Abstract:
A process is provided for producing potassium sulfate by reacting ammonium sulfate and potassium chloride at a temperature of about 30 to 40° C. to produce a slurry containing K 2 SO 4 ·NH 4 ·2SO 4  double salt, and reacting this double salt with an aqueous solution containing potassium chloride at a temperature of about 30° C. to produce a slurry containing potassium sulfate. The slurry containing potassium sulfate is subjected to a solids/liquid separation step to obtain potassium sulfate crystals having a size in the range of about 20 mesh to about 150 mesh.

Description:
This application claims the benefit of U.S. Provisional application Ser. No. 60/089,630 filed Jun. 16, 1998. 
    
    
     FIELD OF THE INVENTION 
     The present invention relates to a method of producing potassium sulfate and more particularly, the invention relates to a method of synthesizing pure potassium sulfate from brines of ammonium sulfate with up to 12% Na 2 SO 4  impurities. 
     BACKGROUND OF THE INVENTION 
     The prior art has established countless methods of preparing potassium sulfate. Typical of the known methods is exemplified by U.S. Pat. No. 4,588,573, issued May 13, 1986, to Worthington et al. In this reference, potassium chloride and sulfuric acid are reacted. Although meritorious, the method requires sulfuric acid which is generally expensive and requires special conditions for handling. 
     The co-production of potassium sulfate, sodium sulfate and sodium chloride is taught in U.S. Pat. No. 5,552,126, issued to Efraim et al., Sep. 3, 1996. Progressive precipitations with an evaporation step are requisite for the process. As is well known in chemical process design, costly energy consuming unit operations add to the overall operating expenses for the process which are translated to the profit margin. Accordingly, it is most desirable to avoid such operations in processes. 
     U.S. Pat. No. 5,549,876, issued Aug. 27, 1996, to Zisner et al., provides methodology for potassium sulfate production involving differential contacting. Potash, water and sodium sulfate are placed in a differential countercurrent contactor to produce the potassium sulfate. 
     Potassium chloride and sulfuric acid are reacted and the resulting mixture kneaded to produce potassium sulfate, as disclosed by Iwashita et al., in U.S. Pat. No. 4,342,737, issued Aug. 3, 1982. 
     Other methods of manufacture include fractional crystallization of sulfate ores or by the Hargreaves process. 
     It would be most desirable for potassium sulfate production to be achieved without the use of acids, high energy input or other such unit operations. The present invention provides for such a process. 
     SUMMARY OF THE INVENTION 
     One object of the present invention is to provide an improvement in potassium sulfate preparation. 
     Generally speaking, the process results in the formulation of useful products during the synthesis of the potassium sulfate with recovery of sulfate and potassium in excess of 95% completely in the absence of evaporation. This significant feature has particular importance in terms of energy efficiency and thus the costs of the process. 
     A further object of one embodiment of the present invention is to provide a method of producing potassium sulfate from a source containing ammonium sulfate, comprising the steps of: 
     contacting potassium chloride and ammonium sulfate in a mixer at a temperature of between 20° C. and 40° C.; 
     precipitating a first precipitate of double salt in a filtrate; 
     mixing, in a second mixing step, the filtrate with potassium chloride; 
     generating a second filtrate containing ammonium and potassium chloride and a second precipitate of double salt; 
     mixing the second double salt precipitate with the first precipitate in a solution of potassium chloride; 
     precipitating a third precipitate of potassium sulfate and a third filtrate; 
     recirculating the third filtrate into the second mixing step; 
     mixing the second filtrate in a mixing tank at a temperature of less than 70° C. in a solution of less than 10% by weight sodium chloride, calcium chloride and sodium sulfate; and 
     generating a syngenite precipitate and a fourth filtrate. 
     Another object of one embodiment of the present invention is to provide a method of producing potassium sulfate from a source containing ammonium sulfate, comprising the steps of: 
     contacting potassium chloride and ammonium sulfate in a mixer at a temperature of less than 30° C.; 
     precipitating a first precipitate of double salt in a filtrate; 
     mixing, in a second mixing step, said filtrate with potassium chloride; 
     generating a second filtrate containing ammonium and potassium chloride and a second precipitate of double salt; 
     mixing said second double salt precipitate with said first precipitate in a solution of potassium chloride; 
     precipitating a third precipitate of potassium sulfate and a third filtrate; 
     recirculating said third filtrate into said second mixing step; 
     mixing said second filtrate in a mixing tank at a temperature of less than 70° C. in a solution of less than 10% by weight sodium chloride, calcium chloride and sodium sulfate; 
     generating a syngenite precipitate and a fourth filtrate; 
     mixing, in a sealed mixing tank at a temperature of about 80° C., said fourth filtrate with less than about 18% by weight sodium chloride, about 23.6% ammonium chloride and lime or hydrated lime; 
     recovering ammonia from said fourth filtrate; 
     passing said fourth filtrate into an air scrubber and further removing ammonia from calcium chloride and sodium chloride; 
     passing said fourth filtrate into an ammonium scrubber to generate ammonium sulfate; 
     passing said syngenite precipitate into a mixing tank at a temperature of about 70° C. in the presence of ammonium bicarbonate; 
     generating a calcium carbonate precipitate and a fifth filtrate containing potassium sulfate and ammonium sulfate; and 
     recycling said fifth filtrate to at least one of the mixing steps. 
     Having thus described the invention, reference will now be made to the accompanying drawing illustrating a preferred embodiment. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     FIG. 1 is a schematic illustration of the process flow diagram according to one embodiment of the present invention; and 
