Abstract:
A process for reducing the sulfur and ash content of coal is provided. The process involves cleaning the coal of debris and pulverizing it. The pulverized coal is contacted with a reagent selected from the group consisting of aqueous solutions of active nitrogen containing compounds, aqueous solutions of organic compounds containing at least one hydroxyl group, surfactants containing active ammonium groups and combinations thereof. The coal is washed with water and dried.

Description:
BACKGROUND OF THE INVENTION 
     The invention relates to a method for treating coal to remove sulfur and ash. 
     Bituminous coal, generally found in the Eastern portion of the United States, contains a large amount of volatile matter, particularly sulfur and ash. Such coal can include as much as 6-8% total sulfur by weight. Inorganic sulfur, generally pyrites or iron sulfide, accounts for between 25% and 75% of the total sulfur content of bituminous coal. 
     Because of the high sulfur and ash content in bituminous coal, it is not practical to burn such coal on a commercial scale. Users cannot easily and economically comply with the clean air standards of the Environmental Protection Agency for SO 2  emissions. Coal burning stationary plants are allowed 1.2 lbs. of SO 2  emission per million BTU&#39;s of hot input according to recent EPA standards. Thus, the coal burned in such plants must contain no more than 1.5% total sulfur by weight. Further, bituminous coal must compete with anthracite coal, generally found in the Western portion of the United States, which contains 1% or less total sulfur by weight, well within the EPA standards. 
     Numerous methods have been proposed for removing all or a substantial amount of the sulfur and ash found in bituminous coal. Many of these methods require external applications of heat and/or pressure, some processes invoke so much heat that char forms. Other methods use sophisticated chemical reagents and equipment. These methods are expensive and, thus, are not economically feasible. Further, the processes create environmental problems in disposing of the by-products. Exemplary of these methods are the processes taught in U.S. Pat. Nos. 3,988,120; 4,162, 898; 4,167,397; 4,169,710; 4,226,601; 4,226,602; 4,256,464; 4,304,573; 4,305,815; and 4,332,593. DOE/ET Exploratory Study of Coal-Conversion Chemistry, Quarterly Report, SRI International (1981); DOE, Advanced Coal Preparation, Engineering Foundation (New York) 1981; Plaksin, New Methods of Increasing the Effectiveness of Concentration of Minerals. Academy of sciences of the U.S.S.R., A.A. Skochinskii Mining Institute (1973); Van Le, Floatability of Coal and Pyrite, M.S. Thesis Iowa State University (1977); Fisher et al., Advanced Development of Fine Coal Desulfurization and Recovery, Ames Laboratory, Iowa Sate University (1977); Hucko, Beneficiation of Coal by Selective Flocculation, a Laboratory Study, Bureau of Mines, Report of Investigations (1977). 
     U.S. Pat. No. 4,328,002 teaches a coal treatment process for desulfurization in which the coal is exposed to an oxidizing reagent/detergent solution and then exposed to a passivating/sequestering reagent and neutralized. The process has the advantage of creating a useful agricultural by-product. Furhter, the process does not require the application of external heat or pressure and the reactions are easily controlled and rapid. However, some of the possible oxidizing reagents are expensive, between two and four cycles of the process are necessary before the sulfur content of the coal is reduced below 1.5%, the process requires several different reagents, the pH of the solutions involved in the process oscillate between 2 and 9, the total reaction time is long, exothermic heating of the coal occurs and noxious odors are created. 
     Although several prior art methods of coal desulfurization have met with some acceptance, there is a need for a rapid, inexpensive method of desulfurization without the attendant disadvantages extant in the prior art. 
     SUMMARY OF THE INVENTION 
     A process treating coal to remove sulfur and ash includes cleaning and pulverizing the coal, treating the coal with an aqueous solution of a compound containing an active nitrogen, an aqueous solution of an organic compound containing at least one hydroxyl group, a surfactant containing active ammonium groups or combinations thereof, and washing and drying the coal. Preferably, the coal is contacted by the aqueous solution for less than one minute. Preferably, the concentration of the reagent or reagents in the solution is between 0.001 and 20% by weight. The process preferably results in an agricultural by-product. 
