Abstract:
A process for treating impure water includes adding magnesium hydroxide and/or ammonium hydroxide to the water. This neutralizes the impure water and reacts with dissolved metals in the water. The metals are precipitated as metal hydroxides/oxides, which are removed from the water. Thereafter barium hydroxide is added to the water. The barium hydroxide reacts with dissolved sulphates to produce barium sulphate and, when magnesium hydroxide is used, with dissolved magnesium, to produce magnesium hydroxide. Barium sulphate and, when present, magnesium hydroxide are removed from the water. When ammonium hydroxide is used, ammonia is stripped from the water. Carbon dioxide is then added to the water. The carbon dioxide reacts with dissolved calcium in the water. The calcium is precipitated as calcium carbonate, which is removed from the water.

Description:
CROSS-REFERENCE TO RELATED APPLICATION 
     The present application is claims priority under 35 U.S.C. §119 (a)-(d) to South African provisional patent application no. 2010/02127 filed on 25 Mar. 2010, which is incorporated by reference herein in its entirety. 
     FIELD OF THE INVENTION 
     THIS INVENTION relates to the treatment of water. It relates in particular to a process for treating impure water containing dissolved metals, calcium and sulphates. 
     BACKGROUND OF THE INVENTION 
     In South Africa, vast quantities of mine water are produced through mining operations such as gold and coal mining. These mine waters contain high levels of dissolved metals such as iron, aluminium and manganese, as well as other impurities. The mine waters are typically stored above ground, but seepage into underground voids or cavities takes place continually. At the same time, the mine waters become even more polluted through pyrite oxidation that generates high levels of acidity and dissolved sulphates in accordance with reaction (1):
 
4FeS 2 +15O 2 +14H 2 O→4Fe(OH) 3 +8H 2 SO 4   (1)
 
     The resultant acid mine drainage (AMD) is thus a major contributor to water pollution. 
     SUMMARY OF THE INVENTION 
     It is accordingly an object of the invention to provide a process whereby acid mine drainage can be treated cost effectively to remove dissolved metals and sulphates therefrom. 
     Thus, according to the invention, there is provided a process for treating impure water containing dissolved metals, dissolved calcium, and dissolved sulphates, which process includes
         in a first treatment stage, adding magnesium hydroxide and/or ammonium hydroxide to the impure water, for neutralization of the impure water and for reaction with dissolved metals in the water, thereby to cause the metals to be precipitated as metal hydroxides or metal oxides;   optionally, in a pretreatment step and/or in the first treatment stage, subjecting the impure water to oxidation treatment thereby to oxidize at least one dissolved metal present in the impure water;   removing precipitated metal hydroxides and metal oxides from the water;   thereafter, in a second treatment stage, adding barium hydroxide to the water, with the barium hydroxide reacting with dissolved sulphates in the water to produce barium sulphate, and, when magnesium hydroxide is used in the first treatment stage, with dissolved magnesium, also to produce magnesium hydroxide;   removing barium sulphate from the water;   removing, when present, magnesium hydroxide from the water;   when ammonium hydroxide is used in the first treatment stage, stripping ammonia from the water;   in a third treatment stage, adding carbon dioxide to the water, with the carbon dioxide reacting with dissolved calcium in the water, to cause the calcium to be precipitated as calcium carbonate; and   removing the precipitated calcium carbonate from the water.       

