO relative to capacity of the copper to be reoxidized is produced.

37. The method of claim 35, wherein molten copper is atomized to molten droplets and reoxidized in a vertical, flash or downer furnace.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 (Prior Art) shows in block diagram form a generalized process flow chart for flash smelting conversion;

(2) FIG. 2 shows in block diagram form a Looping Sulfide Oxidation Process to produce anode copper;

(3) FIG. 2a shows schematically an electric arc furnace used in the smelting conversion;

(4) FIGS. 3-8 are traces of thermodynamic data showing calculations of production conditions (CuO) feed variation on output conditions of the copper melt and slag during the smelting step;

(5) FIGS. 9-15 show traces of thermodynamic data detailing the slag treatment and output of the slag treatment furnace, the treated slag and the copper melt or copper matte;

(6) FIGS. 16-19 show traces of thermodynamic data detailing the smelting of CuFeS.sub.2 with CuCO.sub.3; and

(7) FIGS. 20-22 show traces of thermodynamic data detailing the smelting of CuFeS.sub.2 with CuSO.sub.4.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

Example 1

(8) In the present analytical example (not based on a physical plant actually constructed) the process is described on a production basis of approximately 1000 kg of anode copper. The process flow (all or parts of which can be continuous, semi-continuous or batch format) is shown in FIG. 2 and the preferred basic configuration of the electric furnace (an arc furnace) is shown in FIG. 2a including tuyères for gas injection into a molten slag formed in the furnace.

(9) Electric Furnace

(10) A room temperature copper concentrate comprising 3000 kg CuFeS.sub.2, 173.4 kg FeS.sub.2, and 294.8 kg gangue (CaO, Al.sub.2O.sub.3, SiO.sub.2), preferably in free flowing powder form, is to be mixed with 7400 kg of CuO at 800° C. in the first smelting furnace (Table 1). Heat and material balances were calculated using HSC 7.1 Chemistry for Windows thermochemical software.sup.13. Silica (1000 kg) and lime (500 kg) fluxes are also taken as to be added to the melt. The melt is to be heated to 1300° C. via electrical and/or combustion heating. The reaction produces a metallic copper melt, an oxidized slag, and a rich SO.sub.2 gas stream. In this Example, 14% excess CuO is used to produce an optimal copper melt and an optimal slag (FIGS. 3, 4, and 5). The copper melt is 98.8% copper with 0.002% Fe, and 0.88% S (FIG. 6). The slag includes some copper oxide (as Cu.sub.2O), iron oxides and gangue and flux derivatives. All compositions herein are weight percent unless otherwise noted. .sup.13Roine, A., et al., HSC 7.11, Outotec, Pori, Finland (2011).

(11) As discussed in the above Summary of the Invention, the copper solubility in the slag is largely dependent on the degree of oxidation of the iron also present in the slag. The fluxes added to the furnace are designed to aid in slag formation and produce a low melting, fluid slag. The slag produced in this Example melts at 110° C. with a viscosity of 2.0 poise (at 1300° C.). The Cu.sub.2O content in the slag is 13.2%, and requires treatment to recover as much of this copper as possible (FIG. 7). FIG. 7 demonstrates that during smelting, the copper content in the slag is largely independent of the slag composition and operating temperature. However, as shown in comparing FIGS. 8 and 9, the dramatically higher O.sub.2 partial pressure above the slag in the electric furnace as compared to the O.sub.2 partial pressure above the slag in the slag treatment furnace leads to different slag chemistries. Most notably, the decreased copper solubility in the slag after slag treatment can be explained by considering the lower oxygen partial pressure present in the treatment furnace. This demonstrates that the copper content in the slag can be controlled by the oxygen partial pressure.