     To improve aqueous reagent penetration into harder coal bedding planes and pores and to facilitate ash and sulfur removal, the coal can be pretreated or soaked with any of the reagent solutions (in the preferred concentration range) prior to laboratory or commercial processing. The preferred interval of time for such soaking is between 5 minutes and 48 hours. 
     DESCRIPTION OF THE PREFERRED EMBODIMENT 
     In the process of the present invention the coal is cleaned by one of many known methods to remove non-coal debris and pulverized, preferably to a size of less than 4 inches. The coal is then treated with the reagent solution, preferably for a period of less than one minute, washed with water and dried. Preferably, the concentration of the reagent or reagents in the solution is between 0.001 and 20% by weight. 
     The coal may be treated with the reagent using any one of a number of known processes. One preferred method for processing the coal on a commercial scale is to treat the coal in a dense media classifier using the Tromp method which involves the use of a high density aqueous suspension of magnetite as the dense media. Other methods which may be used include a dense media classifier in which sand or barite is substituted for the magnetite. In the absence of a dense media, processes may be used in which a hydrocyclone jig, screens or centrifugal separation is used to isolate the processed coal. 
     Suitable reagent solutions include aqueous solutions of compounds containing an active nitrogen, aqueous solutions of organic compounds containing at least one hydroxyl group, surfactants containing active ammonium groups and combinations thereof. 
     Suitable compounds containing an active nitrogen include both inorganic and organic ammonium salts, amides and amines. 
     Inorganic ammonium salts suitable for use in the invention include ammonium bicarbonate, ammonium bifluoride, ammonium bisulfide, ammonium bisulfite, ammonium borate, ammonium tetraborate, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium chromate, ammonium dichromate, ammonium ferrous sulfate, ammonium fluoride, ammonium hexafluorosilicate, ammonium iodide, ammonium nitrate, ammonium nitrate sulfate, ammonium nitrite, ammonium perchlorate, dibasic ammonium phosphate, monobasic ammonium phosphate, ammonium silicate, ammonium phosphite, ammonium sulfate, ammonium sulfide, ammonium sulfite, ammonium thiocyanate and ammonium thiosulfate. Preferably, the inorganic salts are ammonium bicarbonate, ammonium borate, ammonium tetraborate, ammonium carbonate, ammonium nitrate sulfate, ammonium nitrite, dibasic ammonium phosphate, monobasic ammonium phosphate, ammonium phosphite, ammonium sulfate and ammonium sulfite. 
     Organic ammonium salts suitable for use in the invention include ammonium acetate, ammonium benzoate, ammonium binoxalate, ammonium bitartrate, ammonium carbamate, dibasic ammonium citrate, ammonium formate, ammonium lactate, ammonium oleate, ammonium oxalate, ammonium palonitrate, ammonium picrate, ammonium stearate and ammonium tartrate. 
     Suitable organic compounds containing at least one hydroxyl group include monohydric alcohols, diols, polyols and carboxylic acids. Suitable monohydric alcohols include methanol and ethanol. 
     Suitable diols include glycol, such as ethylene glycol and dihydricphenols including catechol, resorcinol and giunol. 
     Suitable polyols include gylcerol and pyrogallol. 
     Surfactants suitable for use in the present invention include ammonium anionic surfactants, quaternary ammonium cationic surfactants and non-ionic surfactants as described by Rosen and Goldsmith, Systematic Analysis of Surface-Active Agents, 1972, p. 12-16 and McCutcheon, Synthetic Detergents, 1950, pp. 378-422. The ammonium anionic surfactants include Class IV A1 containing sulfur, but not nitrogen or phosphorus, in the anion and containing nitrogen in the cation, Class IV A2 containing nitrogen and sulfur, but not phosphorus, in the anion and containing nitrogen in the cation and Class V C1 containing phosphorus, but not nitrogen or sulfur in the anion and nitrogen in the cation. The quarternary ammonium cationic surfactants include Class IV A3 and ampholytes containing nitrogen and sulfur, but not phosphorus, in the surface active ion. Non-ionic surfactants include Class V A containing phosphorus. 
     The processing reagent solution(s), at the same concentration or more dilute concentration, can be applied to the more difficult (harder grindability) coals prior to processing for a soak period of 5 minutes to 48 hours. 
     In the prior art, values for reductions in sulfur and ash include final density separations, i.e. the values or analyses are for coal isolated from the reject materials. No physical density separations such as float/sink, magnetic separation, froth flotation, centrifugation or hydrocyclone were used to isolate the coal in Examples 1 through 10. However, a limited density separation is inherent in the apparatus used in Examples 11 through 19. 
    
