# Patent

## Title
Process of producing hydrocarbons from coal

## Abstract

A process for sequentially reducing the amount of pyritic, organic and sulfate sulfur in coal and other carbonaceous materials and for producing synthetic fuels by contacting coal or a carbonaceous material with water, an acid and hydrogen at increased temperature and pressure. Coal or carbonaceous material-volatile products are collected and upgraded to produce synthetic fuels.

## Background
1. Field of the Invention

Coal represents approximately 84 percent of the known recoverable fossil fuel resources in the United States, while petroleum and natural gas account for about 10 percent and shale oil for the remaining 6 percent.

The shrinking petroleum and natural gas reserves around the world, and recently enacted governmental sulfur oxides emission standards in the United States, have highlighted the need to focus attention on coal desulfurization and conversion technology and the production of synthetic fuels therefrom to meet the growing demand for energy in the United States and around the world.

The sulfur content of coals ranges from approximately 0.2 percent to as much as 7 percent as mined. Sulfur does not occur as an element in coal, but three sulfur forms in chemical combination are recognized. Most of the sulfur, approximately 40 to 80 percent, occurs as a constituent of pyrite or marcasite. These polysulfides are deposited as famboids in peat and are formed by the reaction between ferrous ions and hydrogen sulfide which is derived from the action of anerobic bacteria on sulfates. The remainder of the sulfur occurs as hydrous ferrous sulfate (FeSO.sub.4.7H.sub.2 O) derived by weathering of pyrites, as gypsum (CaSO.sub.4.2H.sub.2 O), and as organic sulfur in combination with coal-formed vegetal material (macerals). The amount of sulfate sulfur is very small, generally less than about 0.1 percent. Organic sulfur is presumed to exist as sulfides, disulfides, mercaptans, and heterocyclic rings, for example thiophene.

Sulfur has always been an objectionable constituent of coal and other carbonaceous materials normally used to generate power and energy. Combustion of coal or other carbonaceous materials is by far the largest single source of atmospheric sulfur dioxide pollution in the United States, accounting for approximately two-thirds of the total sulfur oxide emissions.

With the rapidly diminishing oil supply and the present world-wide emphasis on the energy crisis, increased attention by both government and private organizations is being given to coal and synthetic fuels produced therefrom as an alternate energy source. However, depending upon their origin, coals contain varying amounts of sulfur in the form of pyrite, organic sulfur and sulfate sulfur from which sulfur dioxide is formed when coal, and synthetic fuels produced from coal are burned. Hence, there is an ongoing search to convert high sulfur content coal into a usable fuel which would meet current air quality standards and, additionally, help to aleviate the current shortage of crude oil. The best processes which are known to the art, generally do not combine a process for desulfurizing coal or carbonaceous materials and producing a synthetic fuel.

2. Brief Description of the Prior Art

The problem of separating sulfur and other impurities and producing synthetic fuels from coal and carbonaceous materials is known and several processes have been extensively tested over the years. One such process is set forth in U.S. Pat. No. 3,926,575 which discloses a process for reducing the pyritic content of coal, which comprises reacting finely divided coal with sulfuric or hydrochloric acid. An alternate method is disclosed for removing sulfur from coal which involves, in addition to an acid leach, a final extraction step involving use of a solvent, for example, benzene, etc.

Another process is disclosed in U.S. Pat. No. 4,071,328 which relates to a method of removing sulfur from coal which consists of hydrogenating the coal to remove a portion of sulfur therefrom. Next, the hydrogenated coal is contacted with an aqueous inorganic acid solution to remove some of the sulfur initially combined as pyritic sulfur.

U.S. Pat. No. 4,054,421 relates to a process for reducing the sulfur content of chars made from coal, by washing the char with an acid followed by treatment with hydrogen gas. Particularly, coal is converted to char and thereafter introduced into an acid bath, comprising an aqueous solution of a mineral acid, for example hydrochloric acid.

A process for upgrading solid fuels is disclosed in U.S. Pat. No. 4,047,898 which teaches treatment of low rank fuels, for example, subbituminous coals with water under increased temperature and pressure in the presence of hydrogen. Particularly, the patent discloses a method for the benefication of low rank solid fuels which consists of mixing a low rank fuel with water, heating the mixture to a temperature above 300.degree. F. and at a pressure sufficient to maintain water in the liquid phase under reaction conditions, for a time period sufficient to reduce the sulfur and ash content and increase the fuel BTU value. As can readily be determined from the above, there is an ongoing search for new and more efficient processes for desulfurizing coal and carbonaceous materials and for producing useful synthetic fuels therefrom.

