Abstract:
A process for recovering silver from chloride solutions comprising contacting the solution with amalgams of various metals from Groups 2b, 4a, 5a, or 8b of the periodic table or copper to replace the metal with silver and recovering silver from the formed silver amalgam. The process provides an improvement in the process for recovering copper from its ores in which the copper in the ore is solubilized as cuprous copper in a leach liquor and the copper recovered from the leach liquor as cuprous chloride by crystallization, the improvement being the removal of silver from the leach liquor prior to crystallization by use of the amalgam to produce substantially silver-free cuprous chloride crystals.

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The invention lies in the field of recovering silver from cuprous chloride by amalgamation techniques. 
     2. Description of the Prior Art 
     In the recovery of copper from its ores, particularly sulfide ores, it is well known, as disclosed in U.S. Pat. Nos. 3,785,944 and 3,972,711, in order to avoid the disadvantages of recovering copper electrolytically, pyrometallurgically, and by other methods, to solubilize the copper in the ore as cuprous chloride in a leach followed by cooling the slurry to crystallize the cuprous chloride and recover copper from the cuprous chloride crystals. A major disadvantage of wet recovery like this technique, is that impurities like silver, iron and others are carried over during the crystallization into the cuprous chloride crystals and end up as impurities in the final copper product. Some of these impurities are deleterious to the properties of copper and reduce its sale value. While the latter may not be necessarily true of silver, the failure to recover the high priced silver so that it is not sold along with the copper at the price of copper, detracts from the economic feasibility of the overall process. 
     In accordance with prior art, silver is removed from high chloride solution by cementation on copper metal. It was found that the presence of cuprous copper in the solution however renders this technique inoperative. For example, it was found that silver was efficiently removed by cementation with copper metal down to &lt;0.001 g/l Ag from 200 g/l NACl or 182 g/l Fe ++  from solutions containing no Cu + . Also that the presence of 11, 23, or 30 g/l Cu +  in these solutions only permitted the Ag concentration to be lowered to 0.009, 0.016, and 0.026 g/l Ag, respectively. These data illustrate the deleterous effect of Cu +  and therefore demonstrate the need for a reductant which can cement Ag but not cement Cu +  from the solution. 
     Accordingly, it is an object of this invention to provide an effective process for recovering silver from cuprous chloride and additionally produce a silver and iron-free cuprous chloride. 
     It is another object of this invention to provide an improvement in the process for recovering copper from its ores in which the copper is solubilized as cuprous chloride, the cuprous chloride crystallized and the copper produced from the cuprous chloride crystals, the improvement being a procedure for recovering silver from the cuprous chloride crystals before copper is produced from them. 
     SUMMARY OF THE INVENTION 
     A process for recovering silver from solutions comprising contacting the solution with amalgams of various metals from groups 2b, 4a, 5a, or 8b of the periodic table or copper to replace the metal in the amalgam with silver and recovering silver from the formed silver amalgam. Silver is eventually recovered from the amalgam by distillation. A variety of techniques may be employed to pre-concentrate the silver before distillation. The invention includes the use of various sources of chloride ion, such as sodium chloride or ferrous chloride to keep the silver chloride and cuprous chloride in solution. An application of the invention is as an improvement in the process for recovering copper from its ores in which the copper in the ore is solubilized as cuprous copper in a leach and the copper recovered from the leach liquor as cuprous chloride by crystallization, the improvement being the removal of silver from the leach liquor prior to crystallization by use of the amalgam to produce substantially silver-free cuprous chloride crystals. 
    
    
     BRIEF DESCRIPTION OF THE DRAWING 
     FIG. 1 is a flow diagram of the silver recovery process per se of the invention, and 
     FIG. 2 is a schematic flow diagram illustrating where the silver recovery process would be introduced into the flowsheet of a prior art process for the recovery of copper from its sulfides described in U.S. Pat. No. 3,972,711. 
    