(12) TABLE-US-00001 TABLE 1 Electric Furnace Heat & Material Balance Temperature Amount, Amount, Amount, Latent Total © kmol kg Nm3 H, kWh H, kWh INPUT Cu Concentrate 25.000 18.853 3468.198 0.855 0.00 −2180.49 CuFeS2 25.000 16.348 3000.000 0.714 0.00 −864.48 FeS2 25.000 1.445 173.400 0.035 0.00 −71.56 CaO*Al2O3*2SiO2 25.000 1.060 294.798 0.107 0.00 −1244.44 Recycled CuO 800.000 93.029 7400.000 1.173 1025.04 −3040.27 CuO 800.000 93.029 7400.000 1.173 1025.04 −3040.27 Flux 25.000 25.559 1500.000 0.534 0.00 −5783.49 SiO2 25.000 16.643 1000.000 0.385 0.00 −4211.01 CaO 25.000 8.916 500.000 0.150 0.00 −1572.47 Heating 25.000 47.972 1243.806 888.658 0.00 0.00 C 25.000 8.326 100.000 0.044 0.00 0.00 O2(g) 25.000 8.326 266.412 186.609 0.00 0.00 N2(g) 25.000 31.320 877.394 702.005 0.00 0.00 Energy Required 2493.56 OUTPUT Copper Melt 1300.000 105.915 6607.987 31.555 1449.45 1544.56 Cu 1300.000 102.724 6527.713 0.729 1417.28 1417.28 Fe 1300.000 0.003 0.142 0.000 0.03 0.03 S 1300.000 1.814 58.147 0.028 21.91 21.91 O(g) 1300.000 1.374 21.985 30.799 10.22 105.33 Slag 1300.000 47.844 3596.867 0.940 1233.75 −7504.18 Al2O3 1300.000 1.059 108.020 0.027 44.85 −448.28 SiO2 1300.000 18.759 1127.114 0.434 461.01 −4285.28 CaO 1300.000 9.973 559.294 0.167 178.67 −1580.27 FeO 1300.000 11.671 838.491 0.140 240.41 −641.78 Fe2O3 1300.000 3.057 488.235 0.093 154.03 −547.63 Cu2O 1300.000 3.325 475.714 0.079 154.79 −0.93 Flue Gas 1300.000 73.419 3407.221 1645.574 1143.46 −2551.06 SO2(g) 1300.000 33.772 2163.415 756.960 634.42 −2150.05 CO2(g) 1300.000 8.326 366.412 186.609 152.67 −757.38 N2(g) 1300.000 31.320 877.394 702.005 356.37 356.37

(13) TABLE-US-00002 TABLE 2 Slag Treatment Furnace Heat & Material Balance Temperature Amount, Amount, Amount, Latent Total © kmol kg Nm3 H, kWh H, kWh INPUT Slag Furnace Slag 1300.000 47.844 3596.867 0.940 1233.75 −7504.18 Al2O3 1300.000 1.059 108.020 0.027 44.85 −448.28 SiO2 1300.000 18.759 1127.114 0.434 461.01 −4285.28 CaO 1300.000 9.973 559.294 0.167 178.67 −1580.27 FeO 1300.000 11.671 838.491 0.140 240.41 −641.78 Fe2O3 1300.000 3.057 488.235 0.093 154.03 −547.63 Cu2O 1300.000 3.325 475.714 0.079 154.79 -0.93 Reductant 25.000 4.329 52.000 0.023 0.00 0.00 C 25.000 4.329 52.000 0.023 0.00 0.00 S 25.000 0.000 0.000 0.000 0.00 0.00 Energy Required 76.99 OUTPUT Copper Melt 1300.000 6.573 417.129 0.053 90.67 90.68 Cu 1300.000 6.498 412.946 0.046 89.66 89.66 Fe 1300.000 0.075 4.179 0.001 1.01 1.01 O(g) 1300.000 0.000 0.004 0.006 0.00 0.02 Treated Slag 1300.000 47.430 3080.021 0.843 1054.22 −7298.04 Al2O3 1300.000 1.059 108.019 0.027 44.85 −448.28 SiO2 1300.000 18.759 1127.126 0.434 461.01 −4285.33 CaO 1300.000 9.973 559.297 0.167 178.68 −1580.28 FeO 1300.000 17.416 1251.250 0.209 358.75 −957.71 Fe2O3 1300.000 0.147 23.551 0.004 7.43 −26.42 Cu2O 1300.000 0.075 10.778 0.002 3.51 −0.02 Flue Gas 1300.000 4.330 151.739 97.040 62.79 −219.84 CO(g) 1300.000 2.425 67.932 54.358 27.86 −46.60 CO2(g) 1300.000 1.904 83.807 42.682 34.92 −173.23

