Hydrometallurgical process for the production of copper
United States Patent Sardisco Apr. 29, 1975 HYDROMETALLURGICAL PROCESS FOR THE PRODUCTION OF COPPER [75] Inventor: John B. Sardisco, Shreveport, La.  
 [73] Assignee: Pennzoil Company, Houston, Tex.  
 [22] Filed: May 23, 1974 [21] Appl. No.: 472,736  
  Related U.S. Application Data [63] Continuation-impart of Scr. No. 289.980. Sept. 18.  
 1972, Pat. No. 3.817.743.  
 [52] U.S. Cl 204/107; 75/1; 75/101 R; 75/101 BE; 75/114; 75/117; 75/118; 423/557; 423/36; 204/108 [51] Int. Cl. C22d l/16; C22b 15/00 [58] Field of Search 204/107-l08; 75/117-118. 101 R. 101 BE, 114, 72; 423/557, 36  
 [56] References Cited UNITED STATES PATENTS 1.833.682 11/1931 Mcycr 75/116 3.785.944 l/l974 Atwood et al. 75/117 3.817.743 6/1974 Sardisco 75/117 Primary Examiner-R. L. Andrews Allorney, Agent, or FirmLarry B. Feldcamp; Delmar L. Sroufe; Frank B. Pugsley 1 1 ABSTRACT An improved process is described for the recovery of metallic copper from sulfur treated copper iron sulfide ore concentrates. X-bornite may be prepared from the chalcopyrite content of such ore concentrates by reacting said concentrates with sulfur vapor for at least about 6 minutes at 460500C and 200 mm to 750 mm of Hg. By recycling the reaction product through the sulfur vapor reactor, residual chalcopyrite can be reduced but the main product of such recycling is idaite instead of x-bornite. In this improvement the sulfur treated ore concentrate is leached with cupric chloride. The pregnant liquor may be diluted with as much as about one part of water to one part of liquor and/or it may be cooled to precipitate cuprous chloride and silver chloride from the liquor. Metallic &#39;copper may then be produced from the precipitated cuprous chloride. In a preferred method, the cuprous chloride is reacted with sulfuric acid and 0 at 0-50 psig and 1 lO-l 15C to produce cupric sulfate and hydrogen chloride. This cupric sulfate may be electrolyzed in a conventional cell to produce copper metal at the cathode and sulfuric acid and silver compounds at the anode.  
 In one mode of practicing the invention, silver is removed from copper chloride liquor which is separated from the precipitated cuprous chloride. 1n the latter embodiment the liquor is first treated with oxygen to remove iron from the system and to convert the cuprous chloride to cupric chloride. Silver is removed from the resulting solution by anionic ion exchange.  
 20 Claims, 2 Drawing Figures Lia HYDROMETALLURGICAL PROCESS FOR THE PRODUCTION OF COPPER CROSS-REFERENCE TO RELATED APPLICATION This application is a continuation-in-part of copending application Ser. No.289,980, filed Sept. 18, 1972 now U.S. Pat. No. 3,817,743.  
 BACKGROUND OF THE INVENTION 1. Field of The Invention This invention relates generally to hydrometallurgical processes for the production of metallic copper from copper iron sulfide ore concentrates. In particular, this invention is concerned with the treatment of copper iron sulfides to make the sulfides more responsive to hydrometallurgical processing, In accordance with this invention, chalcopyrite and other copper iron sulfides are first reacted with sulfur vapor to transform the sulfides into other compounds which are thereafter leached with cupric chloride to solubilize&#39;the copper content of the ore concentrates. In accord with the improved process of this invention, high grade copper metal may be recovered by processing the resulting copper bearing pregnant liquor.  
 2. Prior Art As noted in the above-referenced parent application, chalcopyrite, which is the principal copper sulfide minnesium chloride, or any mixture thereof. It is used in the leach solution to prevent premature precipitation of the cuprous chloride.  
  The resulting pregnant liquor, which contains cupric chloride, cuprous chloride and ferrous chloride, may be cooled and/or diluted with to 1.0 part of water to 1 part of pregnant liquor to crystallize cuprous chloride and silver chloride. By controlling the temperature and dilution ratio, the amount of cuprous chloride and silver chloride precipitated can be controlled. The silver precipitate may be minimized in this way if high purity cuprous chloride is desired. Moreover, if the ore concentrates contain silver in an amount which causes a higher percentage of silver precipitation than desired, cement copper can be&#39;added in the leach reactor to maintain it within desired limits. Regardless of the deeral in the United States, has been found to be the most resistant to treatment by hydrometallurgical processes. Processes developed for the treatment of chalcopyrite have been plagued with low recoveries of copper from the ore. Some processes have been able to recover a substantial amount of copper in the ore but only after the leaching operation has been carried on for a number of hours which is economically undesirable. A further problem in the processing of copper iron sulfide ores is the simultaneous dissolution of the iron which acts as a contaminant inthe copper recovery steps.  
  In the above-referenced copending application, a process is described whereby chalcopyrite and other copper iron sulfides are reacted with sulfur vapor to form compositions which are highly responsive to leaching. In that process, x-bornite and/or idaite are produced and the latter substances may be leached with chlorides or sulfates to produce copper chlorides or copper sulfates as the case may be. Conventional processing of these copper&#39; salts has achieved satisfactory yields of copper metal but the resulting products do not have the desired degree of purity.  
 SUMMARY OF THE INVENTION An object of this invention is to recover high grade copper metal from sulfur treated copper ore only by hydrometallurgical processing. Another object of this invention is to recover silver from the ore thereby preventing it from contaminating the copper metal. A further object of this invention is to produce purified copper sulfate as a merchantable product.  