     The impure water may contain, as a dissolved metal, iron (II). It may also contain iron (III), aluminium (III) and/or manganese (II) as dissolved metal(s). More particularly, the impure water may be acid mine drainage containing, in addition to iron (II) as a dissolved metal, also iron (III), manganese, zinc, nickel, cobalt, aluminium and/or magnesium as dissolved metal(s), possibly together with some radio activity and free acid. 
     The oxidation treatment may include adding oxygen or air to the impure water ahead of first treatment stage, i.e. in a pretreatment step, or in the first treatment stage, for oxidation of iron (II) to iron (III). In particular, when the impure water is treated with magnesium hydroxide in the first treatment stage, it must also be treated, or pretreated, with air or oxygen for Fe(II) oxidation to Fe(III), in a pH range of 5.0 to 7.5, since magnesium hydroxide will not readily precipitate Fe(II). In the event that ammonium hydroxide is used in the first treatment stage, the oxidation treatment can still be employed beneficially; however, ammonium hydroxide will in any event precipitate at least some Fe(II) as Fe(OH) 2 . The air addition may comprise aerating the impure water. 
     In the first treatment stage, the magnesium hydroxide (Mg(OH) 2 ) and/or ammonium hydroxide (NH 4 OH) thus reacts with the dissolved iron, manganese, aluminium, etc. to cause these metals to be precipitated as metal hydroxides or metal oxides. 
     Furthermore, in the first treatment stage, any iron (II) present in the impure water is oxidized to iron (III) by the oxygen addition or aeration. Iron (III) is typically precipitated as Fe(OH) 3 , while manganese (II) can precipitate either as a metal hydroxide, i.e. Mn(OH) 2 , or as a metal oxide, i.e. Mn 2 O 4 . These precipitates are then removed from the water before treatment thereof in the second treatment stage. 
     When magnesium hydroxide is used in the first treatment stage, the barium sulphate and magnesium hydroxide that are formed in the second treatment stage may be allowed to precipitate out, and may be removed from the water together or simultaneously, e.g. as a sludge. The magnesium hydroxide may thereafter be recovered or separated from the barium sulphate. However, if desired, the precipitated barium sulphate and magnesium hydroxide may be allowed to grow to different sizes, with precipitated barium sulphate then being removed or recovered separately from the precipitated magnesium hydroxide, using the particle size differences of the two precipitated compounds. The magnesium hydroxide that is obtained in the second treatment stage is thus separated from the barium sulphate that is also formed. The magnesium hydroxide that is recovered may be recycled to the first treatment stage. Instead, it can be separated from the barium sulphate after thermal treatment of the barium sulphate/magnesium hydroxide sludge obtained from the second treatment stage, as hereinafter described. 
     When ammonium hydroxide is used in the first treatment stage, the barium sulphate may be allowed to precipitate out in the second treatment stage, while ammonia may be stripped off at high pH. The ammonia may optionally be reacted with water to obtain ammonium hydroxide which may then be recycled to the first treatment stage. 
     The process of the invention is thus characterized thereby that the barium hydroxide is used to treat the magnesium hydroxide- or ammonium hydroxide-treated water directly, without the need for pre-removal of magnesium or ammonium ions. 
     The barium sulphate may be removed from the water as a sludge. The process may then include treating the barium sulphate-containing sludge, either before or after magnesium hydroxide separation therefrom, so as to convert the barium sulphate to barium hydroxide via barium sulphide, either before or after magnesium hydroxide separation therefrom. The conversion of barium sulphate to barium hydroxide may include reacting the barium sulphate with coal, for example, in a furnace, in accordance with reaction (2)
 
BaSO 4 +2C→BaS+2CO 2   (2)
 
thereafter reacting the barium sulphide with steam, preferably under pressure, in accordance with reaction (3)
 
BaS+H 2 O→BaO+H 2 S  (3)
 
and thereafter reacting the barium oxide with water, in accordance with reaction (4)
 
BaO+H 2 O→Ba(OH) 2   (4)
 
     Instead, the barium sulphide may be reacted with sodium hydroxide, to produce barium hydroxide, in accordance with reaction (5)
 
BaS+NaOH+3H 2 O→2Ba(OH) 2 +H 2 S+NaHS  (5)
 
     The barium hydroxide thus produced can naturally be reused in the second treatment stage. 
     Typically, reaction (2) may be effected in a kiln such as a shaft kiln, a rotary kiln or a fluidized bed kiln, and the mole ratio of C:BaSO 4  may be about 1:3 to cater for heat that is required in reaction (2) which is endothermic. 
     Coal contains tar and volatile compounds which will contaminate the products of reactions (2), (3), (4) and (5). To avoid such contamination the coal, instead of being used directly in reaction (2), may first converted to coke in accordance with reaction (6)
 
Coal→C+CO 2 +ash+volatiles+tar  (6)
 
     The resultant coke (C+ash) may then be used, instead of coal, for reaction with barium sulphate in accordance with reaction (2). 
     Reaction (6) may be carried out in a shaft kiln, which may be the same kiln as that in which reaction (2) is carried out. 
     Reaction (3) may be carried out by contacting BaS with water, e.g. as steam, under pressure at a high temperature, e.g. 900° C. to 1050° C. By contacting barium sulphide with steam at 950° C. or higher, H 2 S is released and barium oxide (BaO) produced. It will be appreciated that barium oxide can be produced as a product i.e. reaction (4) can be omitted, if desired. A pressurized reactor is thus typically used for processing BaS to BaO by reacting it with steam in a stage after the reaction stage. 
     The steam required for reaction (3) may be introduced into the kiln below the point where air that is required for reaction (2) is introduced into the kiln. In this manner, hydrogen sulphide produced in accordance with reaction (3) may leave the kiln, together with other off-gases produced, at an upper end of the kiln. The process may then include converting the hydrogen sulphide to a sulphur-containing by product, e.g. sulphur(S), NaHS, H 2 SO 4 , etc. Thus, for example, the conversion of the hydrogen sulphide may include contacting the off gases containing the hydrogen sulphide with sodium hydroxide in accordance with reaction (7):
 
