Patent 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 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.

Full Description:
CROSS-REFERENCE TO RELATED APPLICATIONS AND PUBLICATIONS 
       [0001]    This application claims priority from U.S. provisional patent application 61/662,603 and 61/690,210 both filed Jun. 21, 2012. The full content of the said applications and of all other patents, published patent applications and non-patent publications cited herein are incorporated herein by reference as though set out at length herein. 
     
    
     FIELD OF THE INVENTION 
       [0002]    The present invention relates to improved methods for production of copper from copper sulfide concentrates produced as part of a mineral ore refining. 
       BACKGROUND OF THE INVENTION 
       [0003]    De Re Metallica by Georgius Agricola, published in 1556, details the mining, smelting, and refining techniques and technologies of that era. Since then the basic chemical reactions to produce copper have not significantly changed, while the modern smelting process now treats a concentrate rather than as-mined ore of that time. However, technology has markedly advanced through numerous changes and improvements to copper smelting methodology since De Re Metallica&#39;s publication. The “Welsh” process, based on a series of sequential reverberatory smelting steps, subsequently dominated copper smelting for over a hundred years. In the 1890s, Nicholls and James developed a process (Great Britain Patent 18,898) based on an alternative final step in the traditional “Welsh” copper smelting process. In this invention part of the high-grade white metal stream was diverted for calcination to produce a copper oxide material for subsequent re-use in the oxidation of the main white metal stream to produce metallic copper. The large, fuel-fired reverberatory furnace was later used for concentrate smelting throughout the first three-quarters of the twentieth century. In more modern times, newer flash and bath smelting processes were developed. The flash smelting concept was described by Bryk et al. in U.S. Pat. No. 2,506,557. Later, Gordon et al described a variant of the flash smelting process in U.S. Pat. No. 2,668,107. An alternative to flash smelting is the bath smelting process such as introduced by McKerrow et al. in U.S. Pat. No. 4,005,856 and also Bailey et al. in U.S. Pat. No. 4,504,309. Still another bath smelting approach, referred to as the Isasmelt process, based on a top lance blowing system with the particular lance system described by Floyd in U.S. Pat. Nos. 3,905,807 and 4,251,271, was developed. The lance system is used in the process operating in Arizona as described by Bhappu et al in: EPD Congress 1994, Edited by G. Warren, The Minerals, Metals and Materials Society, 1993, pages 555 to 570. Each of the contemporary processes described above for the modern era produce a medium to high-grade of copper matte which is typically processed in Peirce-Smith converters to blister copper. Following this, the produced copper is transferred to an anode furnace (European Patent 0648849 B2) for finishing to anode copper for subsequent casting and thence to electrolytic refining. The conventional flash furnace and converter process flow sheet is depicted in  FIG. 1 . As shown here, copper concentrate is introduced into the flash smelting furnace (as an example of a modern smelting unit) where the copper sulfide concentrate react with oxygen-enriched air to form a medium grade of matte and a slag. The reaction in the flash furnace can be represented by the following equation (Equation 1). Some nitrogen will also be present with the oxygen, depending on the degree of oxygen enrichment. 
         [0000]    
       
         
           
             
               
                 
                   
                     
                       2 
                        
                       
                           
                       
                        
                       
                         CuFeS 
                         2 
                       
                     
                     + 
                     
                       
                         13 
                         4 
                       
                        
                       
                         O 
                         2 
                       
                     
                   
                   = 
                   
                     
                       
                         
                           Cu 
                           2 
                         
                          
                         S 
                       
                       + 
                       
                         
                           1 
                           2 
                         
                          
                         FeS 
                       
                       + 
                       
                         
                           3 
                           2 
                         
                          
                         FeO 
                       
                       + 
                       
                         
                           5 
                           2 
                         
                          
                         
                           SO 
                           2 
                         
                          
                         Δ 
                          
                         
                             
                         
                          
                         
                           H 
                           o 
                         
                       
                     
                     = 
                     
                       
                         - 
                         250 
                       
                        
                       
                           
                       
                        
                       Wh 
                     
                   
                 
               
               
                 
                   ( 
                   1 
                   ) 
                 
               
             
           
         
       
     