  In accomplishing the foregoing objects, ore concentrates containing x-bornite or idaite as&#39;the main copper-containing material may be prepared by the reaction of copper iron sulfide ore concentrates and sulfur vapor at 460500C. The sulfur-treated ore concensired purity, it is preferable to precipitate (as CuCl) the amount of copper solubilized in the leach reaction. The liquor from which the CuCl and some of the AgCl have been precipitated contains NaCl, some CuCl, CuCl AgCl, and FeCl with the weight ratio of copper to silver being about 1,500. It is necessary to treat this liquor to oxidize the remaining CuCl to CuCl and to remove the iron from the system. By using oxygen at slightly elevated pressure and 125C, the CuCl is oxidized to CuCl and FeCl is oxidized to the ferric state and precipitated as a ferric basic salt.  
  The resulting iron free cupric chloride solution may desirably contain about two-thirds of the silver that enters the system with the ore. The trace amount of silver exists in solution as a complex such as AgCl Since the copper ion exists in the solution as the positive Cu (as CuCl and the silver in the negative complex, AgClf, separation of the two is possible with an anionic exchange resin by adsorption of the AgClf complex. (Separation of silver chloride and cuprous chloride in the NaCl solution is difficult because both the silver and copper ions exist in the negative radicals,  
 AgCl; and CuClf, respectively.)  
  Finally, the solution that contains the regenerated CuCl and the NaCl is recycled to the leach reactor where the sulfidized ore is reacted with CuCl and NaCl.  
  Alternatively the AgCl is allowed to build up to an equilibrium level in the pregnant liquor from the leach reactor. And upon precipitating the CuCl, AgCl is also precipitated. The amount that precipitates does not have to be controlled as discussed above. The CuCl is then converted to CuSO, and HCl by reaction with H 80 and oxygen (by contact with air or 0 at 0-50 psig and 1 15C. The resulting aqueous solution contains Cu, S0,, C1 and Ag from which pure CuSO .5H O can be crystallized by dropping the temperature, or by operating the reaction at a concentration approaching the saturation level of copper sulfate. This copper sulfate is brought into solution and electrolyzed in a conventional cell to produce pure copper trates are leached at 1001 10C with a solution of cupric chloride saturated with a saline metal chloride at a residence time of 0.5 to 1 hour. The saline metal chloride may be sodium chloride, potassium chloride, magthe impurities in solution such as silver, bismuth, etc. precipitate at the cathode along with the copper. As a result high purity copper cannot be produced by direct electrolysis of chlorides. By converting the solid CuCl to CuSO solutions of CuSO can be electrolyzed to produce a high grade copper because during electrolysis the impurities deposit at the anode as a sludge.  
 BRIEF DESCRIPTION OF THE DRAWINGS In the accompanying drawings, FIG. 1 is a flow sheet of the process of this invention for the production of metallic copper from copper iron sulfide ore concentrates utilizing cupric chloride as the leaching agent.  
  FIG. 2 is a flow sheet of a subcombination process of this invention illustrating an alternate method of processing cuprous chloride for the production of metallic copper.  
 DESCRIPTION OF PREFERRED EMBODIMENTS The reaction of the CuCl with the x-bornite is illustrated by the following equation:  
 01 F63 70101 12 NaCl 12NaCuC1 FeC1 4.4s  
 The reaction of CuCl with idaite is as follows:  
 Cu FeS 7CuCl 12 NaCl 12 NaCuCl FeCl Precipitation of CuCl and AgCl from a pregnant 1iquor containing these compounds may be achieved by dilution with water as follows:  
 xNaAgCl yAgC1 l+ (x y) NaAgCl The relatively pure CuCl is preferably converted to CuSO by the following reaction:  
 i CuSO 1/2 H O HCIT This reaction is carried out in CuSO,,HClH SO -H O media. It is necessary to remove from the system 1 mole of HO per mole of CuCl to prevent the chloride ion concentration from building up too high in the liquor from which the CuSO .5H O is crystallized. If the chloride concentration is too high the crystallized CuSO .5H O will contain an excessive amount of chloride. The necessary amount of I-ICI is removed from the CuSO I-ICl--I-I SO aqueous solution by breaking the I-IClH O azeotrope with sulfuric acid.  
 REGENERATION OF CuCl AND IRON REMOVAL 7NaCuCl FeCl 20 SHCI 7CuCl H O 7NaC1 Fe(OH);;  
 (Basic Ferric Salt) Silver can also be removed from the cupric chloridesodium chloride solution which comes from the iron removal reactor by adsorption of the AgCl; complex with an anionic exchange resin.  
 EXAMPLES OF THE LEACl-IING REACTION By this invention 97.0% of the copper can be solubilized in as little as 15 minutes by leaching the sulfidized copper sulfides (x-bornite or idaite) with cupric chloride and NaCl. For the following examples, the copper iron sulfides from the vapor phase reaction between CuFeS and S were screened to remove the plus mesh size particles and then leached in a glass reactor at 1 15C and atmospheric pressure using one or two stages. Table I below shows: (A) the composition of the copper iron sulfide resulting from the vapor phase sulfidizing of chalcopyrite ore concentrates, (B) results of one stage leaching tests on sulfidized ore, (C) comparative results of one stage leaching test on a chalcopyrite ore, and (D) results of second stage leaching test on the residue from the first stage leach of the sulfidized ore. All of these tests were conducted batchwise.  
