Patent Publication Number: US-6036025-A

Title: Mineral flotation separation by deoxygenating slurries and mineral surfaces

Description:
FIELD OF THE INVENTION 
     This invention relates to the physical separation of minerals and, in particular, to the separation of minerals of different mineralogical character. 
     BACKGROUND OF THE INVENTION 
     Many ore bodies comprise a mixture of valuable sulfide minerals with a number of non-sulfide minerals, including carbonaceous minerals (e.g. graphite, carbon-based residues as exist in Mt Isa, Australia ore bodies), talcose minerals (e.g. talc, brucite etc. which are associated with Western Australian nickel deposits and the Woodlawn, New South Wales, Australia base metal deposit) as well as amphiboles. 
     The non-sulfide minerals have naturally hydrophobic characteristics. The degree of hydrophobocity varies according to mineral and ore type from weakly hydrophobic to strongly hydrophobic. As a result, these so-termed &#34;gangue&#34; minerals have a tendency to float and are very difficult to separate from other valuable minerals, notably the sulfide minerals, e.g. chalcopyrite (CuFeS 2 ), pentlandite ((Ni,Fe) 9  S 8 ) and sphalerite (ZnS)). When present in mineral concentrates, these &#34;gangue&#34; minerals often attract penalty charges at the smelter and, indeed, may be the cause of rejection of the ore concentrate by the smelter. 
     In practice, two approaches to this problem exist, namely to minimize the flotation of the non-sulfide &#34;gangue&#34; minerals using specific reagents or, alternatively, to encourage flotation of the &#34;gangue&#34; minerals in a pre-flotation step prior to the flotation of the desired minerals. 
     In the first approach, reagents such as depressants (guar gum, carboxy methyl cellulose and the like) or dispersants, e.g. sodium silicate, are employed to minimize the flotation rate of the non-sulfidic minerals. In some cases, for example with copper-nickel-iron bearing ores, nitrogen is used as a flotation gas in combination with organic depressants. This tends to strengthen pyrrhotite depression and increase nickel recovery. While successful to some extent, the use of these organic depressants is non-specific and adversely affects the flotation behavior of the sulfide minerals in terms of metallurgy as well as froth structure. In addition, the use of such reagents is costly and, if it were possible, should be avoided. 
     Furthermore, the use of such reagents not only adversely affects flotation behavior, it affects downstream operations such as dewatering and settling of the minerals. Additionally, and particularly with depressants, there is a requirement to add more reagent at each stage of the separation process. 
     In the second approach, a separate flotation system is dedicated to the recovery of the naturally floating mineral. Reagents are added to prevent the flotation of the valuable sulfide minerals, however with varying degrees of success. Inevitably, there will be at least some loss of the valuable mineral with the gangue recovered from the pre-flotation system. Such losses represent an economic disincentive and should ideally be avoided. 
     The applicants have previously attempted to address this problem by providing a pre-flotation treatment in which the major proportion of the non-sulfidic or naturally floating materials are separated from the valuable sulfidic mineral prior to the primary flotation step. In this process, which is subject of Australian patent application no 28746/95, a mineral slurry is subjected to a sequence of mineral dressing operations in which an inert gas and/or reducing agent are added to the slurry to maintain an electrochemical potential conducive to the separation of the minerals by flotation. 
     However, apart from the requirement of an additional pre-float stage, such pre-flotation may adversely affect the recovery of the valuable sulfidic mineral in the subsequent primary flotation step. 
     It has been previously reported that nitrogen, with and without organic depressants, may have an effect in the recovery of nickel. These previous disclosures, however, generally use nitrogen as a flotation agent to maximize sulfide flotation, e.g. pyrrhotite, pentlandite or pyrite which has nickel, cobalt or some precious metals associated therewith. Increasing quantities of depressants are required to provide effective separation of the nickel and pyrrhotite for example. 
     In an effort to ameliorate at least some of the disadvantages of the prior art it is proposed to provide a method for conditioning a slurry or flotation concentrate which improves the separation of valuable sulfidic minerals from non-sulfidic &#34;gangue&#34; material. 
     SUMMARY OF THE INVENTION 
     In a first aspect, the present invention provides a method of treating a milled slurry or slurry of a flotation concentrate having a mixture of valuable sulfidic mineral and non-sulfidic gangue material wherein the slurry is conditioned with at least one of an inert, non-oxidizing gas and a reducing, deoxifying agent to achieve a controlled dissolved oxygen content or electrochemical reduction potential conducive to the flotation of the valuable sulfidic material from the non-sulfidic gangue material, followed by flotation of the valuable sulfidic mineral from the non-sulfidic gangue material using an inert, non-oxidizing gas as the flotation gas, the conditioning step being conducted simultaneously with or prior to the flotation step. 
     In a preferred embodiment, the amount of conditioning substance, i.e. inert, non-oxidizing gas and/or reducing, deoxifying agent added to the slurry is sufficient to increase rejection of the non-sulfidic gangue minerals in a subsequent flotation step. Alternatively, the amount of conditioning substance added is sufficient to improve selectivity between the valuable sulfide minerals and non-sulfide gangue minerals. 
    