(14) The SO.sub.2 stream produced during the smelting step is sent to an acid plant for sulfuric acid production. The SO.sub.2 content of the off gas in this Example is 46%. Significant energy can be captured during sulfuric acid production, and this energy can be used to improve the overall energy balance of the Looping Sulfide Oxidation process.

(15) Slag Treatment

(16) The slag produced in the electric furnace (3.0% Al.sub.2O.sub.3, 31.3% SiO.sub.2, 15.5% CaO, 23.3% FeO, 13.6% Fe.sub.2O.sub.3, 13.2% Cu.sub.2O) is transferred to an electrical furnace at 1300° C. for slag treatment (Table 2). In this Example the 3596.9 kg of slag is treated with 52 kg of carbon to reduce Fe.sub.2O.sub.3 and Cu.sub.2O. By reducing the trivalent iron, the solubility of copper in the slag is dramatically reduced. As a result, a copper melt is formed with 97.7% of the copper recovered (417.1 kg melt, 98.997% Cu, 1.0% Fe) (FIGS. 10 and 11). The remaining slag contains only 0.35% Cu.sub.2O and is fit for disposal as waste (melting temperature, 1070° C.; viscosity 1.7 poise at 1300° C.) (FIGS. 12 and 13). The copper melt produced during slag treatment is blended with the copper melt from the electric furnace to produce a copper stream (7025.1 kg, 98.798% Cu, 0.062% Fe, 0.828% S, 0.313% O) for treatment in the anode furnace.

(17) The heat required to perform the slag treatment will be provided by electrical heating via the electric furnace. Natural gas for combustion heating can also be provided via tuyères.

(18) Downer Reoxidation Furnace

(19) In a downer furnace, molten copper is atomized and oxidized in situ to fine particulate CuO. Atomizing the molten copper minimizes mass transfer limitations between the molten copper and the oxygen and leads to near 100% conversion to CuO. This highly exothermic reaction provides significant potential for energy capture. It is understood that molten CuO is highly corrosive, so following oxidation cool air is introduced to solidify the CuO. The CuO is thus cooled down to 800° C. before it exits as a fine particulate and is recycled back at temperature to the first furnace. Looping of this material in this system at temperature and at high processing speed enhances the overall energy balance of the process.

(20) The flue gases are sent to an air/air heat exchanger, where the reaction air for the downer furnace and anode furnace are preheated to 400° C. in order to maximize the thermal efficiency. The flue gas is then sent to a boiler where a significant portion of the energy is captured as high pressure steam.

(21) TABLE-US-00003 TABLE 3 Reoxidation Heat & Material Balance Temperature Amount, Amount, Amount, Latent Total © kmol kg Nm3 H, kWh H, kWh INPUT Reoxidation Copper 1300.000 93.105 5915.483 0.862 1284.49 1285.11 Cu 1300.000 93.029 5911.598 0.660 1283.51 1283.51 Fe 1300.000 0.066 3.676 0.000 0.89 0.89 O(g) 1300.000 0.009 0.144 0.202 0.07 0.69 S 1300.000 0.002 0.065 0.000 0.02 0.02 Reaction Air 400.000 221.497 6390.255 4964.539 690.25 690.25 O2(g) 400.000 46.514 1488.402 1042.553 150.10 150.10 N2(g) 400.000 174.982 4901.853 3921.986 540.15 540.15 OUTPUT Copper Oxides 1243.850 46.514 6661.065 1.109 1421.58 −502.52 Cu2O 1243.850 21.882 3131.100 0.522 585.95 −438.94 Cu2O(1) 1243.850 24.600 3520.000 0.587 832.15 −57.68 Cu2O*Fe2O3 1243.850 0.033 9.965 0.000 3.48 −5.90 Flue Gas 1243.850 198.197 5644.748 4442.302 2161.41 2161.24 N2(g) 1243.850 174.982 4901.853 3921.986 1895.51 1895.51 O2(g) 1243.850 23.212 742.764 520.270 265.86 265.86 SO2(g) 1243.850 0.002 0.131 0.046 0.04 −0.13