NaOH+H 2 S→NaHS+H 2 O  (7)
 
     Instead, hydrogen sulphide can be converted to sulphur in accordance with the Clauss process (reaction (8))
 
2H 2 S+SO 2 →3S+2H 2 O  (8)
 
     The invention will now be described by way of example with reference to the accompanying drawing and the following non-limiting example. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWING 
       In the accompanying drawings, which form a part of the specification and are to be read in conjunction therewith and in which like reference numerals are used to indicate like parts in the various views: 
       The single drawing shows a simplified flow diagram of a process according to the invention for treating acid mine drainage. 
     
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     In the drawing, reference numeral  10  generally indicates a process for treating acid mine drainage according to the invention. 
     The process  10  includes a first treatment stage  12 , fitted with stirrer  14 , with an acid mine drainage line  16  leading into the stage  12 , as do a magnesium hydroxide addition line  18  and an oxygen/air addition line  19 . 
     A water transfer line  20  leads from the first treatment stage  12  to a settler  22 . A metal hydroxide/oxide withdrawal line  24  leads from the settler  22  as does a water transfer line  26 . The line  26  leads to a second treatment stage  28 , fitted with a stirrer  30 . A barium hydroxide addition line  32  also leads into the stage  28 . 
     A water transfer line  34  leads from the stage  28  to a settler  36 . A solids withdrawal line  38  leads from the stage  36 , as does a water transfer line  40 . 
     The water transfer line  40  leads into a third treatment stage  42 , fitted with a stirrer  44 . A carbon dioxide addition line  46  also leads into the stage  42 . 
     A water transfer line  48  leads from the stage  42  to a settler  50 . A treated water line  54  leads from the settler  50 , as does a calcium carbonate withdrawal line  52 . 
     The sludge withdrawal line  38  from the stage  36  leads into a shaft kiln  60 . A coal addition line  62  leads into the kiln  60 . A transfer line  62  leads from the kiln  60  to a pressurized thermal reactor  66 . A steam addition line  68  leads into the reactor  66 . 
     A product withdrawal line  70  leads from the stage  66  to a further treatment stage  72 , with a product withdrawal line  74  leading from the stage  72 . 
     In use, in the first treatment stage  12 , magnesium hydroxide that is added along line  18 , serves to neutralize acid mine drainage that is added along the line  16 . Furthermore, dissolved metals in the acid mine drainage react with the magnesium hydroxide to cause metals such as iron, aluminium and manganese to be precipitated as metal hydroxides or metal oxides i.e. Fe(OH) 3 , Al(OH) 3  and MnO 2 . Oxygen or air entering along the line  19  oxidizes Fe(II) to Fe(III). 
     The metal hydroxide containing water passes to the settler  22  where the metal hydroxides are allowed to settle out, and are withdrawn along the line  24 . 
     The water passes along the line  26  to the second treatment stage  28  where barium hydroxide is added thereto. The barium hydroxide reacts, in the stage  28 , with dissolved sulphates in the water, as well as with dissolve magnesium, to produce barium sulphates and magnesium hydroxides. 
     The water then passes along the line  34  to the settler  36  where the barium sulphide and magnesium hydroxides are allowed to settle out and are withdrawn as sludge along the line  38 . 
     The partially treated water passes along, the line  40  to the third treatment stage  42  where it is contacted with carbon dioxides which enters the stage along the line  46 . The carbon dioxide reacts with dissolved calcium in the water, causing calcium carbonate to be precipitated. The calcium carbonate containing water passes along the line  48  into the settler  50 . Calcium carbonate is withdrawn along the line  52 . Treated water is withdrawn along the line  54 . 
     The sludge that is withdrawn from the settler  36  along the line  38  passes into the shaft kiln  60 . Typically, this shaft kiln can have the following dimensions:
 