         [0000]    A fossil fuel may be used as a supplementary energy source as required for heating/sustaining typical flash temperatures above 1350° C. A silica flux is added during this step to flux with the iron oxide product shown in Equation (1). The resulting flash furnace slag is sent to a slag treatment facility for copper recovery. The process off-gases are first cleaned and are then treated in a sulfuric acid plant for sulfur recovery. 
         [0004]    The remaining molten white metal is transferred to a converter, where it is blasted with oxygen-enriched air to remove remaining sulfides, produce the blister copper, and form an additional slag (Equations 2 and 3). 
         [0000]      Cu 2 S+O 2 =2Cu+SO 2  ΔH°=−59 Wh  (2)
 
         [0000]      FeS+1.5O 2 =FeO+SO 2  ΔH°=−130 Wh  (3)
 
         [0000]    The converter slag is typically higher in copper content, and also requires slag treatment. The flue gases from this step also require processing in the sulfuric acid plant. The copper melt is sent to anode casting (often proceeded by an anode furnace to further purify the copper metal) and then on to electrolysis. 
         [0005]    In total, this flash process has gained wide-spread acceptance in the copper industry. Its advantages over older reverberatory molten bath smelting are manifold: utilization of the heat released during oxidation of sulfides with oxygen, high furnace throughput, high copper recovery into matte, and higher SO 2  content in the off gas relative to the molten bath process. However, and as previously mentioned, significant control must be maintained throughout the process and significant opportunities for improvement exist. Principally, the composition of the feed materials must be well specified, an understanding of the absolute and relative particle sizes is required, moisture and sulfide contents of the concentrates and fluxes must be quantitatively known, and furnace dimensions and temperatures are critical. Precise control over the feed ratios and rate of oxygen injection must be maintained. Similarly, the amount of siliceous flux that must be added is wholly dependent on the sulfide concentrate and the amount of iron that must be oxidized; high copper losses into the slag are still observed and this requires a separate treatment step. The energy demands of the flash process require preheating of the furnace to circa 900-1100° C. to initiate the exothermic reactions involved when oxygen enrichment is not used. This high temperature conversion leads to NO, formation. Oxygen-enriched air is normally used, in which case preheating the air is not common. 
         [0006]    Several variations on flash smelting technology have been developed since the Gordon et al. first work. U.S. Pat. Nos. 5,662,730; 3,790,366; 3,948,639; 3,892,560; 4,615,729; 4,470,845; 3,674,463; 5,607,495; 4,521,245; and US Published Patent Application 2005/0199095 demonstrate oxygen enrichment of air, various techniques for copper recovery from slags as well as partial or dead roasting of the sulfide concentrate prior to flash smelting. 
         [0007]    Work performed in the 1890s by Thomas Davies Nicholls, et al. (Great Britain patent 18,898) details the use of copper oxides in roasting copper mattes to copper metal. During this time period, pneumatic copper converting was just in its infancy, hence this method was considered an improvement over the established contemporary roasting process. Copper (I) sulfide, previously smelted into matte (76-78% copper), is crushed and melted in a reverberatory furnace common at that time with calcined copper. The produced copper was then poled to produce a final copper. In this process, it was difficult to produce CuO during the calcination of Cu metal, so Cu 2 O was used. Production of copper anodes from copper sulfide sources without producing an intermediate copper matte phase has been performed and summarized in the literature 1,2 . In such operations, the copper sulfide concentrate is first dead roasted at elevated temperatures (900° C.) in an excess of oxygen to produce a copper calcine with sulfur levels around 2% (generally 1-1.5% sulfur). The calcine is then transferred to an electric furnace (e.g. the Brixlegg Process) 3,4 , a segregation furnaces 5,6 , a rotary furnace 7 , or a shaft furnace 8,9  where it is further converted to produce blister copper, slag and SO 2  off gases.  