(22) TABLE-US-00004 TABLE 4 Quench Cooling of Reoxidation Products Temperature Amount, Amount, Amount, Latent Total © kmol kg Nm3 H, kWh H, kWh INPUT Reoxidation- Quench Cooling Copper Oxides 1243.850 46.514 6661.065 1.109 1421.58 −502.52 Cu2O 1243.850 21.882 3131.100 0.522 585.95 −438.94 Cu2O(1) 1243.850 24.600 3520.000 0.587 832.15 −57.68 Cu2O*Fe2O3 1243.850 0.033 9.965 0.000 3.48 −5.90 Flue Gas 1243.850 198.197 5644.748 4442.302 2161.41 2161.24 N2(g) 1243.850 174.982 4901.853 3921.986 1895.51 1895.51 O2(g) 1243.850 23.212 742.764 520.270 265.86 265.86 SO2(g) 1243.850 0.002 0.131 0.046 0.04 −0.13 Cooling Air 25.000 528.256 15240.366 11840.122 0.00 0.00 N2(g) 25.000 417.322 11690.618 9353.697 0.00 0.00 O2(g) 25.000 110.934 3549.748 2486.426 0.00 0.00 OUTPUT Copper Oxides 800.000 93.029 7405.274 1.172 1026.09 −3046.62 CuO 800.000 92.996 7397.400 1.172 1024.68 −3039.20 CuO*Fe2O3 800.000 0.033 7.874 0.000 1.41 −7.42 Flue Gas 800.000 703.196 20140.911 15761.146 4705.52 4705.35 N2(g) 800.000 592.305 16592.471 13275.683 3927.10 3927.10 O2(g) 800.000 110.889 3548.310 2485.418 778.39 778.39 SO2(g) 800.000 0.002 0.131 0.046 0.02 −0.15

(23) In this Example, 7400 kg of CuO are required in the electric furnace. As such, 5911.1 kg of molten Cu must be oxidized in the downer reoxidation furnace; the remaining 1020.5 kg of Cu can be sent to electrolysis for final purification (Tables 3 and 4). In the downer reoxidation furnace a significant excess of air will be used to ensure complete reoxidation.

(24) Energy is captured during this step by using the flue gases from the reoxidation furnace to (1) preheat the oxidation air and (2) produce high pressure steam in a boiler after preheating.

(25) Energy Balance

(26) The two primary energy producing steps in the Looping Sulfide Oxidation process are the sulfuric acid production in the acid plant and the reoxidation of the Cu to CuO before it is looped back to the electric furnace. The acid plant per se, is outside the scope of this invention; however, as it is known to those skilled in the art, state-of-the-art processes like the Lurec® process have been shown to capture significant portions of the total energy available during sulfuric acid production.sup.14. On this basis, we have evaluated the energy balance of the Looping Sulfide Oxidation process relative to conventional copper processing. .sup.14Daum K H, The Lurec® Process—Key to Economic Smelter Acid Plant Operation, in The Southern African Institute of Mining and Metallurgy Sulfur and Sulfuric Acid Conference 2009, 1-22.