 TABLE I A. Composition of the sulfidized Copper Iron Sulfide (S-Ore) and Chalcopyrite (cpy) Chemical Analysis (Wt.%)  
 Cu Fe S X-ray Diffraction Ag Analysis (Approx. Wt.%)  
 cpy 27.63 27.14 30.6 0.019 80% cpy and 10% FeS (S-Ore) 24.24 26.42 36.6 0.016 4% cpy, 3% Bomite, 3% Idaitc;  
 remainder is x-bomite and pyrite Onc Stage Leaching Tests on Sulfidizcd Ore per equations 1 and 2 (basis one gram of S-Ore):  
 Gms  
 Test 4 is a repeat of Test 3 TABLE I Continued A. Composition of the sulfidized Copper Iron Sulfide (S-Ore) and Chalcopyrite (cpy) Chemical Analysis (Wt.%) X-ray Diffraction Cu Fe S Ag Analysis (Approx. Wt.%)  
 One Stage Leaching Test on Chalcopyrite Ore (For this test, the conditions were the same as for Test 3 and 4 above) Wt.% Solubilized Material Balance (Wt.%) Cu Fe Cu Fe 73.6 60.5 95.6 97.3  
 . D. Second Stage Leaching of Sulfidized Ore The residue containing 1.4% Cu from Test 1 above was leached under the following conditions:  
 CuCl Gms Gms Reactor Solubilized Solubilized H2O HOH NaCl Time Across 1 Stage Across 2 stages S-Ore SOre S-Ore (Hours) Cu Fe Cu Fe Table 1 shows that only 73.6 copper is solubilized Table 11 clearly illustrates that the amount of CuCl when leaching chalcopyrite ore in one stage as comand AgCl precipitated from the pregnant liquor can be pared to 9898.5% solubilization when leaching sulficontrolled by the degree of cooling and the amount of dized ore. Moreover, only about -30% of the iron in water added to the pregnant liquor.  
 TABLE II Results of the Cuprous Chloride and Silver Chloride Precipitation Tests (Equation 3) A. Ag Content of the Pregnant Liquor: 0.0008-0001 Wt.% Cu Content of the Pregnant Liquor: 12.0-14.0 Wt.%  
  Gms HOH Added Per Gm Gms Cu ppt Gms. of Ag ppt Temp. of Preg. per Gm Wt.% Cu per Gm Wt.% Fe (C) Liquor Cu in S-Ore in Cucl of Cu 10 in CuCl the sulfidized ore was solubilized. 5O EXAMPLES OF THE REACTION FOR EXAMPLES OF THE C S C O DE REGENERATING THE CUCI AND REMOVING THE IRON AND SILVER CHLORIDE PRECIPITATION REACTION As set forth in the Atwood and Curtis US. Pat. No. The hot pregnant liquor from tests 3 and 4 were di- 3,785,944, oxygen, either as&#39;O gas or air may be used vided into a number of equal parts. Some of aliquots in a reaction for regenerating the CuCl and removing were cooled to 35C, 25C or to 18C. Different the iron from the system. Their system, however, conamounts of water were added to the aliquots at the retains considerably more iron than the cupric chloride spective temperatures and equilibrated. The addition system. For the anionic ion exchange embodiment of 01&#39; water breaks the NaCuCl and NaAgCl complexes, the present invention, essentially all of the iron must be thereby precipitating CuCl and AgCl, respectively. Firemoved from the solution prior to silver removal with nally, each aliquot was filtered to remove the solid the ion exchanger since iron interferes. CuCl and AgCli For&#39;these&#39;tests, the total amount of sil- Below are the results for a number of runs that were ver in the pregnant liquor was thesilver derived from carried out batchwise in a titanium autoclave. For all the sulfidized ore by CuCl and. NaCl leaching. Silver the tests, oxygen gas was bubbled through the solution content of the pregnant liquor was abOut 0.0008 t0 forareaction time ofl hour atatemperature of C. 0.001 Wt.%. Results of these tests are given in Table II. The partial pressure of 0 was 7 psia.  
 Input (Grams) Results Wt.% Iron Cu Cone. of Fe Wt.% Copper Run No. Cu Fe Removed Oxidized in liq. Wt.% Precipitated I 50.5 3.19 99.8 100 0.0005 9.8 2 52.71 3.33 99.8 100 0.0007 17.4 3 51.72 2.53 99.6 I 0.0004 5.9 4 48.36 3.20 99.9 I00 0.0004 11.0  
  Essentially all the iron was precipitated as basic ferric salts along with 5 to of the copper. In a continuous operation this solid precipitate containing primarily iron and some copper may be re-cycled to the leach reactor to recover the copper content.  
 SILVER REMOVAL USING ANIONIC EXCHANGE RESINS In one embodiment of this invention basic ion exchange resins containing tertiary amine functionality on a styrene-divinyl benzene matrix have been found to be suitable for the removal of silver ions from the ironfree liquor discharged from the regeneration step. Such materials may be prepared by the suspension copolymerization of styrene and divinyl benzene to produce a polymer matrix having the desired degree of porosity. Such degree of porosity may be controlled by varying the amount of cross-linking. The amount of crosslinking varies with the amount of the cross-linking agent divinyl benzene. As the amount of cross-linking agent is decreased the greater the porosity of the polymer beads.  
  In a typical process, styrene and divinyl benzene are thoroughly mixed and an organic peroxide is dissolved in the mixture. This solution is poured into an equal or larger quantity of water and the suspension is heated until polymerization (an exothermic reaction) begins after which the temperature is controlled by cooling. After the beads of polymer harden, the polymerization is completed by continued heating in the reaction vessel, or the beads may be filtered from the water and the polymerization may be completed by heating in an oven.  