     FIG. 2 is a schematic illustration of the process flow diagram according to another embodiment of the present invention. 
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     Potassium sulfate is a valuable chemical commodity, typically employed in analytical chemistry, cement mixes and fertilizer for chloride sensitive crops such citrus and tobacco crops. The compound is also used in the manufacture of glass, alum and is used as a food additive. 
     Referring now to the drawing, the overall process is broadly denoted by numeral  10 . The feedstock material  12  includes solid potassium chloride and ammonium sulfate in an amount less than about 40% by weight (NH 4 ) 2 SO 4 . The compounds are mixed in a mixing tank  14 , which tank  14  is heated to between 25° C. and 30° C. in order for the conversion of the compounds to double salt. After sufficient mixing, the solution is passed into a separator  16 , an example of which is a cyclone. The resulting solid is K 2 SO 4 ·(NH 4 )·2SO 4 , double salt. The first filtrate is subsequently passed into a second mixing container  18  into which is added additional potassium chloride brine. The container is heated similarly to container  14  and once mixed, the solution is separated by separator  20 . The resulting second filtrate is subjected to further unit operations to be discussed hereinafter. 
     The second precipitate from mixing tank  18  as well as the first precipitate from tank  14  are combined in a third heated container  22  together with saturated potassium chloride brine. The product is then separated by separator  24  into a third filtrate for recycle into container  18  and a third solid comprising potassium sulfate crystals in a size distribution of approximately 20 mesh to about 150 mesh. In this portion of the circuit, the yield is approximately 95% SO 4  and 80% potassium. 
     Returning now to the second filtrate from the separator  20 , the same contains ammonium chloride, sodium chloride (approximately 10%) and potassium chloride. This is passed into a fourth mixing container  26  together with calcium chloride and sodium sulfate. The container  26  is kept at a temperature of between 25° C. and 70° C. The resulting mixture is separated with separator  28  into a solid, namely syngenite (CaSO 4 ·K 2 SO 4 ·xH 2 O) which washed with water and retained for additional unit operations. The liquid is passed into a fifth sealed mixing container  30  containing lime or hydrated lime. The container is maintained at a temperature of about 80° C. in order to liberate ammonia (approximately 98% by volume). Residual ammonium is passed into air scrubber  32  resulting in the generation of calcium chloride/sodium chloride brine. This may be subjected to further processing to produce CaCl 2  or NaCl, disposed of in deep well injection or returned to the ocean. 
     Further processing includes additional scrubbing of the ammonium in scrubber  34  to which may be added sulfuric acid to result in the generation of ammonium sulfate, a useful fertilizer. Returning to the syngenite, the same is passed into a sixth mixer  36  maintained at 70° C. to which ammonium bicarbonate has been added. The mixture is passed into a separator  38  to generate calcium carbonate precipitate with a +95 brightness and a filtrate containing potassium sulfate and ammonium sulfate. The filtrate may be recycled to the initial steps of the process. 
     In an alternative method, FIG. 2 illustrates a flow chart where potassium sulfate is formulated from ammonium sulfate contaminated with sodium sulfate. As is well known in the art, contaminated ammonium sulfate is not useful as a vendible high quality fertilizer. 
     Numeral  40  denotes the overall process for FIG.  2 . Ammonium sulfate and potassium chloride are mixed together in mixing tank  42  at a temperature of between 30° and 40° C. such that there is only enough water to saturate either the ammonium sulfate or potassium chloride. The mixture is passed into a separator  44  to produce 80% to 90% potassium sulfate crystal containing approximately 10% to 20% ammonium sulfate. The crystal product is filtered and/or washed (not shown) added to a solution of saturated potassium chloride brine in mixing vessel  46  at a temperature of 30° C. The solution is filtered with filter  48  with the solid fraction containing in excess 98% pure ammonium sulfate. The crystals, once centrifuged and washed have been found to have a purity in excess of 99.5%. 
     The potassium chloride brine from vessel  46  is recycled to mixing vessel  42 ; the brine from vessel  42  contains between 20% and 30% ammonium chloride and preferably between 22% and 25%, 10% or less sodium chloride and 15% or less potassium chloride. 
     The heated brine is reacted with sodium sulfate and either calcium chloride or calcium sulfate dihydrate in vessel  50  at approximately 30° C. to precipitate the soluble potassium chloride as syngenite, CaSO 4 ·K 2 SO 4  (x)H 2 O at separator  52 . 
     The syngenite salt is then filtered and washed (not shown) to remove the residual chloride brine. The salt is then heated in vessel  54  at a temperature of between 70° C. and 90° C. together with water and a source of ammonia and carbon dioxide or ammonium bicarbonate to convert the calcium sulfate to calcium carbonate. The calcium carbonate is separated in separator  56 . Since the ammonium sulfate and the SOP are soluble, the calcium carbonate precipitate is filtered and washed with water to remove entrained ammonium sulfate etc. 
     The calcium carbonate precipitate is of a sufficiently high quality and size to provide utility as a bulk paper filler of +95 brightness on blue light. The filtrate is recycled to vessel  42  as indicated by A in FIG.  2 . 
     The filtrate from separator  52  is heated in vessel  58  at a temperature of between 60° C. and 100° C. and reacted with lime to yield a brine of calcium chloride, sodium chloride and ammonia gas. The ammonia gas is recovered for further purposes. 
     As an example, the following is a calculation and the chemistry involved in the process of FIG.  2 . 
     EXAMPLE 1 
     Sodium Sulfate/Ammonium Sulfate is a Solid 
     Step 1 
     