    
     DESCRIPTION OF THE PREFERRED EMBODIMENT 
     The invention has application in processes for recovering copper from its ores containing iron and silver as impurities and in which process the copper sulfide ore is leached with ferric chloride and the soluble cupric chloride reduced to the cuprous form, followed by recovering cuprous chloride from the leach liquor by crystallization and recovery of copper from the crystallized cuprous chloride. It is difficult in this process to prevent silver from being carried over into the cuprous chloride crystals from which product copper is recovered by reduction with hydrogen. 
     The invention can be adapted to the above process for the recovery of silver either as shown in FIG. 2, or after the cuprous chloride crystallization from sodium chloride solution, or earlier in the flowsheet after the initial leach. Whichever option is used, any cupric ions in the cuprous chloride solution must be reduced by copper metal to the cuprous state. The reduced cuprous chloride solution is then contacted with an amalgam to replace the metal in the amalgam with silver thus removing silver from the solution. Obviously, the preferred metal for replacing silver is copper because the use of copper does not introduce any additional impurities which could co-precipitate with cuprous chloride. 
     After the amalgamation step, the mother liquor is cooled to produce cuprous chloride crystals which are substantially free of silver and iron. Copper is then recovered from the cuprous chloride crystals, preferrably by reduction with hydrogen. 
     The invention is not restricted in its application to processes for recovering copper from its ore, but applies broadly to the recovery of silver from silver chloride solutions and from solutions containing both silver chloride and cuprous chloride, irrespective of the origins of these solutions. 
     It was found that very little silver can be cemented with the amalgam in the presence of cupric ions. It was also found that the invention is much more efficient in the absence of cupric and other ions which have a more oxidizing emf than silver. Accordingly, in the preferred modification, a reduction step is performed on the cuprous chloride solution or leach liquor prior to amalgamation to reduce any cupric and ferric ions present. 
     Although the description of the invention and the flowsheet illustrating it are based on the application of the invention to a process for recovering copper from its ores, the invention is not limited to this application as it includes the recovery of silver from solution broadly. Furthermore, even though the process is described and illustrated in the flowsheet as starting with cuprous chloride crystals produced in a process for recovering copper from its ores in which the copper is recovered as cuprous chloride crystals, it is not limited to this modification as the feed material can be a solution containing cuprous chloride. 
     The invention will now be described with reference to the accompanying drawings. Referring specifically to FIG. 1 of the drawing, the feed material is shown as cuprous chloride crystals which is the crystallization product of the process illustrated in FIG. 2, that is, a process for recovering copper from a sulfide ore in which the copper is recovered as cuprous chloride crystals. 
     The cuprous chloride crystals are dissolved in a dissolution step to produce a cuprous chloride solution. The cuprous chloride solution is then contacted with copper to reduce any cupric copper to cuprous copper. A non-oxidizing atmosphere is maintained to prevent reoxidation of cuprous ion. 
     From the reduction step the cuprous chloride solution goes to the silver removal column where it is contacted with the amalgam to replace the metal in the amalgam with silver. The silver is then recovered in the silver recovery circuit by distilling the mercury. 
     Following the amalgamation step the cuprous chloride solution goes to a mercury absorption column for removal of any dissolved mercury and after this step the cuprous chloride solution goes to the recrystallizer where it is cooled to produce cuprous chloride crystals, and the crystals filtered to provide a product of cuprous chloride which is substantially free from silver. Part of the mother liquor from the cuprous chloride crystallization step is returned to the dissolution step and part of it is bled off to the main circuit of a copper process for recovering copper from its ore as illustrated in FIG. 2 for removal of some iron before its return to the ferric chloride leach. 
     The flowsheet of FIG. 2 depicts a prior art process for the recovery of copper from a copper sulfide ore in which the ore is leached with ferric chloride to provide a leach liquor, cuprous chloride crystallized from the leach liquor followed by a liquid solids separation to recover the cuprous chloride crystals which are reduced with hydrogen to provide the final copper product. In order to insure that this product is substantially free of silver, iron and other impurities, the silver recovery process of the invention is introduced before the cuprous chloride crystals are recovered by cooling, followed by recovery of copper from the cuprous chloride crystals. 
     To illustrate the operation of the invention, tests were made by dissolving the feed material, cuprous chloride, as shown in FIGS. 1 and 2, in sodium chloride solutions and removing the silver with various amalgams as shown in Table 1 below. 
     