1 Opie W R, (1981) Pyrometallurgical processes that produce blister grade copper without matte smelting. IMM, 137-140. 2  (1980) Dead Roast-Shaft Furnace copper smelting, World Mining, Vol 33, Issue 12, 40-41. 3  Kettner P, Maelzer C A, and Schwartz W H, (1972) The Brixlegg Electro-Smelting Process Applied to Copper Concentrates, AIME Annual Meeting, San Francisco. 4  Paulson D L, Worthington R B, and Hunter W L, (1976) Production of Blister Copper by Electric Furnace Smelting of Dead-Burned Copper Sulfide Concentrates, U.S. Bureau of Mines, RI-8131. 5  Opie W R, and Coffin L D, (1974) Roasting of Copper Sulfide Concentrates Combined with Solid State Segregation Reduction to Recover Copper, U.S. Pat. No. 3,799,764. 6  Pinkney E T, and Plint N, (1968) Treatment of Refractory Copper Ores by the Segregation Process, Transactions of AIME, Vol 241, 373-415. 7 Rajcevic H P, Opie W R, and Cusanelli D C (1978) Production of Blister Copper in a Rotary Furnace from Calcined Copper-Iron Concentrates, U.S. Pat. No. 4,072,507. 8 Rajcevic H P, Opie W R, and Cusanelli D C (1977) Production of Blister Copper Directly from Dead Roasted-Copper-Iron Concentrates Using a Shallow Bed Reactor, U.S. Pat. No. 4,006,010. 9  Opie W R, Rajcevic H P, Querijero E R, (1979) Dead Roasting and Blast-Furnace Smelting of Chalcopyrite Concentrates, Journal of Metals, Vol 31, Issue 7, 17-22. 
         [0008]    It is an object of the present invention to provide a better method to recover copper from copper sulfide concentrates via a process chemistry previously unused by the copper smelting industry. This process is referred to as the “Looping Sulfide Oxidation” (or “LSO”) process. 
       SUMMARY OF THE INVENTION 
       [0009]    Many of the opportunities for improvement in flash smelting outlined above stem from the incremental removal of sulfur in two separate processing steps. As a result, the concentrations of the SO 2  streams, which while higher than the concentrations in the roaster and reverberatory furnace off gases (ca. 15-20% SO 2 ), the presence of two sulfurous off gas streams requires handling and treatment, and slags with relatively high copper contents are produced in both the flash furnace and the converter. The Looping Sulfide Oxidation process for copper production removes sulfur in a single step while using copper oxides (Cu 2 O and CuO) as oxidizing agents to either replace or augment oxygen (O 2 ) from natural air without producing a matte phase. Reference herein to copper oxide oxidizing agents include copper carbonates, sulfates and other oxygen containing copper compounds thermodynamically suitable for use in the Looping Sulfide Oxidation process following the guidelines shown in this application. 
         [0010]    Looping Sulfide Oxidation features three distinct steps: conversion of the copper sulfide concentrates into copper and copper oxides (wholesale desulfurization), recovery of copper from the slag, and looping oxide regeneration ( FIG. 2 ). This process primarily uses CuO as the oxidizing agent instead of O 2  in order to eliminate oxygen-enriched air utilization in the sulfur removal step and to generate energy from the reoxidation of copper downstream. Looping Sulfide Oxidation allows for greater energy capture by performing all the desulfurization of concentrates in a single step. Metal refining and slag treatment are handled simultaneously in the second step. Overall copper yield matches well with recovery levels achieved in the conventional flash process. 
         [0011]    In this first step of the Looping Sulfide Oxidation process, the copper concentrate is blended with fluxes and the oxidizing agent, CuO. In alternative embodiments, the CuO may be augmented with oxygen from air in a fashion such that the total stoichiometry of the system is maintained. The reaction that takes place in this furnace is presented below. 
         [0000]    
       