       
         (NH 4 ) 2 SO 4(S) +KCl (l) +H 2 O+Na 2 SO 4(S) →(K 2 SO 4 ) 8 ·(NH 4 ) 2 SO 4 ) 2(S) +NH 4 Cl (l) +KCl (l) +NaCl (l) +H 2 O 
       
     
     Step 2 
     
       
         (K 2 SO 4 ) 8 ·((NH 4 ) 2 SO 4 ) 2(S) +KCl (l) +H 2 O→(K 2 SO 4 ) (S) +(NH 4 ) 2 SO 4(l) +KCl (l)   
       
     
     Step 3 
     
       
         NH 4 Cl (l) +NaCl (l) +KCl (l) +H 2 O+CaCl 2(l) +Na 2 SO 4(S) +→CaSO 4 ·K 2 SO 4 xH 2 O+NH 4 Cl (l) +Na 4 Cl (l) +KCl (l) +H 2 O 
       
     
     Step 4 
     
       
         CaSO 4 ·K 2 SO 4 xH 2 O+NH 4 HCO 3(l) →CaCO  3(S) +(NH 4 ) 2 SO 4(l) +(K 2 SO 4 ) (l)   
       
     
     Step 5 
     
       
         NH 4 Cl (l) +Na 4 Cl+H 2 O+CaO→NH 3(g) +CaCl 2 +NaCl+KCl+H 2 O 
       
     
     Some of CaCl 2  can be recycled to Step 3 but if that Cl builds up in the circuit; then one has to precipitate the CaCl 2  as CaSO 4 ·2H 2 O and send the solid gypsum as the recycle. 
     Sample Calculation 
     Feed 25% (NH 4 ) 2 SO 4  with 10% Na 2 SO 4  @ 30° C. S.G. 1.300 therefore solution contains: 
     
       
         
               
               
               
               
             
               
               
             
               
               
               
               
             
               
               
               
               
               
             
               
               
             
               
               
               
               
             
               
               
               
               
               
             
               
               
             
               
               
               
               
             
               
               
             
               
               
               
             
               
               
             
               
               
               
             
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                  325 
                 g (NH 4 ) 2 SO 4   
                  80% conversion 
               
               
                   
                 130 
                 g Na 2 SO 4   
                 100% conversion 
               
               
                   
                 845 
                 g H 2 O 
               
               
                   
                 1300 
                 g 
               
             
          