  The polymerized styrene divinyl benzene beads are then transferred to another vessel where they are treated with chloromethyl ether using a catalyst such as aluminum chloride or zinc chloride. This reaction introduces Cl-I Cl groups on the benzene rings. This product is then aminated with an amine of the general formula RRNH where R and R are each an alkyl group. A suitable reactant is, for example, dimethyl amine. After washing with water, the resin is then neutralized to the free base form. The functional sites of this type resin are tertiary amine groups, and a suitable ion exchange resin of this type is available under the trademark AMBERLITE IRA-93 sold by Rohm and Haas.  
  Other basic ion exchange materials which may be used for removal of silver may be made by following .essentially the same process for the production of a co- .polymer of styrene and divinyl benzene; however, after chloromethylation the product may be aminated with a tri-substituted amine such as, for example, trimethylamine to produce an ion exchange resin having as a functional group the highly ionized quaternary ammonium group:  
  CIl1 CH Ii1+ CH A product of this type which has been found satisfactory is available under the trademark AMBERLITE IRA-400 sold by Rohm and Haas Company. Other suitable Type I basic anionic exchange resins are available under the following brand names or trademarks: DOWEX I, DOWEX II and DOWEX 21K (sold by Dow Chemical Company) and DUOLITE A-42 (sold by the Chemical Process Company).  
  In the embodiment of this invention in which silver is recovered by contact with an ion exchange resin, the absorbtion of silver may be illustrated by the following chemical equation in which Res represents the ion exchange resin:  
 Res OH AgCl Res AgCl OH- Regeneration of the resin is accomplished by contacting the loaded resin with a basic material such as a solution containing sodium hydroxide, ammonium hydroxide or sodium carbonate. In the practice of this invention, a presently preferred regeneration solution is about 5 to 10 percent ammonium hydroxide at a flow rate of about 0.5 gal/cu ft/min for a total of about 2.4 pounds of ammonium hydroxide per cu. ft. of resin. Since the resin will usually be contaminated with iron, it is desirable that a preliminary flush of about 2.4 lbs. HCl/cu. ft. resin be used to remove the iron from the resin, a flow rate of about 0.5 to 1.0 gal/cu. ft/min. may be used for this&#39;purpose. I  
  The regeneration solution releases AgCI from the ion exchange resin as may be illustrated in the following equation:  
 Res AgCl NI-LOH Res OH Ag(NH C1 The silver salt complex in the regeneration solution may be processed to recover silver by an oxidation reduction reaction by employing electrolytic reduction of the silver salt solution or by reacting the salt with an element above silver in the electro&#39;rno&#39;t&#39;ive series. It is presently preferred to precipitate the silver by reacting the silver salt with zinc or aluminum metal.  
 EXAMPLE NO. 1  
  For this series of tests a column 66cm in height with a diameter of 2.4 cm containing 300 cc of Rohm and Haas Amberlite IRA-93 was used. The&#39;entire column. was heated to 50C by an exterior water jacket. Aqueous solutions of NaCl, CuCl AgCl and FeCl;; were passed through the bed at a flow rate 7-10 cc/min.  
 EXAMPLE NO. 2  
  For these tests we useda 1.3 cm diameter column, 2 feet high filled with 91 cc of Amberlite IRA-93. The tests conducted at room temperature (25C) using synthetic aqueous solutions of NaCl, CuCl AgCl and FeCl at a feed rate of 77 cc/min. 500 cc aliquots were taken for analysis. The bed was regenerated with HCl and NH OH after 2,000 cc of each solution was passed 4,000 cc of each solution were passed through the bed 10 through the bed. Below are the results.  
 and then the resin was regenerated with HC1 and NH OH. The next solution was passed through the bed. 1,000cc aliquots were taken for analyses. The results are given below.  
  The synthetic solutions, A, B, and C, were prepared from reagent grade materials. The actual solution, D, was the liquid product from a previous regeneration example.  
 &#39; TABLE III EXAMPLE NO. 3  
  For this example, Rohm and Haas Amberlite IRA- 400 (a strongly basic, Type I, quaternary ammonium anion exchange resin of standard porosity) was used to remove the silver. The results follow:  
 } The technique for the tests of this example was the same as that for Example No. 2.  
 Example I Results ccs Composition of 1000 cc Aliquots (Wt%) 1 Solution Passed thru Bed Cu Ag Fe Na A 0 (initial) 3.5 0.00165 .0074 3.01 (Synthetic) 1.000 3.20 0.00004 0.0001 1 3.46 2.000 3.64 0.00008 0.00032 3.46  
  3.000 3.70 0.0003 0.00054 4,000 3.77 0.00074 0.00070 B 0 (initial) 3.32 0.0010 0.00062 2.72 (Synthetic) 1,000 3.23 0.00025 0.00009 3.69 2.000 3.29 0.00028 0.00025 2.61 3.000 3.55 0.00050 0.00043 3.06 4,000 3.65 0.00068 0.00083 3.18 C 0 initial) 3,84 0.00115 0.00051 3.09 (Synthetic) 1,000 3.22 0.00005 0.00008 3.09  
  2.000 3.94 0.00015. 0.00024 2.98 3,000 3.85 0.00065 0.00036 2.96 4,000 4.00 0.00070 0.001 12 2.70 D 0 (initial) 3.18 0.00090 0.014 2.12 (Actual 1,200 2.99 0.00002 0012 2.43 Solution) TABLE V Composition W ccs of Solution of 500 cc Aliquot (Wt.%) 1 Solution Passed thru Bed 7 Cu Ag Fc Na G 0 (initial 4.54 0.00015 0.00043 3.38 (Synthetic) 500 3.96 0.00005 0.00026 3.52 1,000 4.80 0.00051 0.00033 3.49 1.500 4.68 0.00092 0.00035 3.31 2,000 4.79 0.00132 0.00048 3.14 H 0 (initial). 5.67 0.00191 0.00046 3.18 (Synthetic) 500 5.12 0.0001 1 0.00027 3.04 1,000 5 .67 0.00085 0.00039 2.93 1,500 5.70 0.00151 0.00048 2.99 2,000 5.31 0.0016 0.00083 2.18  
 EXAMPLES OF THE METHOD OF PREPARING CUSO A series of batch tests was made in an aqueous solu- CuSO and HCl was distilled to remove at least 1 mole of HCl per mole of CuCl input. In the third step the solution was cooled to crystallize 1 mole of CuSO per mole of CuCl input. The conditions and results of these tion of HClCuSO H SO to simulate recycling of 5 runs are in Table V1.  