Height=4 m; width=1.8 m; length=1.8 m
 
     Instead of a shaft kiln  60 , a rotary kiln, a fluidized bed kiln or a tunnel kiln can be used. 
     In the shaft kiln  60 , coal, introduced along the line  62 , is first converted to coke in accordance with reaction (6). The coke then reacts with the barium sulphate in accordance with reaction (2), to produce barium sulphide. The barium sulphide passes along the line  64  to the reactor  66 , where it is reacted with steam entering along the line  64  in accordance with reaction (3), and at a temperature of 950° C. to 1050° C. 
     Reaction (3) is thus carried out in a separate reactor ( 66 ) in which steam is contacted separately with the barium sulphide in accordance with reaction (3). This unfortunately means that the high energy of the barium sulphide, i.e. reaction (3), is not available for heating the feed air entering the kiln  60 ; however, since low cost coal can be used in the kiln, this is not perceived to be a major disadvantage. 
     In order to demonstrate the viability of the process according to the invention, and particularly to show the following:
         to demonstrate the metals can be completely removed with Mg(OH) 2 ;   that sulphate concentration can be lowered to less than 200 mg/l   that the magnesium concentration can be reduced to less than 10 mg/l with Ba(OH) 2      that high pH water can be stabilized with CO 2      and to get an estimate of the running costs of the process       

     The following laboratory experiment was conducted: 
     EXAMPLE 1 
     Materials &amp; Methods 
     Feedstock 
     Mine waters from a coal mine and a gold mine were used as feed waters containing between 2 400 and 4 800 mg/l sulphate (for chemical analyses, see Tables 1 and 2). Magnesium hydroxide and barium hydroxide were used for pH adjustment and sulphate removal, respectively. CO 2  gas (obtained locally from Afrox Ltd) was used for pH adjustment after sulphate removal. 
     Equipment 
     Neutralization studies with Mg(OH) 2  and sulphate removal with Ba(OH) 2  were studied using stirred beakers. 
     Experimental Procedure 
     Feed water was mixed in a beaker (5 l), aerated for iron(II) oxidation and stirred for 30 min for completion of the oxidation/precipitation reactions. The sludge was allowed to settle and the clear water decanted. Ba(OH) 2  was mixed with the decant water (1000 ml glass beakers). Stabilization of the Ba(OH) 2  treated water was achieved by passing CO 2  through the water. 
     Experimental Program 
     The following parameters were investigated:
         Metal removal with Mg(OH) 2 .   Magnesium and sulphate removal with Ba(OH) 2 .   Calcium removal with CO 2 .
 