    
     BRIEF DESCRIPTION OF THE DRAWING 
     FIG. 1 is a flow diagram of a typical flotation circuit in accordance with an embodiment of the present invention. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     The method of treating a slurry or flotation concentrate having a mixture of valuable sulfidic mineral and non-sulfidic gangue material in accordance with the present invention is premised upon the discovery that non-sulfidic gangue minerals have an affinity for oxygen. Oxidation or attachment of oxygen to talc, for example, renders the material even more hydrophobic i.e. floatable, than in its natural state. Therefore, the inventive method for conditioning a milled slurry or slurry of a flotation concentrate from a previous flotation cell overcomes at least some of the difficulties associated with the naturally floatable non-sulfide gangue minerals. Not wishing to be bound by any particular theory, the applicants believe such a conditioning step with nitrogen or other inert, non-oxidizing gas, and optionally a reducing agent, creates an environment which physically and chemically removes oxygen from non-sulfide gangue minerals. This subsequently improves their rejection in the flotation process while not adversely affecting the recovery of the valuable sulfide minerals. 
     The conditioning step can be conducted simultaneously with or prior to the flotation step. To explain, as will be clear to persons skilled in the art, flotation may be carried out in a mechanical flotation vessel or a pneumatic column. Such vessels and columns can have substantial residence times. While a milled slurry or slurry of a flotation concentrate is resident in the flotation vessel or column, conditioning may be effected. Indeed, some flotation machines lend themselves to being used for conditioning prior to or simultaneously with the flotation step. 
     The inventive process is suitable for ores related to mafic and ultramafic intrusions typically containing metal sulfides and precious metals and non-sulfide gangue minerals. Suitable ores for application of the process are shown in Table 1. Specifically, the inventive process is particularly suitable for recovery of nickel eg millerite, valerite, pentlandite; copper eg chalcopyrite, chalcocite; precious metals such as gold, silver, platinum group metals (pgms) and commonly associated sulfides including pyrite, marcasite, pyrrhotite, cobalt and the like. 
     Suitable non-sulfide gangue materials which may be subjected to the present invention include magnesium bearing minerals, talc, lizardite, brucite etc. and others such as antigorite, chlorite, certain micas, amphiboles and the like and generally other so-called naturally floating minerals. 
     
