Patent Publication Number: US-4579650-A

Title: Coal enhancement process and equipment

Description:
CROSS REFERENCE TO THE RELATED APPLICATION 
     This application is a continuation-in-part of application Ser. No. 567,434 filed Dec. 30, 1983 and now abandoned. 
    
    
     BACKGROUND OF THE INVENTION 
     There are many patents and literature references, too numerous to mention, which disclose techniques as well as chemicals useful to separate coal from the gangue. The most widely used of these techniques employs the sink-float principle using magnitite as the heavy medium. The literature, however, teaches literally hundreds of compounds, most halogenated hydrocarbons, as equally useful. 
     So far the substitution of this later genus of compounds has not had much, if any, commercial success although several pilot plants are now running using perchloroethylene. One disadvantage associated with the use of this later class of compounds is that the coal retains a considerable amount of the halogenated compound and if not removed by stringent heating its retention, on burning, causes excessive corrosion in boilers and furnaces. 
     Representative of recent patents disclosing equipment employed in heavy media separations are U.S. Pat. Nos. 3,348,675, 2,150,917, 2,150,899, and 2,151,578. In addition, sales and promotional literature of Otisca and McNally show licensed processes. 
     BRIEF DESCRIPTION OF THE INVENTION 
     In accordance with the present invention a halogenated hydrocarbon the bromo chloro fluoro and mixed halogen hydrocarbons, particularly tetrachloroethylene (perchloroethylene), trichloroethylene, 1,1,1-trichloroethane (methylchloroform), or methylene chloride (dichloromethane) is slurried with a crushed (preferably 1/16 to 1/2 inch) run of the mine coal for a short period of time, usually from about 15 to 10 minutes, at temperatures of from about -10° C. to about 80°-90° C. The slurry is allowed to settle under substantially quiescent or mild agitation conditions. The coal rich particles will float free of the gangue rich particles which settle. Each body of settled and floated particles are removed for separate treatment. Following such separation, each body is independently treated with hot, 90°-100° C., water for a time sufficient to azeotrope off the separating liquid, i.e., the chlorinated solvent. Such treatment reduces the retained liquid to between about 100 parts to about 19000 parts liquid per million parts of coal. Many coals can be freed of solvent to less than 400 parts liquid per million parts coal usually in about 1/2 to 5 minutes contact. This is equivalent to less than 0.8 pound of liquid per ton of coal. Mild agitation may accompany the hot water treatment. 
     Representative results of processes which use steam or hot air show residual liquid in the order of 0.095% (950 ppm) at 180° F. steam; while oven heating for one hour at 100° C. leaves 0.655% (6550 ppm) liquid, at 175° C. 0.08% (800 ppm) or at 200° C. for one hour 0.02% (200 ppm) liquid retained compared to the 400 parts using only 98° C. water and only one minute contact in accordance with the present invention. Thus it is seen that, unexpectedly, the use of hot water vis-a-vis steam, hot air or ovens (kilns) removes more of the retained heavy media quicker than these prior art higher temperature processes. The invention allows essentially full recovery of the halogenated solvent. Both the steam and hot air (ovens) make it very difficult to have a good recovery of the halogenated because substantial amounts generally escape to ambient air. The ability to have a quick solvent removal is beneficial because the solvent may permiate the tars in a coal with time. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     EXAMPLE 1 
     To illustrate the effect hot water has on removing the heavy media from coal, 200 grams Aryshire coal, ROM, 1/2 inch to pan, about 31/2% less than 100 mesh, was added to a liter of perchloroethylene with mixing for 5 minutes. Mixing was rapid but insufficient to attrite any appreciable amount of the coal. Following cessation of mixing the slurry was allowed to settle and about 3/4 of the liquid, containing most of the coal, was separated and the liquid filtered away. This float filter cake portion, filtered free of the body of liquid perchloroethylene, was slurried into hot water at 99° C. The temperature dropped to between 88° C. and 93° C. due to mixing the wetted coal which was at ambient temperature, ca 23° C., with the hot water. Heat was applied to the container to maintain the temperature of the slurry at 88° C. and heating was continued until the slurry temperature rose to about 100° C. at which temperature about 10 cc of water substantially free of perchloroethylene was distilled over. Thereafter the coal was filtered free of the water and analyzed. 
     Analysis showed the coal had 
     
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water            9%                                                       
perchloroethylene                                                         
                 1.3%                                                     
ash              6%                                                       
sulfur           3.4%                                                     
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     The original coal had 
     
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        ash   11.7%                                                       
        sulfur                                                            
              4.5%                                                        
        water 6.3%                                                        
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     The bottom portion (sink) of the sink float step treated in the same manner as the float had an analysis of 
     
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ash               42%                                                     
sulfur           6.9%                                                     
perchloroethylene                                                         
                 0.5%                                                     
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     The above analysis illustrates that the hot water treatment effectively removes perchloroethylene from coal. 
     In comparison the same coal, treated by the same sink float technique using perchloroethylene as the heavy medium, when dried in a hot air convection oven at 120° C. air had a retained perchloroethylene content of 1.44% in the float portion after 1/2 hour, 1.10% after 1 hour, 0.96% after 2 hours, 0.86% after 3 hours and 0.68% after 4 hours. 
     EXAMPLE 2 
     Ayrshire coal, R.O M. from Amax, Ind. was processed by a sink float method in one of the following solvents then freed of residual solvent by the hot water treatment of Example 1. Comparison is also reported using the convection oven drying technique. The following table lists the results of the hot water heavy media removal technique: 
     