         
           
             
               
                 
                   
                     
                       CuFeS 
                       2 
                     
                     + 
                     aCuO 
                     + 
                     
                       
                         ( 
                         
                           
                             5 
                             - 
                             a 
                           
                           2 
                         
                         ) 
                       
                        
                       
                         O 
                         2 
                       
                     
                   
                   → 
                   
                     
                       
                         ( 
                         
                           1 
                           + 
                           a 
                         
                         ) 
                       
                        
                       Cu 
                     
                     + 
                     FeO 
                     + 
                     
                       2 
                        
                       
                           
                       
                        
                       
                         SO 
                         2 
                       
                     
                   
                 
               
               
                 
                   ( 
                   4 
                   ) 
                 
               
             
           
         
       
     
         [0000]    In such a reaction scheme, the value of a is allowed to vary such that ratio of CuO to O 2  might range from 5:0 to minimal CuO with greater portions of O 2  while still satisfying the reaction stoichiometry. While the relative ratio of CuO and O 2  is important, the total amount of oxidizer may be equal to or in excess of the amount required to completely oxidize the copper concentrate. Consideration must be made that excess of the oxidizer can influence the copper melt and/or slag compositions. In this sense, CuO functions to oxidize the iron in the concentrate and/or slag in addition to oxidizing (desulfurizing) the copper in the concentrate. A fraction of copper will be present in the slag as Cu 2 O due to the equilibrium established between the slag and the copper metal phase. As such, the calculated stoichiometry of the oxidizing agents is minimal, and will be exceeded. 
         [0012]    One possible embodiment of the furnace is a Vanyukov-type furnace 10,11  (exemplars of which appear in U.S. Pat. Nos. 4,252,560 and 4,294,433), i.e. the concentrate and fluxes are added through the slag, which is agitated by the injection of N 2 , hot combustion products, and/or air through tuyères; additionally, the energy is supplied via electrodes submerged in the slag. Due to the high energy demand of the endothermic reaction that takes place, additional heat must be provided to the first furnace. This heat will be supplied either solely through the electrical heating of the furnace or through electrical heating augmented by combustion of fuels, whose heat will be transmitted to the furnace through the hot gases in the tuyères and whose chemically inert combustion product gases will be injected into the molten slag to facilitate mixing. Another embodiment may use a top-blown lance in the slag in an Isasmelt-type furnace; this embodiment may also include electrode heating.  10 Bystov, V P, Fyodorov, A N, Komkov A A, and Sorokin M L (1992) The use of the Vanyukov process for the smelting of various charges, in Extractive Metallurgy of Gold and Base Metals, Australasian Institute of Mines and Metallurgy, Pardville, Vic., 477-482. 11 Bystrov, V P, Komkov A A, and Smimov L A (1995) Optimizing the Vanyukov process and furnace for treatment of complex copper charges, in  Copper  95- Cobre  95 , Vol. IV—Pyrometallurgy of Copper , ed. Chen W J, Diaz C, Luraschi A, and Mackey P J, The Metallurgical Society of CIM, Montreal, Canada, 167-178. 
         [0013]    The process chemistry that takes place in the first furnace is of critical importance. Most notably, metal not matte is formed during this step. This marks a significant differentiation and improvement over the present state of the art. The molten copper metal produced in the furnace is very low in iron and is sent directly to the anode furnace. The oxidized iron slag contains copper that must be recovered during slag treatment. As previously mentioned, the complete desulfurization of the concentrate is accomplished in this single step. This allows for significant energy capture during sulfuric acid production in an acid plant. Additionally, because no sulfurous/sulfuric gases will be produced in the downstream processing, aggressive energy capture can be performed on the off gases without fear of acid condensation. The major differences between this invention and the closest prior art (Nicholls et al.) are:
       1. The raw material is neither blister copper nor matte, but is rather copper sulfide concentrate   2. The raw material and copper oxide are simultaneously fed into the molten slag in the smelting furnace; the slag is agitated via the injection of combustion product gases or chemically inert gases   3. The use of oxygen is controlled and special care is taken to ensure that the total oxygen from air and copper oxide does not exceed 20% excess of the required stoichiometric amounts.
 
Slag composition in the smelting step can be further optimized by changing the amounts of fluxes (CaO, SiO 2 , Al 2 O 3 ) added to reduce the viscosity, lower the melting temperature, and increase copper recovery into the copper melt. Increased calcium oxide will decrease the copper solubility in the slag. The amount of Fe 2 O 3  (i.e. the amount of Fe 3+ ) in the slag must be reduced.
       