 TABLE VI Step 1: Reaction of one mole of CuCl with four moles of H SO.  
  in a CuSO -H SO -HCI media. Conditions: Temp (C) 105 Tot. Pressure (psig) 40 Reaction Time min.)  
  Input (Gms) Ag Cu Cl HOH Total Component Wt.  
 97.5% H 80. 240 CuCl 0.0009 36.7 21.6 61 0150.. H SO 73.8 66.0 38% HO Media 350 703 Total 0.0009 1 10.5 87.6 350 1004* Output (Gms) Ag Cu Cl Total Component Filtrate 0 96.1 54.5 1375 Residue 0.0009 1 1.2 6.5 20.5 NaOH Trap 0 O l 1.8  
 Total 0.0009 107.3 72.8 1395.5&#34;  
 Step 11: Distillation of HCl-HOH to remove at least 1 mole of HCl per mole of CuCl (liquid 120-135C; vapor l 10C.).  
  Input (Gms) Ag Cu Cl Total Component Feed 0.0005 79.4 24.0 1040 Output (Gms) Ag Cu Cl HOH Total Component Distillate 1 3.0 l Pot Liquid 0.0005 78.1 8.7 895 Total 0.0005 78.1 21.7 1025 Step III: Crystallization of Copper Sulfate Conditions: Temp (C) 70 Retention Time (min) 120 lnput (Gms) Cu Cl Total Component Wt.  
 Feed Soln. 78.1 8.70 1012* Output (Gms) Cu Cl Total Component Wt.  
 Filtrate 45.2 6.21 928 Crystallization 30.2 0.1 1 99.6 Product Total 75.4 6.32 1027.6*  
 &#34;The poor material balances from C1 is probably due to the evolution of HCl while processing the components from each step.  
 the mother liquor from the crystallization step to the CuCl-l-1 SO.,O reaction step of Equation 4. 1n the first step of this series the CuCl, H 80 and 0 were reacted in an aqueous media of HClCuSO H SO in an autoclave at 40 psig. (A NaOH trap was put on the exit line to trap any HCl given off during the reaction.) Secondly, the resulting HClCuSO.,H SO rich in It has been found that the three steps of reaction, HCl removal and CuSO crystallization (all as generally indicated by Equation 4) may be combined into one step. CuCl, H 50 and were reacted at 120C for 60 minutes, followed by nitrogen purge for 90 minutes to remove l-lCl. (Solid material was present throughout the entire 90 minutes.) Then the slurry was filtered at l00l20C to remove the solid copper sulfate and the solid was washed with a small amount of water. Test results of the combined process are set forth below in Table VIII.  
 TABLE Vlll Step 1: Reaction of one mole of CuCl with one mole of H SO in a CuSO -H SO -HCl media Conditions: Temp (C) 120 Total Pressure Atmospheric Reaction Time (Min) 60 Time of Nitrogen Flush (Min) 90 Total Cu Cl Component Wt. lnput (Cums) 96% H 80 1 38 CuCl 22.8 13.4 38 CuSO -H SO -38% HCl Media 41.3 41.2 636 Total 64.1 54.6 712* Total Cu Cl Component Wt. Output Filtrate v 37.8 21.2 727 Cake Produce 24.1 0.1 61.7 NaOH Trap 0 15.5  
 Total 61.9 36.8 7887* *ln the above Tables Vl. Vll and VIII. the apparent increase in the weight of the output components in Steps 1 and 3 was due to wash water retained in the filtrate.  
  FIG. 1 is a schematic diagram of the proposed continuous process to produce copper from a copper iron sulfide ore concentrate containing chalcopyrite.  
  In the sulfidizing of copper iron sulfide ore concentrates, such as chalcopyrite ore, the ore concentrates are added to the sulfidizing reactor through line 11. Molten sulfur is introduced into reactor 10 through line 13 wherein it is vaporized before being mixed with the ore concentrates. The vaporized sulfur is preferably maintained at a partial pressure of at least about 200 mm of Hg. In the reactor the ore concentrates are sulfidized in as little as six minutes at a temperature of about 470C, thereby converting most of the chalcopyrite content of the ore concentrates to x-bornite and pyrite. Excess sulfur is discharged through line 14. The  
 sulfidized ore from reactor 10 is then passed through line 16 to leach reactor 17 into which is also passed cupric chloride and sodium chloride solution through line 20.  