                       Table 1______________________________________Recovery of Ag from CuCl-NaCl SolutionsFree-flowing AmalgamFeed solution:       (Upflow)       CuCl = 100-185 g/l       NaCl = 200 g/l       Ag.sup.+ = 0.03-0.05 g/l       Temperature = 75-85° CColumn:Dimensions:       1&#34; ID × 9&#34; longPacking:    Porcelain berl saddles, 6 mm (41% void vol)Temperature:       75-85° C______________________________________             Residence Time of             Feed SolutionTest              in the Column, % AgNo.     Amalgam   min            Removed______________________________________1       Cu, 3%    9.3            892       Cu, 3%    13.1           943       Fe, 3%    13             834       Fe, 3%    14.4           755       Fe, 3%    14.9           946       Fe, 3%    4              897       Fe, 0.5%  15.88       Fe, 0.5%  7.79       Zn, 0.5%  15             8210      Zn, 0.5%  13.7           9111      Zn, 0.5%                 95______________________________________ 
    
     The data of Table 1 show that copper, iron or zinc amalgams effectively remove silver from sodium chloride solutions. 
     The rationale for utilizing the amalgams is as follows. Both zinc and iron metal are strong reductants and will completely cement Cu +  as well as silver from a sodium chloride solution making them unsuitable as reductants. If, however, they are amalgamated with mercury metal and then utilized, little Cu +  is cemented while silver is still rapidly and completely cemented. 
     Copper metal will not cement silver from this system in the presence of Cu + . If the copper metal is amalgamated with mercury, this Cu-Hg amalgam will then cement silver from the solution but not Cu + . 
     Copper is the most desirable amalgam as it is more compatable with the system and, therefore, additional tests were completed using copper amalgams and the data are shown in Tables 2, 3 and 4. 
     Two types of copper-Hg mixtures, which are referred to herein as amalgams were tested, a free-flowing copper (≈0.1-0.5% Cu) amalgam and a high percent Cu (≈90% Cu) amalgam which was essentially copper shot coated with mercury. It was found that contact of the feed solution with the amalgam can be effected batchwise, but is most conveniently accomplished in a column configuration. In one series of tests (Table 2) a low copper free-flowing amalgam was contacted with the hot CuCl-NaCl feed solution by flowing each counter-currently through a column packed with berl porcelain saddles. 
     In a second series of tests (Tables 3 and 4), essentially the same type of apparatus was used for the amalgamated copper shot, similar to an ion exchange column, and the feed solution upflowed through the shot. No mercury was pumped into the column. 
     
                       Table 2______________________________________Recovery of Ag from CuCl-NaCl SolutionFree-flowing Cu AmalgamColumn: Dimensions:              15&#34; long × 1.8&#34; ID (0.022 ft.sup.3)   Packing:   Porcelain berl saddles, 6 mm              (60% void vol)   Temperature:              85-90° CAmalgam:           ≦0.5% Cu (downflow); flow rate =              23-35 ml./min.Feedliquor:            (Upflow); flowrate = 19-36 ml./min.              CuCl = 169 g/l              NaCl = 200-220 g/l              Ag.sup.+  = 0.022-0.040 g/l              Temperature = 80-90° C              Free HCl = ≈ 2 g/l (pH = 0.0)______________________________________ Residence Time of Feed Solution in                Ag ConcentrationTest  the Column     Feed/Effluent % AgNo.   (min)          (g/l)         Removed______________________________________1     16.0           0.028/0.005   822     19.0           0.040/0.005   883     10.0           0.040/0.006   854     17.5            0.022/&lt;0.001 &gt;95______________________________________ 
    