(27) During conventional copper processing, the only major energy producing step is the acid production. It is estimated that the theoretical total amount of energy that can be produced during this step is 54.7 Wh per mole of CuFeS.sub.2 processed.
2SO.sub.2+O.sub.2.fwdarw.2SO.sub.3 ΔH.sub.600° C.=−54.7 Wh  (6)
In this analysis, production of sulfuric acid is estimated to result in the production of 2462 kg of high pressure steam (100 bar, 350° C.) per 1000 kg of Cu produced during heat capture in boilers and cooling jackets (Tables 5 and 6).

(28) TABLE-US-00005 TABLE 5 Acid Plant Boiler Heat & Material Balance Temperature Amount, Amount, Amount, Latent Total © kmol kg Nm3 H, kWh H, kWh INPUT Acid Plant System- Boiler 1 Gas from Smelting 1300.000 73.419 3407.221 1645.574 1143.46 −2551.06 SO2(g) 1300.000 33.772 2163.415 756.960 634.42 −2150.05 CO2(g) 1300.000 8.326 366.412 186.609 152.67 −757.38 N2(g) 1300.000 31.320 877.394 702.005 356.37 356.37 Gas from Anode 1200.000 50.173 1437.869 1124.550 580.51 −561.04 Furnace N2(g) 1200.000 35.269 987.991 790.495 367.09 367.09 SO2(g) 1200.000 1.810 115.964 40.575 31.08 −118.18 O2(g) 1200.000 0.003 0.082 0.057 0.03 0.03 NO(g) 1200.000 0.001 0.026 0.019 0.01 0.03 SO3(g) 1200.000 0.001 0.052 0.015 0.02 −0.06 H2O(g) 1200.000 8.273 149.040 185.428 108.08 −447.65 CO2(g) 1200.000 3.849 169.393 86.270 64.33 −356.39 CO(g) 1200.000 0.514 14.407 11.528 5.41 −10.38 H2(g) 1200.000 0.453 0.914 10.163 4.46 4.46 Cooling Water 25.000 89.461 1611.655 1.617 0.00 −7098.80 H2O(100 barl) 25.000 89.461 1611.655 1.617 0.00 −7098.80 OUTPUT Gas to Scrubbing 400.000 123.591 4845.090 2770.123 465.76 −4370.31 SO2(g) 400.000 35.583 2279.379 797.534 171.29 −2762.43 CO2(g) 400.000 12.175 535.805 272.879 55.58 1275.20 N2(g) 400.000 66.589 1865.385 1492.500 205.55 205.55 O2(g) 400.000 0.003 0.082 0.057 0.01 0.01 NO(g) 400.000 0.001 0.026 0.019 0.00 0.02 SO3(g) 400.000 0.001 0.052 0.015 0.00 −0.07 H2O(g) 400.000 8.273 149.040 185.428 30.33 −525.40 CO(g) 400.000 0.514 14.407 11.528 1.62 −14.17 H2(g) 400.000 0.453 0.914 10.163 1.37 1.37 High Pressure 350.000 89.461 1611.655 2005.140 485.79 −5840.59 Steam H2O(100 barg) 350.000 89.461 1611.655 2005.140 485.79 −5840.59