The present invention resides in a process for desulfurizing coal or other carbonaceous materials and producing synthetic fuels which comprises contacting coal or a carbonaceous material with hydrogen, water and/or an aqueous media in an amount sufficient to maintain the pH from about 1.0 to about 6.0, at a temperature of from about 350.degree. F. to about 650.degree. F., a pressure from about 100 p.s.i.g. to about 4,000 p.s.i.g. for about 0.5 hour to about 30 hours; contacting the coal or carbonaceous material with hydrogen at a temperature of from about 800.degree. F. to about 1,700.degree. F., a pressure of from atmospheric pressure to about 500 p.s.i.g., at a hydrogen flow rate of from about 100 to about 5,000 volumes of hydrogen per volume of coal or carbonaceous material per hour, for about 0.1 hour to about 50 hours. The volatile products produced in the process are collected and upgraded to produce synthetic fuels.

The drawing is a simplified flow diagram schematically illustrating the process disclosed herein.

The present invention resides in a process for desulfurizing coal and other carbonaceous materials, and additionally for producing synthetic fuels therefrom, using hydrogen, water and an acid in combination with a second hydrogenation step at increased temperature.

Sulfur, bonded in pyritic and organic compounds, is converted into a sulfide compound which may be extracted or leached from the coal or carbonaceous material with an acid. Extraction of the sulfides with an acidic compound results in dissolution of the sulfide compounds and the release of sulfur as hydrogen sulfide. The hydrogen sulfide is, then, sent to a hydrogen sulfide absorbing solution, for example an amine solution, where hydrogen sulfide is recovered.

Organic sulfur is removed from the coal or carbonaceous material by contacting extracted coal or carbonaceous material with hydrogen at high temperatures. At these temperatures, hydrogen reacts with organic sulfur compounds to form hydrogen sulfide which is readily recovered as sulfur.

Anthracitic materials, bituminous and subbituminous coal, lignitic materials, peat, coke and other types of coal products referred to in ASTM Designation: D-388-66 (reapproved 72) are examplary of the solid carbonaceous materials which may be treated in accordance with the process of the present invention to produce low sulfur coal and synthetic fuels therefrom. The coal, prior to use in the process of the invention, is preferably pulverized using a suitable apparatus, for example, a hammermill, etc., to a size such that at least 90 percent of the coal will pass through a 200 mesh (U.S. Series) sieve. The ground coal is then slurried in a suitable solvent, for example, water or a water-acid mixture, before introduction into a pressurized reaction vessel to be contacted with other components to promote sulfur removal thereform.

Coals and other solid carbonaceous materials that may be used herein, include any high sulfur coal or carbonaceous material, preferably of the following composition on a moisture free basis. ______________________________________ Weight Percent Broad Range Typical Range ______________________________________ Carbon      45-95         60-92 Hydrogen    2.5-7.0       4.0-6.0 Oxygen      2.0-45        3.0-25 Nitrogen    0.75-2.5      0.75-2.5 Sulfur      0.3-10        0.5-6.0 ______________________________________

Illustrative examples of suitable coals or carbonaceous materials include anthracite, lignite, peat, coke, Pittsburgh seam coal, Kentucky coal, Indiana #3 coal, Wyoming coal and the like. It should be noted that the sulfur content of the above-described coals or carbonaceous materials may vary greatly even in one particular coal field and the above coals and carbonaceous materials are illustrative of coals and carbonaceous materials that may be treated in accordance with the process herein.

A coal, selected from the group consisting of anthracite, bituminous, subbituminous, lignite, etc., or other carbonaceous material described in ASTM Designation: D-388-66 (reapproved 72), is crushed to a suitable particle size using conventional apparatus. A desirable particle size range is from about 60 to about 400 standard mesh, preferably from about 100 to about 300 standard mesh, especially where 90 percent passes through a 200 standard mesh sieve.