                                           TABLE 1                                 
__________________________________________________________________________
           MAJOR    METALS                                                
TYPE       MINERALS*                                                      
                    EXTRACTED                                             
                             EXAMPLES                                     
__________________________________________________________________________
ORES RELATED TO MAFIC AND ULTRAMAFIC INTRUSIONS                           
Sudbury nickel-copper                                                     
           po, pn, py, cpy, viol                                          
                    Ni, Cu, Co, PGM                                       
                             Sudbury, Ontario                             
Merensky reef platinum                                                    
           po, pn, cpy                                                    
                    Ni, Cu, PGM                                           
                             Merensky Reef South                          
                             Africa                                       
                             JM Reef Montana                              
ORES RELATED TO FELSIC INTRUSIVE ROCKS                                    
Tin and tungsten skarns                                                   
           py, cass, sph, cpy,                                            
                    Sn, W    Pine Creek, California                       
           wolf                                                           
Zinc-lead skarns                                                          
           py, sph, gn                                                    
                    Zn, Pb   Ban Ban, Australia                           
Copper skarns                                                             
           py, cpy  Cu, Au   Carr Fork, Utah                              
Porphyry   py, cpy, bn, mbd                                               
                    Cu, Mo, Au                                            
                             Bingham Canyon, Utah                         
copper/molybdenum            Climax, Colorado                             
Polymetallic veins                                                        
           py, cpy, gn, sph, ttd                                          
                             Camsell River, NWT                           
ORES RELATED TO MARINE MAFIC EXTRUSTVE ROCKS                              
Cyprus-type massive                                                       
           py, cpy  Cu       Cyprus                                       
sulfides                                                                  
Besshi-type massive                                                       
           py, cpy, sph, gn                                               
                    Cu, Pb, Zn                                            
                             Japan                                        
sulfides                                                                  
ORES RELATED TO SUBAERIAL FELSIC TO MAFIC EXTRUSIVE ROCKS                 
Creede-type epithermal                                                    
           py, sph, gn, cpy,                                              
                    Cu, Pb, Zn, Ag, Au                                    
                             Creede, Colorado                             
veins      ttd, asp                                                       
Almaden mercury type                                                      
           py, cinn Hg       Almaden, Spain                               
ORES RELATED TO MARINE FELSIC TO MAFIC EXTRUSIVE ROCKS                    
Kuroko type                                                               
           py, cpy, gn, sph,                                              
                    Cu, Pb, Zn, Ag, Au                                    
                             Japan                                        
           asp, ttd                                                       
ORES IN CLASSIC SEDIMENTARY ROCKS                                         
Quartz pebble                                                             
           py, uran, Au                                                   
                    Au, U    Witwatersrand, South                         
conglomerate gold-           Africa                                       
uranium                                                                   
Sandstone-hosted lead-                                                    
           py, sph, gn                                                    
                    Zn, Pb, Cd                                            
                             Laisvall, Sweden                             
zinc                                                                      
Sedimentary exhalative                                                    
           py, sph, gn, cpy,                                              
                    Cu, Pb, Zn, Au, Ag                                    
                             Sultivan, BC                                 
lead-zinc (Sedex)                                                         
           asp, ttd, po      Tynagh, Ireland                              
ORES IN CARBONATE ROCKS                                                   
Mississippi Valley type                                                   
           py, gn, sph                                                    
                    Zn, Pb, Cd, Ga                                        
                             SE Missouri                                  
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 *ABBREVIATIONS used as follows: po = pyrrhotite, pn = pentlandite, py =  
 pyrite, cpy = chalcopyrite, viol = violarite, cass -- cassiterite, sph = 
 sphalerite, wolf = wolframite, gn = galena, bn = bornite, mbd =          
 molybdenite, ttd = tetrahedrite, asp = arsenopyrite, cinn = cinnabar, ura
 = uraninite                                                              
 
    
     Any inert, non-oxidizing gas may be used with the present inventive process but nitrogen, argon, CO 2 , SO 2  or admixtures thereof are particularly suitable. It will be understood that the term &#34;inert, non-oxidizing gas&#34; used throughout this specification refers to commercial grades of such gases. In a preferred embodiment, the conditioning substance comprising at least one of an inert, non-oxidizing gas and the reducing, deoxifying agent are added to the slurry in a quantity sufficient to produce a dissolved oxygen content of less than 1 ppm. In another preferred embodiment, the conditioning substance is added in an amount sufficient to produce an electrochemical potential of between 0 to -700 mV, more preferably between -100 mV and -500 mV, which is conducive to depression of the non-sulfidic &#34;gangue&#34; minerals. 
     Suitable reducing, deoxifying agents include sulfoxy agents, SBS (sodium bisulfite), MBS (metabisulfites), sulfites, their potassium, calcium or ammonium salts, NaSH, Na 2  S and the like and organic depressants for naturally floating minerals such as carboxy methyl cellulose, dextran, guar gum, derivatives thereof and mixtures thereof. 
     The applicants have found that the present inventive process provides improved oxygen removal from surfaces of non-sulfide gangue minerals thereby increasing gangue mineral rejection and improving valuable sulfide, particularly nickel, flotation metallurgy e.g. better concentrate grade in the flotation circuit. It has also been found that the present inventive process increases non-sulfide gangue mineral rejection and rejection of MgO, if present, while maintaining existing valuable sulfide mineral, specifically nickel, recovery. 
     The present inventive process may be used for conditioning a freshly milled slurry or a slurry of a flotation concentrate from a previous flotation cell that has been exposed to reagents including collectors, frothers, activators and organic depressants and the like. According to the present invention, such a slurry is conditioned with a conditioning substance comprising at least one of nitrogen and a reducing agent, e.g. an NaSH group, for a specific conditioning period prior to flotation to provide a controlled dissolved oxygen content or electrochemical reduction potential suitable for floating the valuable sulfidic minerals and sinking the non-sulfidic gangue minerals. Preferably, the conditioning period is between one and six minutes. 
     Subsequent flotation is then carried out preferably using nitrogen as the carrier gas. This process improves the selectivity between valuable sulfides and non-sulfide gangue minerals thereby improving the concentrate grade of the valuable sulfide at the same recovery levels and improving rejection of the non-sulfide &#34;gangue&#34; mineral. 
     The present invention will now be described by way of example only with reference to the accompanying FIG. 1 which is a flow diagram of a typical flotation circuit in accordance with an embodiment of the present invention. As shown in FIG. 1, the present invention is particularly suitable for, but not limited to, the final cleaning/scavenger circuits in which the valuable concentrate from the previous flotation circuit is dosed with a suitable reducing, deoxifying agent, such as NaSH or Na 2  S, and subjected to final flotation with nitrogen gas. The nitrogen gas and NaSH-type reducing agent effectively suppress flotation of the non-sulfidic gangue minerals thereby increasing the recovery of the valuable sulfidic mineral. 
     EXAMPLE 1 
     N 2  /NaSH conditioning with nitrogen flotation. 
     By way of example, two tests were conducted in which 1 kg charges of crushed ore containing disseminated nickel sulfide were slurried in salt water to obtain a pulp density of 60 wt % solids and milled in a stainless steel rod mill employing stainless steel rods to achieve P80 of approximately 160 microns. An appropriate quantity of a collector, e.g. sodium ethyl xanthate, was added to the mill. 
     The milled slurry was then repulped and deslimed in the 25 mm diameter Mosley cyclone. The cyclone underflow stream was collected for flotation testing. 
     The deslimed milled slurry was transferred to a 2.5 litre Denver flotation cell. Frother and additional collector was added and the slurry was conditioned for a period of time prior to flotation. 
     Flotation with air was commenced and a rougher concentrate and scavenger concentrate were produced from 3 and 27 minutes respectively of flotation. Additional collector and frother was added during flotation. The scavenger concentrate was then reflotated in 0.5 Denver cell at 700 rpm according to the following two methods: 
     Test A--Control Tests Using Air As The Flotation Gas Scavenger Concentrate Stage Reflotation Performance 
     