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                              1,1,1-                                      
          Perchloro-                                                      
                   trichloro- trichloro-                                  
          ethylene ethylene   ethane                                      
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% solids in float                                                         
            82         71         64                                      
% solids in sink                                                          
            18         29         36                                      
% solvent in float                                                        
            1.5        1.8        1.8                                     
solids                                                                    
water temperature,                                                        
            97         97         97                                      
°C.                                                                
time of slurry in hot                                                     
            15 minutes 15 minutes 15 minutes                              
water                                                                     
ppm solvent after                                                         
            1908       1675       1413                                    
hot water                                                                 
treatment                                                                 
% ash orig/float/                                                         
            11.7/5.9/41.9                                                 
                       11.7/4.9/38.6                                      
                                  11.7/2.7/21.6                           
sink                                                                      
% sulfur orig/float/                                                      
            4.5/3.4/6.9                                                   
                       4.5/3.3/4.7                                        
                                  4.5/2.5/4.5                             
sink                                                                      
Specific Gravity of                                                       
            1.62       1.32       1.46                                    
Solvent,                                                                  
25/25° C.                                                          
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     Thus it is seen that the hot water treatment is equivalent to treatment with steam or hot air but equivalency can be achieved in shorter periods of time. The more important advantage is the ability to recover 99+% of the chlorinated solvent with the hot water treatment. 
     EXAMPLE 3 
     Cammeron Coal, R.O.M., Perma Mining, S.E. Colo., was processed by the sink float technique, the sink and float separated and each filtered to remove the solids with only retained solvent. The resulting cakes were each slurried in hot water to remove the residual solvent (heavy medium). The results employing different solvents as the heavy media are set forth below: 
     
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            Perchloro-                                                    
                  1,1,2-trichloro-                                        
                              methylchloro-                               
            ethylene                                                      
                  ethylene    form                                        
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% sink/float                                                              
            2/98  6/94  6/94  44/56                                       
                                  20/80                                   
% solvent on float                                                        
                  6     1                                                 
temperature, sink/float                                                   
            ambient                                                       
                  ambient     25° C.                               
                                  -5°-0° C.                 
treatment                                                                 
temperature hot water,                                                    
            100   100   97    100 100                                     
°C.                                                                
time to dry, min.                                                         
            10    10    1/2   1   1                                       
% solvent remaining                                                       
            0.14  0.061 0.042 --  &lt;0.010                                  
after hot water                                                           
            (1400 ppm)                                                    
                  (614 ppm)                                               
                        (416 ppm) (&lt;100 ppm)                              
treatment (ppm)                                                           
% ash in orig. coal                                                       
            12-15 12-15 12-15                                             
% ash after hot water                                                     
            8.72* 8.35* 8.52*     7.72*                                   
treatment in float                                                        
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 *pretreated ROM had an ash content of 12-15%                             
 
    
     EXAMPLE 4: COMPARATIVE EXAMPLE 
     In a comparative run, the same coal treated by the sink/float technique using trichloroethylene was subjected to convection oven heating at 120° C. and measurements of residual solvent made at 1/2, 1, 2, 3, 4, and 8 hours. The results are set forth below. 
     
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Original residual solvent                                                 
                    3.9%   (38,275 ppm)                                   
content after filtering                                                   
Solvent content after                                                     
1/2        hour         262    ppm                                        
1          hour         270    ppm                                        
2          hours        263    ppm                                        
3          hours        281    ppm                                        
4          hours        172    ppm                                        
8          hours        157    ppm                                        
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     Again, the ability of the hot bath treatment to recover 95-100% of the solvent in less than 10 minutes is shown where the oven treatment does not recover 90% of the solvent in a practical manner in less than 1/2 hour. 
     EXAMPLE 5 
     Rocky Mountain Energy Prospect Point Mine, labeled Leucite Hills, Wyo., 8+ mesh coal from ground and screened R.O.M. coal, was subjected to heavy media separation using perchloroethylene as the heavy media. The specific gravity of each screen aliquot of coal was measured and the float/sink from each screening filtered and the cakes subjected to the hot water treatment of the present invention the results obtained when the specific gravity varied are set forth below. 
     
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(Specific gravity)                                                        
             ROM     1.6    1.5   1.4   1.3                               
% sink/float 0/100   1/99   3/97  22/78 30/70                             
Desolventized Float                                                       
% Ash        8       8      --    3.9   3.3                               
ppm residual solvent                                                      
             --      --     --    650   600                               
Desolventized Sink                                                        
ppm residual solvent              500    10                               
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     It is thus seen that in most instances the hot water treatment, water at or near its atmospheric boiling point, remove in shorter treatment periods more of the residual heavy medium halogenated solvent from the coal than the conventional steam, hot air or kilns.