Analytical
       

     Samples were collected regularly and filtered (Whatman No 1 filter paper). Sulphate, alkalinity, Fe(II), mixed liquor suspended solids (MLSS), volatile suspended solids (VSS), acidity, and pH determinations were carried out according to procedures described in  Standard Methods  (APHA, 1989). Calcium and magnesium were assayed using atomic absorption spectrophotometry. 
     Results &amp; Discussion 
     Water Quality and Chemical Reactions 
     It is concluded that the process of the invention can be used for the treatment of acid mine drainage (AMD). Tables 1 and 2 show the chemical composition of the feed waters before and after treatment with Mg(OH) 2 , Ba(OH) 2  and CO 2  for effluents from coal and gold mines, respectively. The Total Dissolved Solids (TDS) content in the case of coal mine water was lowered from 3 758 mg/l in the feed water to 3 710 mg/l after Mg(OH) 2  treatment, to 1 831 mg/l after Ba(OH) 2  treatment and to 244 mg/l after CO 2  addition (Table 1). Similarly, in the case of gold mine effluent, the overall TDS content was reduced from 6 340 mg/l in the feed water to 355 mg/l after treatment in accordance with the process of the invention (Table 2). During Mg(OH) 2  treatment, free acid and all the metal, excluding calcium and magnesium, concentrations were reduced to low levels. The lowering of the TDS in the case of Mg(OH) 2  treatment was mainly due to the oxidation of Fe 2+  to Fe 3+  (Reaction 9) and precipitation as Fe(OH) 3  (Reaction 10). Similarly, Mn 2+  was oxidised to Me and precipitated as MnO 2 . The other metals: Al 3+ , Co 2+ , Zn 2+ , Pb 2+ , Co 2+  and Ni 2+  precipitated as metal hydroxides. This was owing to the low solubility-products (units) for Fe(OH) 3  (2.64×10 −39 ); Al(OH) 3  (8.5×10 −23 ); Mn(OH) 2  (2.06×10 −13 ); Cu(OH) 2  (2.20×10 −20 ); Zn(OH) 2  (7.71×10 −17 ); Pb(OH) 2  (1.42×10 −20 ); Co(OH) 2  (1.09×10 −15 ) and Ni(OH) 2  (5.47×10 −16 ). 
     In the case of coal mine effluent (Table 1), the Mg concentration increased from 147 mg/l to 243 mg/l during Mg(OH) 2  treatment (Reaction 11). The SO 4   2− -concentration remained constant during Mg(OH) 2  treatment due to the high solubility of MgSO 4  of 26 g/l. 
     During the subsequent, Ba(OH) 2  treatment, Mg 2+  was removed to less than 10 mg/l (Reaction 13) at pH 12. The SO 4   2−  was lowered from 2 680 mg/l to 704 mg/l due to BaSO 4  precipitation (Reaction 14), representing a Ba(OH) 2 .8H 2 O/SO 4  removed ratio of 1.009 mole/mole. The precipitated BaSO 4  and Mg(OH) 2  can be settled rapidly by dosing coagulants. Coagulant dosing can be avoided by controlling the precipitation process to yield particles with improved settling rates. It is known that a multiple point in-line dosing system can produce flocs within the range 10-100 μm. 
     In the final step, the calcium in the feed water was reduced from 578-80 mg/l (as Ca) by stabilizing the water with CO 2  (Reaction 15). During CO 2  addition for pH adjustment, CaCO 3  crystallization occurred, as indicated by the decrease in the calcium concentration. The saturation, under-saturation and super-saturation states of CaCO 3  are theoretically identified by the activity product of Ca 2+  and CO 3   2−  species that is comparable with the solubility product constant, k sp , for CaCO 3 . Above the solubility product, CaCO 3  will precipitate from solution and below, CaCO 3  will dissolve. The rate of precipitation or dissolution is described by Equation (16), where k is the precipitation rate constant, S the surface area of CaCO 3  growth/dissolution sites and the activity in mol/l. The rate of precipitation depends on k, S and the term within the brackets { }. Although k is affected to an unknown extent by crystal structure, S is dependent on the size, mass and structure of the crystals. By controlling S and the degree of super-saturation (term in { } brackets), the rate of precipitation or dissolution of CaCO 3  can be determined. 
     In the case of gold mine effluent (Table 2) the Mg concentration increased from 147 mg/l to 718 mg/l during Mg(OH) 2  treatment (Reaction 11). The SO 4   2− -concentration remained constant during Mg(OH) 2  treatment due to the high solubility of MgSO 4  of 26 g/l. During the subsequent, Ba(OH) 2  treatment at pH 12, Mg 2+  concentration was lowered to 1 mg/L (Reaction 13). The SO 4   2−  was lowered from 4 398 mg/l to 24 mg/l due to BaSO 4  precipitation (Reaction 14), representing a Ba(OH) 2 .8H 2 O/SO 4 -removed ratio of 0.985 mole/mole. Stabilisation with CO 2  resulted in lowering of calcium concentration from 578 to 80 mg/l (as Ca).
 
2Fe 2+ +½O 2 +2H + →2Fe 3+ +H 2 O  (9)
 
2Fe 3+ +6H 2 O→2Fe(OH) 3 +6H +   (10)
 
6H + +3Mg(OH) 2 →3Mg 2+ +6H 2 O  (11)
 
2Fe 2+ ½O 2 +2H + +3Mg(OH) 2 →2Fe(OH) 3 +3Mg 2+ +H 2 O  (12)
 
Mg 2+ +Ba(OH) 2 →Mg(OH) 2 +Ba 2+   (13)
 
SO 4   2− +Ba 2+ →BaSO 4   (14)
 
Ca(OH) 2 +CO 2 →CaCO 3 +H 2 O  (15)
 
− d [Ca 2+   ]/dt=k S{(Ca 2+ ) 1/2 (CO 3   2− ) 1/2   −k   sp   1/2 } 2   (16)
 
     A benefit of using Mg(OH) 2  for neutralization and metal removal is that the precipitated metal hydroxides/oxides are not mixed with gypsum. The sludge from the Mg(OH) 2  stage consists of Fe(OH) 3 , Al(OH) 3 , MnO 2  and Zn(OH) 2 . The Ba(OH) 2  sludge consisted of 70% BaSO 4  and 30% Mg(OH) 2 . 
     Running Cost 
     The running cost of the process according to the invention, on the scale described, amounted to R1.61/m 3  for treatment of coal mine effluent and R2.71/m 3  for goldmine effluent (Table 2). The value of water and by-products recoverable amounted to R6.00/m 3  for coal mine effluent and R6.00/m 3  for gold mine effluent. 
     
       
         
               
             
               
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Chemical composition of feed and treated water when coal mine 
               
               
                 effluent was treated with Mg(OH) 2 , Ba(OH) 2  and CO 2  in accordance 
               
               
                 with the invention. 
               