     
                       Table 3______________________________________Recovery of Ag from CuCl-NaCl Solutions -Amalgamated Cu-Shot ColumnColumn:     Dimensions    15&#34; long × 1.8&#34; ID       Packing       Hg coated Cu Shot                     (3272 g; 9.8% Hg° ).                     Void volume 37.2%       Temperature   85-90° CFeed liquor:              Given belowTemperature:              85-90° C______________________________________Feed LiquorResidence    Effluent AssaysTest Time,       Ag        CuCl   Hg    % AgNo.  min         g/l       g/l    ppm   Removed______________________________________O-feed      0.038     172.8  0.20  --1    20.5        &lt;0.001    172.5  2.74  &gt;972    14.5        &lt;0.001    175.0  2.82  &gt;973    10.5        0.002     173.4  2.36  954     4.75       &lt;0.001    171.2  --    &gt;95O-feed      0.022     --     --    --5    11.0        0.001     181    2.34  950-feed      0.026     177.2  0.11  --6    12.0        0.010     181.9  1.38  627     6.9        0.010     182.2  1.75  62______________________________________ 
    
     
                       Table 4______________________________________Recovery of Ag from CuCl-NaCl Solutions -Amalgamated Cu Shot ColumnColumn:  Dimensions 8.9&#34; × 0.83&#34; ID  Packing    Hg-coated Cu shot (465 g; 6.6% Hg)             Void volume = 38.5%  Temperature             85-90° CFeedliquor:           See below (upflow)______________________________________Feed LiquorResidence     Effluent AssaysTest  Time,       Ag      CuCl   Hg    % AgNo.   min         g/l     g/l    ppm   Removed______________________________________ 0-feed      0.026   177.2  0.11  --1     8           0.002   --     --    922     4.4         0.004   176.9  1.14  853     12.0        0.002   175.5  1.34  92 0-feed      0.176   --     --    --4     8.8         0.012   172.2  1.90  93 0-feed      0.026   177.2  0.11  --5     8.3         0.008   170.8  1.74  69______________________________________ 
    
     The data of Tables 2, 3 and 4 shows that effecient silver recoveries were achieved with both types of copper amalgams. 
     The free-flowing copper amalgam was prepared by shaking the pure mercury with 150-mesh copper powder under a pH 0.5 HCl solution; the copper entered the mercury phase within one half minute of hand shaking. The procedure for the preparation of the iron and zinc amalgams was similar. 
     The amalgamated copper shot was prepared by brightening the copper shot with 1M HCl at room temperature and then contacting the cleaned shot (1/16-1/4 inch diameter) with mercury. Hand shaking the mixture under a pH 0.5 HCl solution produced a mercury-coated shot in less than two minutes. The shot was completely covered with a mercury layer. 
     The hot feed solution is passing through the silver removal column solubilizes some mercury from the amalgam. The removal of this solubilized mercury was accomplished by passing the hot feed solution through a heated column packed with copper metal. The effluent was then cooled to room temperature to produce cuprous chloride crystals. 
     The silver is recovered form the loaded free-flowing Cu amalgam by distillation of the mercury at approximately 280° C, 20 inches Hg vacuum. The residue from the mercury distillation is Cu-Ag dust. The percentage of Ag in this dust is dependent upon how high the mercury has been loaded in Ag and how low the Cu content has been allowed to drop. 
     Sometimes it is not necessary to distill all of the mercury if a copper amalgam is used. If the Ag-loaded amalgam still contains some Cu (&gt;1.0%), a lighter Cu-Hg and Ag-Hg amalgam phase will float to the top of the unstirred amalgam. This top phase can be skimmed off and most of the silver present in the original amalgam recovered from it. The bottom Hg phase, low in copper and Ag, can be returned for recycle. 
     The following Table 5 presents results of skimming tests which were made following the above-outlined skimming procedure. 
     
                       Table 5______________________________________Recovery of Ag from CuCl-NaCl SolutionsRecovery of Ag from Loaded Hg°Skimming            Assay   DistributionTest               Weight  Ag   Cu   AgNo.  Sample Description              %       (%)  (%)  (%)______________________________________1    Feed Hg       100     0.37 2.2  100Top Hg phase  17.7    1.54 11.8   74.4Bottom Hg phase              82.3    0.07 0.19  25/62    Feed Hg       100     0.37 --   100Top Hg phase  20.7    1.50 12.6 82Bottom Hg phase              79.3    0.08 0.68 183    Feed Hg       100     0.38 1.0  100Top Hg phase  6.5     3.5  --   61Bottom Hg phase              93.5    0.15 --   39______________________________________ 
    