  Copper leaching is conducted in leach reactor 17 at 1 10l 15C at atmospheric pressure over a period of 0.5 to 1 hour. After the reaction is completed, the hot slurry passes from the leach reactor through line 21 to a separation device such as filter 25 where the pregnant liquor is separated from the residue. The residue which contains the unreacted pyrite, sulfur and other insolubles leave the separation device through line 26 and the pregnant solution leaves the device through line 27 and enters the crystallizer 28 which is maintained at l040C and has a retention time of 30 minutes to 4 hours. A controlled amount of water from line 30 is introduced to the crystallizer to effect the desired amount of crystallization of the CuCl which leaves the crystallizer through line 29. The resulting lean solution is removed from the crystallizer to the Iron Removal and CuCl Regeneration Reactor through line 31. Through line 32 oxygen or air enter the reactor 35 which is maintained at 90125C and a total pressure of -100 psig for 30 minutes to 4 hours. The resulting slurry leaves the reactor by line 36 and separation of the insoluble basic ferric salts from solution takes place in a separation device such as a centrifuge or filter 40. The insolubles leave the device through line 41 and the solution may be passed through line 50 to the anionic exchange resin columns 52 where silver may be extracted from the solution if desired. The solution then passes through line 53 to an evaporator 55 to remove excess water to maintain an adequate water balance in the system. Finally, the regenerated CuCl NaCl aqueous solution is added to the leach reactor through line 20.  
  The solid CuCl with some AgCl contamination enters the oxidation reactor 58 through line 29 along with air or oxygen from line 60 and recycle aqueous solution of CuSO HClH SO from line 62. One mole of H SO recycled from the electrolytic cell enters the reactor from line 65. In this reactor the CuCl is converted to CuSO at 95110C, 0-50 psig and a contact time of 15-30 minutes. Any HCl gas that is evolved leaves the reactor through 67 and is recycled to the leach reaction system along with l-lCl from line 70. The hot slurry leaves the reactor through line 72 and is passed through the separation device 80. Residue which leaves the separation device through line 81 may contain some unreacted CuCl and AgCl and is recycled to the leach system or processed to extract the silver.  
  The solution from the separation device goes through line 82 to the HCl stripper 85 where the remainder of one mole of l-lCl is removed. Any water in the HCl is recycled with the HCl through line 70 and subsequently removed in the leach system. Water is added to the oxidation reactor to make up the amount removed with the l-lCl.  
  Product from the HCl stripper goes through line 88 to the CuSO crystallizer 89 where CuSO 5H O is crystallized. Crystallization takes place at 4070C at a resident time of 30 minutes 3 hours. The resulting slurry is transferred to a filter or other suitable separation device 91 by line 92. The filtrate from the filter 91 which contains some CuSO with HCI, H SO and water is recycled through line 62 back to the oxidation reactor 58. The solid CuSO 5H O is washed with a H SO solution which is taken by line 95 from recycle line 65. This wash solution removes excess chloride from the cake and it is recycled through line 62 to the oxidation reactor 58.  
  The solid CuSO, 5H O may be removed through discharge conduit 96 as a merchandisable grade of CuSO, SI-I O. In the alternative the CuSO 5H O may be fed through conduit 100 into a vessel or dissolution reactor 102 where it is dissolved by make-up water which enters the vessel through line 105 and a recycle aqueous solution of H SO CuSO entering the vessel through line 106.  
  The rich CuSO, solution is passed through line 110 to a conventional electrolytic cell 99 where it is electrolyzed to produce pure copper at the cathode and silver in the anode sludge. Part of the recycle CuSO, H SO is passed through line 106 to dissolve the solid CuSO and the other part is conveyed through line 115 to evaporator 118 where it is concentrated and recycled through line 65 to the oxidation reactor.  
  The embodiment of the invention illustrated in FIG. 2 shows a useful subcombination of the process wherein cuprous chloride may be processed to produce CuSO, 5H O and/or metallic copper. One suitable method of making cuprous chloride has been heretofore described. Other processes are available for the production of cuprous chloride precipitate from copper ore. For example, a cuprous chloride precipitate may be produced by leaching pyrite ore containing copper with dilute acids and precipitating cuprous chloride from the leach liquor by treating it with cement copper as taught in British Pat. Specification No. 260,294, dated June 2, 1927.  
  FIG. 2 further illustrates a variation of the present invention in which the formation of copper sulfate, hydrochloric acid removal, and copper sulfate crystallization are all conducted in a single reaction vessel.  
  In the embodiment of FIG. 2, cuprous chloride is introduced into the oxidation reactor 258 through conduit 231. Oxygen is introduced by suitable means such as oxygen gas or air passed through line 260 and sulfuric acid is introduced through line 265. In this reactor the CuCl is converted to CuSO, at 95l30C, 0-50 psig and a contact time of 30 minutes to 2 hours. Hydrogen chloride evolved from the reaction is conveyed from the reactor through line 267 to be available as a leach agent, or to be recovered as a byproduct. The copper sulfate slurry discharged from the oxidation re-.  
 actor comprises copper sulfate, hydrochloric acid and sulfuric acid. It is conveyed through line 300 to the separator device 291 which may be any suitable filter, centrifuge or the like.  
  The copper sulfate cake or residue in separator 291 is washed with a sulfuric acid-copper sulfate solution conveyed from the electrolytic cell 299 through line 315, evaporator 318, and lines 265 and 295. After the sulfuric acid wash the copper sulfate crystals may be further washed with a small amount of water through line 294 and a merchandisable grade of copper sulfate, commonly known as blue vitriol, may be removed through conduit 296.  
  In the alternative, the copper sulfate from separator 291 may be conveyed through line 300 to the dissolution reactor 302 where it is dissolved by water which enters the vessel through line 205, and by recycled aqueous solution of H SO CuSO from electrolytic cell 299. The dissolved copper sulfate solution is conveyed into electrolytic cell 299 through line 310 where it is electrolyzed to product pure copper at the cathode and silver in the anode sludge. These products may be removed from the electrolytic cell through suitable discharge conduits or conveyor means such as copper product line 312 and silver product line 313.  