(29) TABLE-US-00006 TABLE 6 Catalyst Bed Heat & Material Balance Temperature Amount, Amount, Amount, Latent Total © kmol kg Nm3 H, kWh H, kWh INPUT Catalyst Bed Post-Scrub Gas Stream 80.000 114.346 4680.570 2562.913 59.08 −4205.41 SO2(g) 80.000 35.583 2279.379 797.534 22.29 −2911.43 N2(g) 80.000 66.589 1865.385 1492.500 29.65 29.65 CO2(g) 80.000 12.175 535.805 272.879 7.14 −1323.64 Reaction Air 25.000 93.193 2688.636 2088.781 0.00 0.00 O2(g) 25.000 19.570 626.230 438.644 0.00 0.00 N2(g) 25.000 73.622 2062.406 1650.137 0.00 0.00 Cooling Water 25.000 47.217 850.633 0.853 0.00 −3746.75 H2O(100 barl) 25.000 47.217 850.633 0.853 0.00 −3746.75 OUTPUT Catalyzed Gas 225.000 189.748 7369.206 4252.926 373.05 −4869.49 SO3(g) 225.000 35.583 2848.680 797.534 114.14 −3797.62 N2(g) 225.000 140.211 3927.791 3142.636 228.08 228.08 CO2(g) 225.000 12.175 535.805 272.879 27.84 −1302.94 O2(g) 225.000 1.779 56.930 39.877 2.98 2.98 High Pressure Steam 350.000 47.217 850.633 1058.314 256.40 −3082.67 H2O(100 barg) 350.000 47.217 850.633 1058.314 256.40 −3082.67

(30) Therefore, with all other factors being equal, conventional copper processing and Looping Sulfide Oxidation processing would theoretically produce equal amounts of energy during sulfuric acid production. However, as the Lurec® process states, the higher the strength of the SO.sub.2 stream, the greater the energy production; therefore, it can be expected that, in practice, the Looping Sulfide Oxidation process would actually produce more energy than the conventional process due to its high strength SO.sub.2 stream. However, if equal energy production is assumed in the acid plant, the only major differentiating factor in energy production will be during the reoxidation of the copper to CuO, which the conventional process does not perform. During reoxidation, the amount of high pressure steam (100 bar, 350° C.) that is estimated to be produced is 4049 kg per 1000 kg of Cu produced (Tables 7 and 8).

(31) TABLE-US-00007 TABLE 7 Reoxidation Reaction Air Preheater Heat & Material Balance Temperature Amount, Amount, Amount, Latent Total © kmol kg Nm3 H, kWh H, kWh INPUT Reoxidation Heat Recovery-Air Preheater New Reaction Air 25.000 266.141 7678.264 5965.184 0.00 0.00 O2(g) 25.000 55.890 1788.402 1252.689 0.00 0.00 N2(g) 25.000 210.252 5889.862 4712.495 0.00 0.00 Reoxidation Flue 800.000 703.196 20140.911 15761.146 4705.52 4705.35 Gases N2(g) 800.000 592.305 16592.471 13275.683 3927.10 3927.10 O2(g) 800.000 110.889 3548.310 2485.418 778.39 778.39 SO2(g) 800.000 0.002 0.131 0.046 0.02 −0.15 OUTPUT New Reaction Air 400.000 266.141 7678.264 5965.184 829.38 829.38 O2(g) 400.000 55.890 1788.402 1252.689 180.35 180.35 N2(g) 400.000 210.252 5889.862 4712.495 649.02 649.02 Reoxidation Flue 671.626 703.194 20140.780 15761.101 3875.97 3875.97 Gases N2(g) 671.626 592.305 16592.471 13275.683 3235.65 3235.65 O2(g) 671.626 110.889 3548.310 2485.418 640.32 640.32 SO2(g) 671.626 0.000 0.000 0.000 0.00 0.00

(32) TABLE-US-00008 TABLE 8 Reoxidation Boiler Heat & Material Balance Temperature Amount, Amount, Amount, Latent Total © kmol kg Nm3 H, kWh H, kWh INPUT Reoxidation Heat Recovery-Boiler Reoxidation Flue 671.626 703.194 20140.780 15761.101 3875.97 3875.97 Gases N2(g) 671.626 592.305 16592.471 13275.683 3235.65 3235.65 O2(g) 671.626 110.889 3548.310 2485.418 640.32 640.32 SO2(g) 671.626 0.000 0.000 0.000 0.00 0.00 Cooling Water 25.000 224.748 4048.881 4.061 0.00 −17833.96 H2O(100 barl) 25.000 224.748 4048.881 4.061 0.00 −17833.96 OUTPUT Reoxidation Flue 150.000 703.194 20140.780 15761.101 715.05 715.05 Gases N2(g) 150.000 592.305 16592.471 13275.683 600.31 600.31 O2(g) 150.000 110.889 3548.310 2485.418 114.73 114.73 SO2(g) 150.000 0.000 0.000 0.000 0.00 0.00 High Pressure 350.000 224.748 4048.881 5037.413 1220.43 −14673.04 Steam H2O(100 barg) 350.000 224.748 4048.881 5037.413 1220.43 −14673.04