             
          
           
               
                   
                 Stage 
               
             
          
           
               
                 Parameter 
                 Feed 
                 Mg(OH) 2   
                 Ba(OH) 2 •8H 2 O 
                 CO 2   
               
               
                   
               
             
          
           
               
                 Dosage (g/l) 
                   
                   0.25 
                   6.55 
                   
               
               
                 Mg(OH) 2 -utilization 
                   
                    1.025 
               
               
                 (mole/mole) 
               
               
                 Barium-dosage/SO4 
                   
                   
                    1.009 
               
               
                 removed 
               
               
                 (mole/mole) 
               
               
                 pH 
                   3.4 
                   8.3 
                  11.9 
                 7.5 
               
               
                 Sulphate (mg/l SO 4 ) 
                 2 690   
                 2 680    
                 704  
                 24 
               
               
                 Chloride (mg/l Cl) 
                 35 
                 37  
                 33  
                 31 
               
               
                 Alkalinity 
                   
                 20  
                 1 050    
                 220 
               
               
                 (mg/l CaCO 3 ) 
               
               
                 Acidity 
                 100  
               
               
                 (mg/l CaCO 3 ) 
               
               
                 Sodium (mg/l Na) 
                 31 
                 32  
                 30  
                 28 
               
               
                 Potassium (mg/l K) 
                  3 
                 3 
                 3 
                 3 
               
               
                 Magnesium 
                 147  
                 243  
                 7 
                 2 
               
               
                 (mg/l Mg) 
               
               
                 Calcium (mg/l Ca) 
                 698  
                 702  
                 695  
                 80 
               
               
                 Barium (mg/l Ba) 
               
               
                 Manganese 
                   9.2 
                   5.1 
                   0.1 
                 0.2 
               
               
                 (mg/l Mn) 
               
               
                 Iron(II) (mg/l Fe) 
                 100  
                 0 
                 0 
                 0 
               
               
                 Iron(III) (mg/l Fe) 
                 20 
                 0 
                 0 
                 0 
               
               
                 Zinc (mg/l Zn) 
                 11 
                 0 
                 0 
                 0 
               
               
                 Nickel (mg/l Ni) 
                  1 
                 0 
                 0 
                 0 
               
               
                 Cobalt (mg/l Co) 
                  1 
                 0 
                 0 
                 0 
               
               
                 Aluminum (mg/l Al) 
                 10 
                 1 
                 2 
                 1 
               
               
                 Total dissolved 
                 3758  
                 3710   
                 1831   
                 244 
               
               
                 solids (mg/l) 
               
               
                 Fe(OH) 3  (mg/l) 
                   
                 230  
               
               
                 Mn(OH) 2  (mg/l) 
                   
                 7 
                 8 
               
               
                 Zn(OH) 2  (mg/l) 
                   
                 17  
               
               
                 Ni(OH) 2  (mg/l) 
                   
                 2 
               
               
                 Co(OH) 2  (mg/l) 
                   
                 2 
               
               
                 Al(OH) 3  (mg/l) 
                   
                 26  
               
               
                 BaSO 4  (mg/l) 
                   
                   
                 4,796    
               
               
                 Mg(OH) 2  (mg/l) 
                   
                   
                 565  
               
               
                 CaCO 3  (mg/l) 
                   
                   
                   
                 1,537 
               
               
                 Suspended solids 
                  0 
                 282  
                 5,369    
                 1,537 
               
               
                 (mg/l) 
               
               
                 Cations (−) (meq/l) 
                   57.03 
                   57.28 
                   36.60 
                 5.77 
               
               
                 Anions (+) (meq/l) 
                   56.93 
                   56.86 
                   36.96 
                 5.57 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
             
               
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Chemical composition of feed and treated water when gold mine 
               
               
                 effluent was treated with Mg(OH) 2 , Ba(OH) 2  and CO 2  in 
               
               
                 accordance with the invention. 
               
             
          
           
               
                   
                 Stage 
               
             
          
           
               
                 Parameter 
                 Feed 
                 Mg(OH) 2   
                 Ba(OH) 2 •8H 2 O 
                 CO 2   
               
               
                   
               
               
                 Dosage (g/l) 
                   
                   1.38 
                   14.16 
                   
               
               
                 Mg(OH) 2 -utilization 
                   
                    0.985 
               
               
                 (mole/mole) 
               
               
                 Barium-dosage/SO4 
                   
                   
                    0.985 
               
               
                 removed 
               
               
                 (mole/mole) 
               
               
                 pH 
                   2.5 
                   8.6 
                  12.2 
                   7.7 
               
               
                 Sulphate (mg/l SO 4 ) 
                 4 424   
                 4 398    
                 24  
                 11  
               