  Recycled electrolyte containing copper sulfate and sulfuric acid are passed through line 315 from which a portion is conveyed through line 306 to the dissolution reactor. Another portion of the recycle from the electrolytic cell is conveyed through evaporator line 318 to line 265 from which a part is conveyed through line 295 into separator device 291 where it is used to wash the copper sulfate crystals. The remainder of the recycle sulfuric acid from the electrolytic cell is conveyed by line 265 to the oxidation reactor. Washwater from separator device 291, containing copper sulfate, hydrochloric acid, sulfuric acid and water is also conveyed through line 262 to the oxidation reactor.  
  As previously noted, the ion exchange columns indicated at numeral 52 of FIG. 1 may be omitted in the practice of the present invention since the purified cuprous chloride is converted to copper sulfate in the oxidation reactor 58 or 258. When the ion exchange unit 52 is omitted, silver will be permitted to build up in the filtrate recycled from crystallizer 28 to the leach reactor. The silver chloride is thus permitted to build, up until its concentration is such that it will precipitate with the cuprous chloride in the crystallizer 28.  
  This embodiment, the silver chloride passes through the oxidation reactor and is crystallized out with the copper sulfate. It will be understood that in this process the amount of silver chloride that is precipitated does not have to be controlled since the separation of silver chloride from a copper sulfate solution may be readily effected in the electrolytic cell. In the electrolysis of a copper sulfate-silver chloride solution the copper is deposited at the cathode and the silver is precipitated with the anodic sludge. Thus a high purity copper may be obtained without regard to the silver content of the electrolyte.  
  It has been found that the present invention provides an economical means of producing high purity copper. By the use of a cupric chloride as a leaching agent a faster leach reaction may be achieved than the equivalent sulfate leach system, and lower pressures may be used. There is less formation of sulfates during chloride leaching, and the leaching process is more selective in that less iron and sulfur are leached with the copper in the ore. Moreover, the conversion of the relatively pure cuprous chloride cyrstals to copper sulfate as further taught by this invention has the advantage that a copper sulfate electrolyte may be electrolyzed to produce copper of higher purity than can be produced from a copper chloride electrolyte having the same level of contamination.  
 I claim:  
  1. In a process for the production of metallic copper from copper iron sulfide ore concentrates containing chalcopyrite in which the ore concentrates are first reacted with sulfur vapor to form a sulfur-treated concentrate containing a member from the class consisting of x-bornite, idaite and mixtures thereof, the improved hydrometallurgical process comprising:  
 a. Leaching said sulfur treated concentrate with cupric chloride to achieve substantial solubilization of the copper content of the ore concentrate, thereby forming a leached solution containing cuprous chloride; 7  
 b. Crystallizing cuprous chloride from said leach solution and separating the cuprous chloride crystals therefrom;  
 c. Reacting said cuprous chloride crystals with sulfuric acid and oxygen to produce copper sulfate crystals;  
 d. Separating said crystals from the copper sulfate liquor; I  
 e. Dissolving the separated copper sulfate crystals in a sulfuric acid media; and v f. Electrolyzing the resulting copper sulfate solution to produce metallic copper at the cathode.  
  2. The method according to claim 1 wherein said sulfur treated ore concentrate consists primarily of xbomite.  
  3. The method according to claim 1 wherein said sulfur treated ore concentrate consists primarily of idaite.  
  4. The method according to claim 1 wherein said sulfur treated concentrate&#39;is leached at a temperature in the range from about 100C to about 110C for such period of time as to achieve substantial solubilization of the copper content of the ore concentrates.  
  5. The method according to claim 1 wherein a saline metal chloride selected from the group consisting of sodium chloride, potassium chloride, magnesium chloride and mixtures thereof is maintained present during the leaching step at a concentration sufficient to avoid precipitation of cuprous chloride during said leaching step.  
  6. The process of claim 1 wherein the lean leach solution filtrate remaining after separation of crystals of cuprous chloride is reacted with oxygen to precipitate the iron content as insoluble basic ferric salt; said basic ferric salt is separated from the filtrate; and the resulting iron free filtrate is contacted with an ion exchange resin containing a styrene-divinyl benzene matrix having functional sites provided by chemical groups selected from the groups consisting of tertiary amines and quaternary ammonium groups to remove silver ions from said filtrate.  
  7. The process of claim 1 wherein the amount of copper in the cuprous chloride crystallized out of the leach solution is equal to the copper content of the solubilized sulfur-treated ore concentrate.  
  8. The process of claim 1 wherein the leach solution is reacted with oxygen to regenerate cupric chloride and to precipitate iron as basic iron salts; absorbing silver chloride salts from the resulting substantially iron free solution by contact with a basic synthetic resin having a styrene-divinyl benzene matrix and further having functional sites provided by functionally active ion exchange groups selected from chemical groups consisting of tertiary amines and quaternary ammonium groups; recovering the silver content therefrom by regenerating the ion exchange material with a basic solution to produce a solution containing silver ions; and recycling the regenerated cupric chloride solution to the leaching step.  
  9. The process of claim 1 wherein the cuprous chloride in step (b) is crystallized from the leach solution at l835C and l.0 part of water is added for one part of leach solution.  
  10. The process of claim 1 wherein the reaction of step (c) is conducted at a ratio of 1 mole CuCl with 1 mole of H 30 at about l30C ,for about 30 minutes to 2 hours to produce. a solution containing solid copper sulfate crystals.  