(33) Taking into consideration the total estimated energy output during Looping Sulfide Oxidation, the amount of energy available for capture during the reoxidation of the molten copper is approximately 1.64 times greater than the amount available for capture during sulfuric acid production alone. This comparison is vital because during conventional processing, significant energy consumptions and productions have been observed at different processing facilities.sup.15. Therefore, on the basis of potential energy available for capture, the Looping Sulfide Oxidation process provides significant improvements over the conventional technology; the increased energy production drastically mitigates the net energy consumption during copper processing. .sup.15Coursol P, Mackey P J, and Diaz C M (2010) Energy Consumption in Copper Sulphide Smelting, in Proceedings of Copper 2010, 1-22.

Example 2

(34) Using the same feed conditions and smelting furnace parameters as those presented in Example 1, the slag produced in the smelting furnace can be treated in the slag treatment furnace by sulfidation. During sulfidation, iron pyrite (FeS.sub.2) is added to the molten slag to sulfidize the copper, causing it to separate out of the slag into a copper matte (FIGS. 14 and 15). In this scheme, the copper recovery from the slag ranges from 99 to 96% in the temperature range of 1200-1400° C. The slag has a melting temperature of 1120° C. and a viscosity of 0.709 poise at 1300° C. The treated slag is fit for disposal as waste. The copper matte, which is now rich in copper sulfide, must be processed in the smelting furnace again before the copper can be sent to the anode furnace as blister copper.

Example 3

(35) Copper sulfide concentrate (CuFeS.sub.2) is smelted with CuCO.sub.3 to produce copper metal, iron oxide slag, and rich SO.sub.2 off gas (FIGS. 16-18). In such a reaction, 3000 kg of CuFeS.sub.2 (with 173.4 kg of FeS.sub.2 and 294.8 kg of CaAl.sub.2Si.sub.2O.sub.8) is reacted with 11500 kg of CuCO.sub.3 and 1000 kg of SiO.sub.2 and 500 kg of CaO between 1200° C. and 1400° C. The products of this reaction will include an off gas that is comprised mainly of CO.sub.2 and SO.sub.2 (FIG. 19). At 1300° C., 6654 kg of molten Cu will be produced containing 0.30% S, 0.21% O and 0.0028% Fe. The 3490 kg of slag produced contains 10.7% Cu.sub.2O.

Example 4

(36) Copper sulfide concentrate (CuFeS.sub.2) is smelted with CuSO.sub.4 to produce copper metal, iron oxide slag and rich SO.sub.2 off gas (FIG. 20-22). In such a reaction, 3000 kg CuFeS.sub.2 (with 173.4 kg FeS.sub.2, 294.8 kg CaAl.sub.2Si.sub.2O.sub.8) is reacted with 7423 kg CuSO.sub.4 and 1000 kg SiO.sub.2 and 500 kg CaO between 1200° C. and 1400° C. The products of this reaction will include an off gas that is comprised of SO.sub.2 that is diluted with any combustion gases or inert gases. At 1300° C., 3658 kg of molten copper will be produced containing 1.1% S, 0.33% O and 0.0025% Fe. The 3559 kg of slag produced contains 12.3% Cu.sub.2O.

(37) It will now be apparent to those skilled in the art that other embodiments, improvements, details, and uses can be made consistent with the letter and spirit of the foregoing disclosure and within the scope of this patent, which is limited only by the following claims, construed in accordance with the patent law, including the doctrine of equivalents.