               
                 Chloride (mg/l Cl) 
                 37 
                 37  
                 37  
                 37  
               
               
                 Alkalinity 
                   
                 20  
                 1,607    
                 369  
               
               
                 (mg/l CaCO 3 ) 
               
               
                 Acidity (mg/l 
                 500  
               
               
                 CaCO 3 ) 
               
               
                 Sodium (mg/l Na) 
                 96 
                 96  
                 96  
                 96  
               
               
                 Potassium (mg/l K) 
                  3 
                 3 
                 3 
                 3 
               
               
                 Magnesium 
                 147  
                 718  
                 1 
                 2 
               
               
                 (mg/l Mg) 
               
               
                 Calcium (mg/l Ca) 
                 569  
                 572  
                 578  
                 80  
               
               
                 Barium (mg/l Ba) 
               
               
                 Manganese 
                 75 
                 19  
                   0.2 
                   0.2 
               
               
                 (mg/l Mn) 
               
               
                 Iron(II) (mg/l Fe) 
                 920  
                 0 
                 0 
                 0 
               
               
                 Iron(III) (mg/l Fe) 
                 20 
                 0 
                 0 
                 0 
               
               
                 Zinc (mg/l Zn) 
                 11 
                 0 
                 0 
                 0 
               
               
                 Nickel (mg/l Ni) 
                 13 
                 0 
                 0 
                 0 
               
               
                 Cobalt (mg/l Co) 
                  5 
                 0 
                 0 
                 0 
               
               
                 Aluminum (mg/l Al) 
                 10 
                 1 
                 2 
                 1 
               
               
                 Total dissolved 
                 6 340   
                 5 850    
                 1 288    
                 355  
               
               
                 solids (mg/l) 
               
               
                 Fe(OH) 3  (mg/l) 
                   
                 1 798    
               
               
                 Mn(OH) 2  (mg/l) 
                   
                 91  
                 30  
               
               
                 Zn(OH) 2  (mg/l) 
                   
                 17  
               
               
                 Ni(OH) 2  (mg/l) 
                   
                 21  
               
               
                 Co(OH) 2  (mg/l) 
                   
                 8 
               
               
                 Al(OH) 3  (mg/l) 
                   
                 26  
               
               
                 BaSO 4  (mg/l) 
                   
                   
                 10 616    
               
               
                 Mg(OH) 2  (mg/l) 
                   
                   
                 1 720    
               
               
                 CaCO 3  (mg/l) 
                   
                   
                   
                 1 245    
               
               
                 Suspended solids 
                  0 
                 1 960    
                 12 366    
                 1 245    
               
               
                 (mg/l) 
               
               
                 Cations (−) (meq/l) 
                   93.21 
                    93.07 
                    33.67 
                   8.63 
               
               
                 Anions (+) (meq/l) 
                   93.60 
                    92.74 
                    33.48 
                   8.53 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
             
               
               
               
               
               
             
           
               
                 TABLE 3 
               
               
                   
               
               
                 Running costs of the process according to the invention, and 
               
               
                 value of the products (water, sulphur and calcium carbonate 
               
               
                 and magnesium hydroxide) 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Coal mine 
                 Gold mine 
               
             
          
           
               
                   
                   
                 Cost 
                   
                 Cost 
               
               
                 Item 
                   
                 (R/m 3 ) 
                   
                 (R/m 3 ) 
               
               
                   
               
               
                 Feed sulphate (mg/l) 
                 2,680.00 
                   
                 4,398.00 
               
               
                 Treated sulphate (mg/l) 
                 704.00 
                   
                 24.00 
               
               
                 BaSO 4  production (kg/m 3 ) 
                 4.80 
                   
                 10.62 
               
               
                 Barium losses (%) 
                 5.00 
                   
                 5.00 
               
               
                 BaSO 4  purity (%) 
                 93.00 
                   
                 93.00 
               
               
                 BaSO 4  required (kg/m 3 ) 
                 0.26 
                   
                 0.57 
               
               
                 BaSO 4  price (R/t) 
                 2,500.00 
                   
                 2,500.00 
               
               
                 BaSO 4  cost (R/m 3 ) 
                   
                 0.64 
                   
                 1.43 
               
               
                 Carbon content of coal (%) 
                 70.00 
                   
                 70.00 
               
               
                 C:BaSO 4 -ratio 
                 3.00 
                   
                 3.00 
               
               
                 Coal required (kg/m 3 ) 
                 1.06 
                   
                 2.34 
               
               
                 Coal price (R/t) 
                 250.00 
                   
                 250.00 
               
               
                 Coal cost (R/m 3 ) 
                   