 
         [0017]    During slag treatment, the goal is to recover as much copper as possible from the slag phase so that it can be returned to the processing loop for copper anode production. In general, the slag from the first furnace will contain ca. 10-15% copper in the slag as Cu 2 O. The slag, which is still molten, is treated with either carbon (from coal or natural gas) to reduce the copper oxides to copper metal (and the trivalent iron to divalent iron), or oxidized with sulfur (e.g., as iron pyrite), to produce copper matte. With carbon reduction the copper from the slag treatment furnace can be mixed with the copper rich material from the smelting furnace; with sulfidation, the matte will be returned to the smelting furnace to be reprocessed. 
         [0018]    Slag treatment must reduce the copper content in the waste slag to levels below ca. 0.4 weight percent. The copper solubility in the slag is a function of many variables; one of critical importance is the Fe(III):Fe(II) ratio. In this process, the copper solubility in the slag is reduced (and thereby the copper recovery is increased) by significantly reducing the Fe(III) content in the slag. Additionally, when the product from slag treatment is copper metal, the iron content must be sufficiently low enough for an anode furnace. In the process presented here, the copper metal from the slag treatment step is blended with the copper metal from the first furnace to produce a copper-rich stream to be processed in the anode furnace. If sulfidation is performed, the copper matte produced will be processed in the first furnace. This step in the process is carried out in a traditional slag treatment furnace, e.g. an electric furnace. 
         [0019]    The anode furnace operates in the same fashion as conventional anode furnaces. The copper melt is first oxidized to oxidize any residual iron to a dry slag; in this step some of the copper metal may be co-oxidized. The slag is tapped off and the remaining copper melt is then deoxidized prior to casting to anodes ready for electrolytic refining. 
         [0020]    The fraction of copper that is sent to electrolysis is determined by the stoichiometry of the reaction in the smelting furnace (i.e. the amount of copper in the concentrate is equal to the amount of copper in the anodes for electrolysis). The necessary amount of copper to produce the requisite copper oxide for oxidation of the copper concentrate is sent to the reoxidation furnace. In this furnace, the copper melt is atomized and oxidized to CuO with air. This highly exothermic reaction can be harnessed for energy capture. The molten copper is oxidized at high temperatures in a downer or vertical furnace (ca. 1500° C.), and cooled below freezing to ca. 800° C. The powdered CuO is then looped back to the smelting furnace to complete the reaction cycle. 
         [0000]      2Cu+O 2 →2CuO ΔH 1500° C. =−59.5 Wh  (5)
 
         [0000]    This invention provides an improvement over the closest prior art wherein Cu 2 O was produced (Nicholls et al.) in which copper matte is oxidized to produce copper oxide. In this work, copper is reoxidized after atomization to promote rapid and complete oxidation. 
         [0021]    Alternatively, other sources of copper oxides can be used as oxygen carriers during Looping Sulfide Oxidation. For example, CuO is used in the industry as pigments in ceramic materials, battery materials and catalysts. These materials can be fed to the smelting furnace to augment the copper oxides that are produced in the reoxidation furnace. Similarly, several copper oxide minerals are processed by the copper industry; these minerals can be used as source of copper oxides during Looping Sulfide Oxidation. Thermodynamic calculations, made with FactSage 6.4 12  thermodynamic software, detailing such operation are disclosed below.  12 Bale, C. W., et al., FactSage™ 6.4.1, Thermfact and GTT-Technologies, CRCT, Montreal, Canada (2013). 
         [0022]    Copper scrap is also an important copper stream for Looping Sulfide Oxidation. Copper scrap metals and copper alloy scrap can be processed in Looping Sulfide Oxidation via either smelting in the smelting furnace in the presence of copper oxides (potentially augmented with air), or via initial oxidation to copper oxides in the reoxidation furnace. In the former embodiment, the copper scrap is melted in the smelting furnace and converted to copper metal in the same fashion as copper concentrate. Depending on the composition of the scrap, alloyed metals will report to either the slag or the copper phase. The use of this embodiment can gain an increase in the iron content in the molten copper due to the reduction of the iron oxides present in the slag with any reducing metals (e.g. aluminum or silicon) present in the scrap. In the latter embodiment, the copper scrap is processed to enable its rapid atomization and oxidation (in one embodiment, in a plasma furnace) to copper oxides that can be looped to the smelting furnace. 
         [0023]    Other objects, features and advantages will be apparent from the following detailed description of preferred embodiments taken in conjunction with the accompanying drawings in which: 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0024]      FIG. 1  (Prior Art) shows in block diagram form a generalized process flow chart for flash smelting conversion; 
           [0025]      FIG. 2  shows in block diagram form a Looping Sulfide Oxidation Process to produce anode copper; 
           [0026]      FIG. 2   a  shows schematically an electric arc furnace used in the smelting conversion; 
           [0027]      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; 
           [0028]      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; 
           [0029]      FIGS. 16-19  show traces of thermodynamic data detailing the smelting of CuFeS 2  with CuCO 3 ; and 
           [0030]      FIGS. 20-22  show traces of thermodynamic data detailing the smelting of CuFeS 2  with CuSO 4 . 
       