         ______________________________________                                    
          Assay    Distribution (%)                                       
Product    Ni       MgO    Wt     Ni   MgO                                
______________________________________                                    
Conc 1     5.63     28.9   1.9    4.7  1.6                                
Conc 1 + 2 6.53     27.5   7.7    22.2 6.1                                
Conc 1 + 2 + 3                                                            
           6.20     27.5   20.4   56.1 16.3                               
Feed       2.25     34.3                                                  
______________________________________                                    
 
    
     Test B--Test Using N 2  /NaSH Conditioning Followed By Flotation With N 2  Gas. 
     In accordance with the present invention, in this test the scavenger concentrate was conditioned in a 0.5 L Denver cell at 700 rpm for 2.5 minutes with 1 L/min of nitrogen gas and NaSH additions as the reducing, de-oxifying agent. The NaSH addition was controlled by measuring and maintaining the sulfide potential (Es) at approximately -500 mV. Flotation with nitrogen was commenced after conditioning. 
     Scavenger Concentrate Stage Reflotation Performance 
     
         ______________________________________                                    
          Assay    Distribution (%)                                       
Product    Ni       MgO    Wt     Ni   MgO                                
______________________________________                                    
Conc 1     9.63     23.2   3.2    11.6 2.2                                
Conc 1 + 2 9.78     22.7   10.1   37.7 6.8                                
Conc 1 + 2 + 3                                                            
           8.02     25.2   21.8   67.1 16.3                               
Feed       2.61     33.8                                                  
______________________________________                                    
 
    
     Conc 1 is the first concentrate floated in the flotation test. Conc 1+2 and Conc 1+2+3 are the combination of the first and second concentrates, and first, second and third concentrates, respectively, floated in the flotation test. It is clear from the above results that Test B, using the inventive conditioning step provides a higher concentrate nickel grade and higher flotation recovery of nickel with a lower concentrate of MgO grade. 
     EXAMPLE 2 
     Nitrogen Conditioning With Nitrogen Flotation 
     In this example, two tests were conducted where 1 kg charges of crushed ore containing disseminated nickel sulfides were slurried in salt water and ground in similar equipment as example 1 to achieve P80 of 75 microns. 
     The milled slurry was then transferred to 2.5 L Denver flotation cell and floated in a manner similar to example 1 to produce a rougher concentrate and scavenger concentrate. 
     The scavenger concentrate was then refloated in a 0.5 L Denver flotation cell as discussed in example 1. 
     Test C--Control Test Using Air As The Flotation Gas 
     Scavenger Concentrate Stage Reflotation Performance 
     