           
               
                   
                 Add solid KCl 291 + 135 + 120 (excess) = 546 g 
               
             
          
           
               
                 A) 
                 Solids 
                 B) 
                 Liquid 
               
             
          
           
               
                   
                  500.8 
                  g K 2 SO 4   
                 304 
                 g NH 4 Cl 
               
               
                   
                 65 
                 G (NH 4 ) 2 SO 4   
                 106 
                 g NaCl 
               
               
                   
                 566 
                 g Double Salt 
                 120 
                 g KCl 
               
               
                   
                   
                   
                 30 
                 g KSO 4   
               
               
                   
                   
                   
                 845 
                 g H 2 O 
               
               
                   
                   
                   
                 1405 
                 g 
               
             
          
           
               
                  A) 
                 Double Salt + 150 g KCl + 470 H 2 O 
               
             
          
           
               
                   
                 Solids 
                 B) 
                 Liquid 
               
             
          
           
               
                   
                 556 
                 g K 2 SO 4   
                 68 
                 g NH 4 Cl 
               
               
                   
                   
                   
                 30 
                 g K 2 SO 4   
               
               
                   
                   
                   
                 77 
                 g KCl 
               
               
                   
                   
                   
                 470 
                 g H 2 O 
               
               
                   
                   
                   
                 645 
                 g 
               
             
          
           
               
                  B) 
                 Liquid 
               
             
          
           
               
                   
                  304 
                  g NH 4 Cl 
                   
               
               
                   
                 106 
                 g NaCl 
                 168.2 g CaSO 4  H 2 O + 102 g Na 2 SO 4   
               
               
                   
                 120 
                 g KCl 
               
               
                   
                 30 
                 g K 2 SO 4   
               
               
                   
                 845 
                 g H 2 O 
               
               
                   
                 1405 
                 g 
               
             
          
           
               
                 D) 
                 Solids (sygenite) - 140 g K 2 SO 4  +168 g  → CaSO 4 .2H 2 O = 309 g 
               
               
                 E) 
                 Liquid 
               
             
          
           
               
                   
                 304 
                  g NH 4 Cl 
               
               
                   
                 189 
                 g NaCl 
               
               
                   
                 14 
                 g KCl 
               
               
                   
                 14 
                 g K 2 SO 4   
               
               
                   
                 845 
                 g H 2 O 
               
               
                   
                 1366 
                 g 
               
             
          
           
               
                 D) 
                 Solids (sygenite) - 308 g + 152 g NH4HCO 3  + 750 g H 2 O → 
               
               
                   
                    F(solids) + G(liquid) 
               
               
                 F) 
                 CaCO 3   
               
               
                 G) 
                 Liquid Recycle to Step 1 
               
             
          
           
               
                   
                 129 
                 g NH 4 SO 4   
               
               
                   
                 140 
                 g K 2 SO 4   
               
               
                   
                 750 
                 g H 2 O 
               
               
                   
                 1019 
                 g 
               
             
          
           
               
                 E) 
                 Liquid 
                 (Brine) 
               
             
          
           
               
                   
                 304 
                  g NH 4 Cl + 
                 253 
                  g CaCl2 
               
               
                   
                 189 
                 g NaCl + 130 g CaO → NH 3(gas)   
                 189 
                 g NaCl 
               
               
                   
                 120 
                 g KCl 
                 14 
                 g KCl 
               
               
                   
                 30 
                 g K 2 SO 4   
                 14 
                 g K 2 SO 4   
               
               
                   
                 845 
                 g H 2 O 
                 845 
                 g H 2 O 
               
               
                   
                 1405 
                 g 
                 1315 
                 g 
               
               
                   
                   
               
             
          
         
       
     
     Recycle of G increases the circuit efficiency and one can adjust the material balance to the desired recycle and recovery. Discharge brine is deep well injected or evaporated to produce CaCl 2  brine for sales. Estimated K recovery can be calculated to be:                    KCl                 exit                               =     14                 g                     K   2          SO   4                   exit                =       14                 g     =     11.9                 g                 KCl               }                                26                 g                         Therefore:               1     -       26   546     ×   100       =     95.2      %                   SO   4                     Recovery:           1     -       8   324     ×   100       =     97.5      %                            
     This process compares favourably to any current commercial process, but without evaporators. 
     Although embodiments of the invention have been described above, it is not limited thereto and it will be apparent to those skilled in the art that numerous modifications form part of the present invention insofar as they do not depart from the spirit, nature and scope of the claimed and described invention.