     The results presented in Table 5 show that 80% of the Ag can be skimmed off in the top phase which is 20.7% of the total weight of the feed amalgam. A 61% Ag recovery can be realized if only a 6.5 wt% fraction is skimmed off. The bottom phase which can be recycled contained 0.2-0.68% Cu and 0.07-0.15% Ag. The feed amalgam contained 1-2.2% Cu and 0.37% Ag. In order to apply the skimming technique, the feed amalgam must contain at least 1% Cu by weight or no Ag-Hg phase will float to the top of the amalgam. 
     Silver was recovered from the loaded amalgamated copper shot by elution with mercury. The loaded shot was placed in a glass column along with the Hg and some HCl solution (pH 0-1). The mixture was inverted periodically during the contact time. The free mercury was then drained from the column. Tests showed that 85-91% of silver can be removed from the loaded Cu shot (0.35 - 0.79% Ag) by contacting with free Hg. The Hg effluent contains 0.25 - 0.38% Ag and the stripped shot contained 0.05% Ag. This stripping procedure also re-amalgamates any Cu shot that may have become depleted in Hg and, therefore, rejuvenates the column for its next service cycle. A series of tests were made using the elution procedure and the results are presented in the following Table 6. 
     
                                           Table 6__________________________________________________________________________Recovery of Ag from CuCl-NaCl SolutionsRecovery of Ag from Loaded Amalgamated Cu ShotElution with Hg°Procedure:   Mix free-flowing Hg with the loaded amalgamated Cu   shot and drain off free-flowing Hg°Temperature:   25° C__________________________________________________________________________              AssayTest    Sample     Wt  Ag  Cu Hg  AgNo.   Description (g) (%) (%)                     (%) Recovery__________________________________________________________________________1  Loaded Cu shot          80  0.024                  93.4                     ≈6.6   Free Hg°, before elution          229 0.002                  0.34                     99.66   Free Hg°, effluent          --  0.01                  0.10                     99.9                         ≈53%   Stripped Cu shot          --  0.0102  Loaded Cu shot          74  0.79                  85.9                     13.3   Free Hg, before elution          200 0.002                  -- 99.9   Free Hg, effluent          200 0.25                  -- 99.75                         ≈91%   Stripped Cu shot          69.5              0.051                  -- --3  Loaded Cu shot          77  0.35                  89.9                     9.8   Free Hg, before elution          66  0.002  99.9   Free Hg, effluent          61.5              0.38       ≈85%   Stripped Cu shot          81  0.49__________________________________________________________________________ 
    
     It will be noted from the results that up to about 91% silver was recovered using the elution procedure. 
     A detailed incorporation of the above procedure as shown in FIG. 1 is presented below. 
     The CuCl crystals (150 ppm Ag, 200 ppm Fe) were dissolved in the Ag circuit mother liquor (≈200 g/l NaCl, ≈140 g/l CuCl, 0.001 g/l Ag + , 0.0003 g/l Hg) at ≈90° C. After reduction of any soluble Cu ++  with metallic copper, this hot solution (200 g/l NaCl, 205 g/l CuCl, 0.011 g/l Ag + , 90° C) was passed through the Ag removal column. The column effluent (200 g/l NaCl, 0.001 g/l Ag, ≈0.0025 g/l Hg) was passed through a column packed with Cu metal to reduce the soluble Hg level to 0.0004 g/l Hg before cooling to 35° C. The resulting CuCl crystals (65 g/l CuCl crop) contained &lt;20 ppm Ag, ≈1.2 ppm Hg, and &lt;20 ppm Fe. The mother liquor from crystallization was recycled. The Ag can be periodically recovered from the loaded Cu amalgam by the techniques described above. 
     A series of tests were conducted utilizing amalgams of other metals and the procedure outlined above. The results of these tests are reported in Table 7 below which also presents a comparative test using a copper amalgam. 
     