  11. In a process for the production of metallic copper from copper iron sulfide ore concentrates containing chalcopyrite in which the ore concentrates are first reacted with sulfur vapor to form a sulfur-treated concentrate containing a member from the class consisting of x-bornite, idaite and&#39;mixtures thereof, the improved hydrometallurgical process comprising:  
 a. Leaching said sulfur treated concentrate with cupric chloride to achieve substantial solubilization of the copper content of the ore concentrate, thereby forming a leached solution containing cuprous chloride;  
 b. Crystallizing cuprous chloride from said leach solution and separating the cuprous chloride crystals therefrom;  
 c. Reacting said cuprous chloride crystals with sulfuric acid and oxygen to produce a copper sulfate solution;  
 d. Crystallizing copper sulfate from said copper sulfate solution at 4070C for 30 min. to 3 hours;  
 e. Separating said copper sulfate from the resulting lean copper sulfate solution;  
 f. Dissolving the separated copper sulfate crystals in a sulfuric acid media; and  
 g. Electrolyzing the resulting copper solfate solution to produce metallic copper at the cathode.  
  12. The process of claim 11 wherein the reaction of step (e) is conducted with approximately 1 mole of CuCl and 4 moles of H 80, in a CuSO l-l SO -HCl media at about 95l 10C for about 15 to 30 minutes.  
  13. The process of claim 11 wherein said copper sulfate solution of step (e) is distilled at a liquid temperature of about l20-135C for sufficient time to remove about 1 mole of HCl for each mole of cuprous chloride entering the reaction step (e).  
  14. In a process for the production of metallic copper from copper iron sulfide ore concentrates containing primarily chalcopyrite ore in which the ore concentrates are reacted with sulfur vapor to form a sulfurtreated concentrate containing as the principal coppercontaining material therein a member from the class consisting of x-bornite, idaite and mixtures thereof, the improvement comprising:  
 a. Leaching said sulfur treated concentrate with cupric chloride to achieve substantial solubilization of the copper content of the ore concentrate, thereby forming a leached solution containing cuprous chloride;  
 b. Crystallizing cuprous chloride from said leach solution and separating the cuprous chloride crystals therefrom;  
 c. Reacting said cuprous chloride crystals with sulfuric acid and oxygen to produce a cupric sulfate solution. I  
 d. Crystallizing cupric sulfate from said solution and separating the cupric sulfate crystals from said solution.  
  15. A process for the production of metallic copper from cuprous chloride comprising the steps of:  
 a. Reacting said cuprous chloride with sulfuric acid and oxygen to produce a copper sulfate solution;  
 b. Crystallizing said copper sulfate from said solution and removing the resulting crystals therefrom;  
 c. Dissolving the copper sulfate crystals in a water and sulfuric acid media; and  
 d. Electrolyzing said copper sulfate solution to produce copper metal at the cathode.  
  16. The process of claim wherein the crystallization of copper sulfate in step (b) is conducted at about 40-70C temperature, and for about 30 minutes to 3 hours.  
  17. A process for the production of metallic copper from cuprous chloride comprising the steps of:  
 a. Reacting said cuprous chloride with sulfuric acid and oxygen at a ratio of about 1 mole of cuprous chloride and 1 mole of sulfuric acid in the presence of oxygen to produce copper sulfate crystals;  
 b. Separating said copper sulfate crystals from said solution;  
 0. Dissolving the copper sulfate crystals in a water and sulfuric acid media; and  
 d. Electrolyzing said copper sulfate solution to produce copper metal.  
 18. The process of claim 17 wherein said crystallization of copper sulfate in step (b) is conducted at about to C for about 30 minutes to 2 hours.  
  19. The process of claim 15 wherein the solubilization of copper sulfate crystals in step (c) is conducted at about 30-60C for about 15 minutes to 2 hours; said water being added in an amount from Ol .0 lb. water per pound of CuSO and said sulfuric acid being added as a l5% sulfuric acid solution in an amount ranging from about 5 to 10 lbs. of said sulfuric acid solution per pound of CuSO 20. The process of claim 17 wherein the solubilization of copper sulfate crystals in step (c) is conducted at about 30-60C for about 15 minutes to about 2 hours; said water being added in an amount from 0-l .0 lb. water per pound of CuSO and said sulfuric acid being added as a 1-5% sulfuric acid aqueous solution in an amount ranging from about 5 to 10 pounds of said sulfuric acid solution for l pound of CuSO UNITED STATES PATENT OFFICE ETIFICATE OF CORRECTION Patent No. 3:880&#39;732 Dated April 29, 1975 lnventofls) John B. Sardisco It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:  
 Col. 1, line 53, &#34;only&#39;! should be deleted Table II, Col. 6, fourth heading, &#34;Cucl should be CuCl Table III, Col. 9, first numeral in fourth column, .0074&#34; should be 0.0074  
  Table III, Col. 9, second column, first line after &#34;C&#34;, &#34;3,84&#34; should be 3.84  
 Col. 13, Table VII, &#34;Atomspheric&#34; should be Atmospheric Col. 16, line 4, &#34;product&#34; should be produce Col. 16, line 133, delete the word &#34;line&#34; before the numeral Col. 18, line 31, olf t should be sulfate o Signed and Emailed this second Day Of September 1975 [SEAL] Attest:  
 RUTH C. MASON C. MARSHALL DANN Arresting Officer (nnunissinner of Patents and Trademarks FORM USCOMM-DC 60376-P69 Q U.5. GOVERNMENT PRlNTING OFFICE 1 I969 0*366-334