         ______________________________________                                    
          Assay    Distribution (%)                                       
Product    Ni       MgO    Wt     Ni   MgO                                
______________________________________                                    
Conc 1     2.47     34.8   3.1    4.0  3.0                                
Conc 1 + 2 3.29     33.5   11.1   19.0 10.5                               
Conc 1 + 2 + 3                                                            
           4.50     31.7   20.1   47.2 18.1                               
Feed       1.92     35.3                                                  
______________________________________                                    
 
    
     Test D--Test Using N 2  Conditioning Followed By Flotation With N 2  Gas 
     In this test, the scavenger concentrate was conditioned in a 0.5 L Denver flotation cell with 1 L/min nitrogen gas addition. Flotation with nitrogen was commenced after conditioning. 
     Scavenger Concentrate Stage Reflotation Performance 
     
         ______________________________________                                    
          Assay    Distribution (%)                                       
Product    Ni       MgO    Wt     Ni   MgO                                
______________________________________                                    
Conc 1     2.94     33.7   3.0    4.2  2.9                                
Conc 1 + 2 4.06     32.3   10.8   21.0 10.0                               
Conc 1 + 2 + 3                                                            
           5.09     30.7   23.2   56.5 20.4                               
Feed       2.10     35.0                                                  
______________________________________                                    
 
    
     The test data indicate a slightly higher concentrate nickel grade, higher flotation recovery of nickel and a slightly lower concentrate MgO grade in test D using the nitrogen conditioning step followed by nitrogen gas flotation. 
     EXAMPLE 3 
     Nitrogen Flotation 
     In this example, two tests were conducted on fresh samples of reagentized flotation plant feed slurry from an ore containing a mixture of massive and disseminated nickel sulfide. This slurry assayed 1.7% nickel and 24% MgO. 
     The slurry was transferred to a 2.5 L laboratory flotation cell and flotated according to the following operations and reagent additions. 
     
         ______________________________________                                    
              Time     Guar Addition,                                     
                                  SEX Addition                            
Operation     Minutes  gpt        gpt                                     
______________________________________                                    
Conditioning  2        30         --                                      
Flotation - Concentrate 1                                                 
              4        --         --                                      
Conditioning  2        --         2                                       
Flotation - Concentrate 2                                                 
              4        --         --                                      
Conditioning  2        10         --                                      
Conditioning  2        --         2                                       
Flotation - Concentrate 3                                                 
              4        --         --                                      
Conditioning  2        --         2                                       
Flotation - Concentrate 4                                                 
              4        --         --                                      
______________________________________                                    
 SEX  Sodium Ethyl Xanthate                                               
 
    
     Each test produced four flotation concentrates and one flotation tail. 
     Test E--Control Test Using Air As The Flotation Gas 
     Flotation Feed Stage Flotation Performance 
     
         ______________________________________                                    
           Assay     Distribution (%)                                     
Product      Ni       MgO    Wt     Ni   MgO                              
______________________________________                                    
Conc 1       8.30     12.2   15.6   77.6 8.0                              
Conc 1 + 2   6.36     15.5   22.7   86.5 14.8                             
Conc 1 + 2 + 3                                                            
             5.70     16.4   26.3   89.7 18.2                             
Conc 1 + 2 + 3 + 4                                                        
             5.34     17.1   28.5   91.0 20.4                             
______________________________________                                    
 
    
     Test F--Test Using N 2  For Flotation Gas 
     Flotation Feed Stage Flotation Performance 
     
         ______________________________________                                    
           Assay     Distribution (%)                                     
Product      Ni       MgO    Wt     Ni   MgO                              
______________________________________                                    
Conc 1       11.00    8.40   11.3   72.7 3.9                              
Conc 1 + 2   8.61     11.9   16.8   84.6 8.3                              
Conc 1 + 2 + 3                                                            
             7.33     13.5   20.8   89.0 11.6                             
Conc 1 + 2 + 3 + 4                                                        
             6.65     14.6   23.3   90.6 14.1                             
______________________________________                                    
 
    
     The above test data clearly indicates higher concentrate nickel grade and lower concentrate MgO grade in Test F than Test E. 
     It will be understood by persons skilled in the art that the present invention may be embodied in forms other than that shown in the present invention without departing from the spirit or scope of the present invention.