    
    
     DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS 
     Example 1 
       [0031]    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. 2   a  including tuyères for gas injection into a molten slag formed in the furnace. 
       Electric Furnace 
       [0032]    A room temperature copper concentrate comprising 3000 kg CuFeS 2 , 173.4 kg FeS 2 , and 294.8 kg gangue (CaO, Al 2 O 3 , SiO 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 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 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 2 O), iron oxides and gangue and flux derivatives. All compositions herein are weight percent unless otherwise noted.  13  Roine, A., et al., HSC 7.11, Outotec, Pori, Finland (2011). 
         [0033]    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 2 O 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 2  partial pressure above the slag in the electric furnace as compared to the O 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. 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Electric Furnace Heat &amp; 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*Al203*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 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Slag Treatment Furnace Heat &amp; 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 
               
               
                   
               
             
          
         
       
     
         [0034]    The SO 2  stream produced during the smelting step is sent to an acid plant for sulfuric acid production. The SO 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. 
       Slag Treatment 
       [0035]    The slag produced in the electric furnace (3.0% Al 2 O 3 , 31.3% SiO 2 , 15.5% CaO, 23.3% FeO, 13.6% Fe 2 O 3 , 13.2% Cu 2 O) 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 2 O 3  and Cu 2 O. 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 2 O 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. 
         [0036]    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. 
       Downer Reoxidation Furnace 
       [0037]    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. 
         [0038]    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. 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                 Reoxidation Heat &amp; 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 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
           
               
                 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 
               
               
                   
               
             
          
         
       
     
         [0039]    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. 
         [0040]    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. 
       Energy Balance 
       [0041]    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 14 . On this basis, we have evaluated the energy balance of the Looping Sulfide Oxidation process relative to conventional copper processing.  14  Daum 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. 
         [0042]    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 2  processed. 
         [0000]      2SO 2 +O 2 →2SO 3  ΔH 600° C. =−54.7 Wh  (6)
 
         [0000]    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). 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 5 
               
             
             
               
                   
               
               
                 Acid Plant Boiler Heat &amp; 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 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 6 
               
             
             
               
                   
               
               
                 Catalyst Bed Heat &amp; 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 it 
                 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 
               
               
                   
               
             
          
         
       
     
         [0043]    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 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 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). 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 7 
               
             
             
               
                   
               
               
                 Reoxidation Reaction Air Preheater Heat &amp; 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 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 8 
               
             
             
               
                   
               
               
                 Reoxidation Boiler Heat &amp; Material Balance 
               
             
          
           
               
                   
                 Temperatur 
                 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 
               
               
                   
               
             
          
         
       
     
         [0044]    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 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.  15 Coursol P, Mackey P J, and Diaz C M (2010) Energy Consumption in Copper Sulphide Smelting, in  Proceedings of Copper  2010, 1-22. 
       Example 2 
       [0045]    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 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 
       [0046]    Copper sulfide concentrate (CuFeS 2 ) is smelted with CuCO 3  to produce copper metal, iron oxide slag, and rich SO 2  off gas ( FIGS. 16-18 ). In such a reaction, 3000 kg of CuFeS 2  (with 173.4 kg of FeS 2  and 294.8 kg of CaAl 2 Si 2 O 8 ) is reacted with 11500 kg of CuCO 3  and 1000 kg of SiO 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 2  and SO 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 2 O. 
       Example 4 
       [0047]    Copper sulfide concentrate (CuFeS 2 ) is smelted with CuSO 4  to produce copper metal, iron oxide slag and rich SO 2  off gas ( FIG. 20-22 ). In such a reaction, 3000 kg CuFeS 2  (with 173.4 kg FeS 2 , 294.8 kg CaAl 2 Si 2 O 8 ) is reacted with 7423 kg CuSO 4  and 1000 kg SiO 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 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 2 O. 
         [0048]    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.

Technology Classification (CPC): 2