    
     EXAMPLES 1-10 
     One hundred grams of a Pennsylvania Bakerstown seam coal, 3/8×0 grind, of 3.14% sulfur by weight were reacted with 50 g. of a reagent solution by ball milling for 2 minutes. The coal was screened to 200 mesh and washed with tap water for about 1 minute. All reagent concentrations were 5 to 10% by weight. The surfactants were less than 1% by volume. The processed coal was then washed, dried and analyzed to determine the sulfur content. 
     
         ______________________________________                  % S (dry)                  by weight % decreaseExample  Reagent(s)      processed in S content______________________________________1      hydrogen peroxide/urea                  1.26      59.92      urea            1.29      58.93      anionic &#34;S&#34; surfactant                  1.28      59.24      ammonium nitrate/                  1.31      58.3  &#34;S&#34; surfactant5      nonionic &#34;W&#34; surfactant                  1.19      62.16      nonionic &#34;T&#34; surfactant                  1.21      61.57      ethyl silicate  1.39      55.78      ammonium nitrate/                  1.14      63.7  ammonium hydroxide9      ammonium nitrate/                  1.14      63.7  nitric acid10     methanol        1.09      65.3______________________________________ 
    
     EXAMPLE 11 
     Between 200 and 270 tons per hour of #11 Waynesburg seam coal, 4×0 grind, were treated in a hydrocyclone with a solution containing about 1% by weight ammonium nitrate. The coal was exposed to the reagent solution for a period of between 22 and 26 seconds. The processed coal was then dried and analyzed to determine the sulfur, ash and heat content. 
     
         ______________________________________     raw, dry             processed, dry                         % change______________________________________% ash, by weight        27.71     14.88      -46.3% sulfur, by weight        4.62      3.77       -18.4BTU/lb.     10,057    11,317      +21.0______________________________________ 
    
     EXAMPLE 12 
     Between 300 and 330 tons per hour of #8 Waynesburg seam coal, 4×0 grind, were treated in a hydrocyclone with a solution containing between 2 and 3% by weight ammonium nitrate. The coal was exposed to the reagent solution for a period of between 22 and 26 seconds. The processed coal was then dried and analyzed to determine the sulfur, ash and heat content. 
     
         ______________________________________     raw, dry             processed, dry                         % change______________________________________% ash, by weight        14.50     9.20       -36.6% sulfur, by weight        5.20      3.38       -35.0BTU/lb.     12,250    13,250       +8.2______________________________________ 
    
     EXAMPLE 13 
     About 770 tons of Bakerstown/Freeport/Kittanning blend seam coals, 4×3/8 grind, were treated in a dense media classifier using the Tromp process with a reagent solution of between 0.8 and 1.2% by weight ammonium nitrate in a closed circulating reagent system of 1,800 gallons (15,000 lbs.) of water. The coal was exposed to the reagent solution for a period of about 30 seconds. The processed coal was then dried and analyzed to determine the sulfur, ash and heat content. 
     
         ______________________________________     raw, dry             processed, dry                         % change______________________________________% ash, by weight        31.61     12.66      -60.0% sulfur, by weight        2.58      1.10       -55.6BTU/lb.     10,257    13,455      +31.2______________________________________ 
    
     EXAMPLE 14 
     About 90 tons of Bakerstown coal, 2×0 grind, were treated in a dense media classifier using the Tromp process with various reagent solutions. The coal was exposed to the reagent solution for a period of about 30 seconds. The coal was then dried and analyzed to determine the sulfur and ash content. 
     
         ______________________________________       % S by     % S by       weight     weight   % decreaseReagent     raw        processed                           in S content______________________________________1.2% ammonium       3.08       1.78     -42.4nitrate1.4% ammonium       3.98       2.00     -49.7nitrate + 0.01%nonionic surfactant(Class I A2.2)______________________________________ 
    
     EXAMPLE 15 
     Over 1,100 tons of Bakerstown/Kittanning/Freeport (1:1:1 blend) coal were treated in a dense media classifier using the Tromp process with a reagent solution of 5% by weight ammonium nitrate. The coal of 4×3/8 grind was exposed to the reagent solution for a period of 30 seconds. The coal finer than 3/8 grind was shunted around and blended back in with the processed coal. The coal was then dried and analyzed to determine the sulfur, ash and heat content. The tabulated results include the non-treated (3/8 minus) coal (blend). 
     
         ______________________________________    raw, dry processed, dry                         % change______________________________________% ash, by weight       17.30      14.25      -17.6% S, by weight       2.73       1.72       -37.0BTU/lb.    11,300     13,600      +20.0______________________________________ 
    
     EXAMPLES 16-19 
     Ten tons of a Pennsylvania Bakerstown seam coal, 2×0 grind, were treated in a dense media classifier using the Tromp process without any reagent. The dry, processed coal had an ash content of 13.88%, a sulfur content of 3.52% and a heat content of 13,455 BTU/lb. Four additional ten ton portions of the same coal were processed using reagent solutions. The coal was exposed to the reagent for a period of about 30 seconds. The processed coal was then dried and analyzed to determine the sulfur, ash and heat content. 
     
         ______________________________________              % S, by wt.                         % ash, by wt.Ex-                processed, processed,                                  BTU/ample Reagent      dry        dry      lb.______________________________________16    1.2%         1.98       13.11    13,513 ammonium nitrate17    1.0%         1.88       13.55    13,465 ammonium nitrate18    1.0%         1.98       12.37    13,609 ammonium nitrate +0.01% &#34;W/S&#34; nonionic/anionic surfactant19    1.0%         1.81       13.01    13,560 ammonium nitrate +0.01% &#34;W/S&#34; nonionic/anionic surfactant______________________________________ 
    
     Although the invention has been described with reference to specific processes and specific materials, the invention is only to be limited so far as is set forth in the accompanying claims.