                 0.26 
                   
                 0.59 
               
               
                 Sulphur production 
                   
                 0.20 
                   
                 0.20 
               
               
                 (citric acid, KOH) (R/m 3 ) 
               
               
                 Energy requirement (kWh/m 3 ) 
                 1.00 
                   
                 1.00 
               
               
                 Electricity cost (R/kWh) 
                 0.30 
                   
                 0.30 
               
               
                 Energy cost (R/m 3 ) 
                   
                 0.30 
                   
                 0.30 
               
               
                 Labour 
                   
                 0.20 
                   
                 0.20 
               
               
                 TOTAL RUNNING COST 
                   
                 1.61 
                   
                 2.71 
               
               
                   
               
               
                   
                   
                 Value 
                   
                 Value 
               
               
                 Products 
                   
                 (R/m 3 ) 
                   
                 (R/m 3 ) 
               
               
                   
               
               
                 Water value 
                   
                 3.00 
                   
                 3.00 
               
               
                 Sulphur (kg/m 3 ) 
                 0.66 
                   
                 1.46 
               
               
                 Sulphur value (90% 
                   
                 0.47 
                   
                 1.05 
               
               
                 recovery, R800/t) (R/m 3 ) 
               
               
                 CaCO 3  (kg/m 3 ) 
                 1.54 
                   
                 1.24 
               
               
                 CaCO 3  value (90% recovery, 
                   
                 2.07 
                   
                 1.68 
               
               
                 R1500/t) (R/m 3 ) 
               
               
                 Mg(OH) 2  (kg/m 3 ) 
                 0.35 
                   
                 0.35 
               
               
                 Mg(OH)2 value (70% 
                   
                 0.40 
                   
                 0.40 
               
               
                 recovery, R1600/t) (R/m 3 ) 
                   
                   
               
               
                 TOTAL VALUE OF 
                   
                 5.94 
                   
                 6.12 
               
               
                 BY-PRODUCTS 
               
               
                   
               
               
                 Note: 
               
               
                 Potential value of metals not included 
               
             
          
         
       
     
     It was thus demonstrated with the process of the invention, that:
         1. Mg(OH) 2  precipitated all metals as metal hydroxides or metal oxides. Iron(II) was first oxidised to iron(III) before it was precipitated.   2. Ba(OH) 2  reacted rapidly with dissolved sulphate, and simultaneously precipitated sulphate as BaSO 4  and magnesium as Mg(OH) 2 . Sulphate removal was stoichiometrically equal to the Ba(OH) 2  dosage.   3. CO 2  precipitated calcium as CaCO 3 .   4. The running cost of the barium sulphide process for the removal of 2000 mg/l of sulphate totaled R2.12/m 3 .   5. Lime pre-treatment for pre-removal of Mg 2+  or NH 4+  was not required.       

     As hereinbefore set out, mining is a significant contributor to water pollution, due primarily to pyrite oxidation that generates potentially high levels of acidity, metals, and sulphate in accordance with reaction (1): 
     South Africa&#39;s Witwatersrand Basin produces 340 Ml/d of mine water, of which 50 Ml/d is produced by the Western Basin. All the underground mining operations in the Western Basin were closed by 1990. By 2004 the underground voids were filled by rising water levels and acid water started to decant at the surface. Contaminated void spaces increase with time and result in: (a) less water suitable for irrigation of crops, (b) less potable water available for local, growing communities, (c) the natural drying up of rivers and (d) stream bed losses. The water of mining origin in the Western Basin contains on average 4 800 mg/l sulphate, 800 mg/l iron(II), 100 mg/l iron(III), 230 mg/l manganese, 11 mg/l zinc, 18 mg/l nickel, 5 mg/l cobalt, 6 mg/l aluminium, 150 mg/l magnesium, some radioactivity and 700 mg/l free acid (as CaCO 3 ). This acid water source creates the following concerns: (i) The Cradle of Humankind, World Heritage Site is close to the decant point. (ii) Acid mine drainage (AMD) will flow into the Krugersdorp Nature Reserve and possibly even the Sterkfontein Cave system which includes the Cradle of Humankind, where the earliest known hominid fossil remains were discovered and where palaeontological excavations continue. 
     It is essential that a technically sound and cost-effective solution be found for the acid mine water problem. South Africa is water constrained and also has a mature mining economy with numerous mines having closed or are in the process of closing down. Should a technical solution be found that generates income, the acid mine water problem could be solved via economic principles rather than through government intervention via policies and legislated control measures. It is believed that the process of the invention complies with these requirements.