                       Table 7______________________________________Recovery of Ag from CuCl-NaCl SolutionsInvestigation of Various AmalgamsTemperature:    25° CFeed     0.055 g/l Ag, 176 g/l CuCl, 300 g/l NaCl, 0.9-3.7solution:    g/l Fe.sup.+2, pH = 0.0, 100 ml.Amalgam: 60 gProcedure:    Mix amalgam and solution batchwise______________________________________                Reaction  % RemovedTest  Feed Amalgam   Time      From SolutionNo.   Metal    %         (hr)    Ag      Cu______________________________________1     Bi       0.64      2.5      98     32     Pb       1.6       2.5     &gt;98     --3     Cd       3.1       2.5     &gt;98     13.14     Ni       0.38              &gt;98     -- Zn       0.46      2.5     &gt;98     --5     Zn       0.5       0.5     &gt;95     --6     Fe       0.5       0.5     &gt;95     --7     Cu       0.1       2.5      98     --______________________________________ 
    
     The results show that up to 98% of silver is removed from the cuprous chloride-sodium chloride solution and that the bismuth, lead, cadmium, nickel, zinc and iron amalgams are as effective as the copper amalgam for silver removal. These other amalgams were prepared by a method similar to that used for preparing the copper amalgam as described above. 
     Additional tests were completed (Table 8), illustrating the applicability of the invention to the removal of silver from ferrous containing leach liquors. 
     
                                           Table 8__________________________________________________________________________Amalgam Description           Feed Solution                     Product Filtrate    ReactionTest     g Metal           Fe.sup.+2              Cu.sup.+1                 Ag  Fe.sup.+2                         Cu.sup.+1                             Ag  Zn Hg   Time Ag RemovalNo. Metal     g Hg  (g/l)              (g/l)                 (g/l)                     (g/l)                         (g/l)                             (g/l)                                 (g/l)                                    (g/l)                                         (hr) %__________________________________________________________________________1  Hg coated   Zn    5 g/l. coating           166              67 0.034                       50.7                         0.008                             3.4 0.02                                    1    762  Zn    5 g/l. coating           126              70 0.34                     126.8                         69  0.018                                 1.04                                    0.002                                         1    953  Zn    5 g/l. coating           143              60 0.24                     141 56  0.05                                 1.70                                    0.024                                         4    794  Hg only    --        77 0.56    77  0.50   0.006                                         18   115  Zn-Hg 0.3/13.8           155              78 0.032                     154 76  0.015                                 1.68                                    0.0034                                         2    536  Zn-Hg 1.8/14 155              78 0.032                     162 76  0.022                                 0.6                                    0.006                                         2    317  Zn-Hg 1.4/14 164              103                 0.050                     172 84  0.014  0.002                                         4    728  Zn-Hg 1.91/191           167              89 0.044                     --  84  &lt;0.001                                 5.3                                    0.01 0.5  1009  Hg coated   Cu    5 g/coating           -- 77 0.56                     --  80  0.34                                 -- 0.128                                         18   3910 Fe-Hg 1.9/190           167              89 0.044                     177 73  &lt;0.001 0.003                                         1.0  100__________________________________________________________________________ [Note:Cu.sup.+2 = 0.sub.2 g/l in all tests]- 
    
     The solution contained ferrous, ferric, cuprous and cupric ions along with silver. The types of amalgams employed were Zn-Hg, Hg pool, Cu-Hg and Fe-Hg. All tests were run at 65°-75° C with feed liquors which contained 126-176 g/l Fe ++  at a pH of 0.5. Various weight ratios of zinc to mercury amalgams were used and, in addition, various ratios of processed liquor to amalgams were tried. 
     The results show that Zn, Cu and Fe amalgams effectively remove silver from these leach liquors. Mercury alone was ineffective in removing silver. 
     It is seen from the above description and results that a process has been provided for the effective recovery of silver from cuprous chloride solutions. The process is seen to be particularly effective for use in combination with processes for the recovery of copper from its sulfide ores in which the copper is solubilized as the cuprous ion and recovered by cuprous chloride crystallization. The process results in a successful recovery of substantially all of the valuable silver in the ore with a consequent result that a salable copper product is produced which is substantially free from silver.