In a preferred mode, crushed coal, water and acid are introduced through lines 2 and 4 into mixing vessel 6 to prepare a slurry. A wide variety of acids may be used in the process herein; suitable acids include hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid or acetic acid and mixtures thereof. It should be noted that the acid is introduced into the process as an aqueous media which comprises a mixture of acid and water, normally in a volume ratio of from about 1:20 to about 20:1. The aqueous media, preferably, maintains the coal slurry pH level at less than 6.0, especially from about 1.0 to about 6.0. Normally, the coal and aqueous media are combined in a weight ratio of from about 1:20 to about 20:1.

The coal slurry, including water and aqueous media, is transferred through lines 7 and 10, using pump 8 or similar device, with hydrogen from line 12, to heating zone 14 where the temperature is increased to 650.degree. F., especially from about 350.degree. F. to about 650.degree. F. Pump 8 is representative of devises normally used to transport the coal slurry through the system herein; it should be noted that pumps, such as pump 8, compressors or blowers, may be strategically placed throughout the system to ensure a smooth flow of components through said system.

Next, the coal slurry, including water, acid and hydrogen, is transported through line 16 to pressurized reaction zone 18, where the pressure is increased up to 4,000 p.s.i.g., preferably from about 100 p.s.i.g. to about 4,000 p.s.i.g., especially from about 500 p.s.i.g. to about 1,500 p.s.i.g., for about 0.5 hour to about 30 hours. Essentially all of the pyritic sulfur is removed from the coal during this stage of the process, however, most of the organic sulfur remains. Additionally, metals such as iron sulfide are reduced by the action of hydrogen and the acid, to hydrogen sulfide, soluble ferrous ions, and possibly elemental iron.

It should be noted that heating zone 14 and pressurized reactor 18 may be either separate units as depicted in the drawing or may be combined as one unit without detrimental effect to the process. In a second mode, water may be introduced into mixing vessel 6 with coal and transported through line 7, pump 8 and line 10, with hydrogen from line 12, to heating zone 14, line 16 and pressurized reactor 18. The coal is, next, washed with an aqueous media, introduced through line 19, which maintains the pH level of this step of the process below 4.0, especially from about 1.0 to about 4.0.

The reactants are transferred through line 20 to high pressure separator 22 where a reactant gas phase, comprising hydrogen and hydrogen sulfide, is separated from the reactant solid and/or liquid phase comprising coal, an aqueous media comprising water and an acid, and metals produced in the reduction of pyritic sulfur. Hydrogen and hydrogen sulfide are transported through line 24 to hydrogen sulfide removal unit 36 where hydrogen sulfide is separated from hydrogen using, for example, a hydrogen sulfide adsorbent such as mono or diethanol amine. Hydrogen sulfide is transported through line 74 to sulfur removal unit 76 where sulfur is recovered, for example, by using the Claus process or some similar procedure. Hydrogen is recirculated through line 38 into line 10 and heating zone 14 and through lines 50 and 52 into heating zone 54.

The coal slurry, including solids and liquids, is transferred from high pressure separator 22 through line 26 to filter zone 28, where coal is separated from metals and aqueous media comprising water and acid. The aqueous media is recirulated through lines 30 and 4 into mixing vessel 6. Make-up aqueous solution is introduced through lines 34, 30 and 4 into vessel 6. Alternatively, the aqueous media may be recirculated to contact the coal after treatment in the pressurized reactor.

Metals are transported through line 32 to metals recovery facilities. Coal is transferred through line 40 into high temperature reactor 42, where hydrogen is introduced through lines 50 and 52 into heating zone 54 where the hydrogen is heated to a temperature above about 800.degree. F. and introduced through line 55 into high temperature reactor 42 where organic sulfur is removed from the coal. It should be noted that heating zone 54 may be either a separate unit as depicted in the drawing or it may be combined as a single unit with high temperature reactor 42.

The reaction temperature is maintained using any suitable heating apparatus, for example, a furnace, electrical heater or the like. The temperature at which the reaction is carried out, normally, is within the range of from about 800.degree. F. to about 1,700.degree. F., especially from about 1,200.degree. F. to about 1,500.degree. F., a pressure of from atmospheric pressure to about 500 p.s.i.g., preferably from atmospheric pressure to about 100 p.s.i.g., for about 0.1 hour to about 50 hours, preferably from about 0.1 hour to about 10 hours. Hydrogen is introduced into the reaction vessel at a minimum rate of 100 volumes of hydrogen per volume of coal per hour, preferably from about 100 to about 5,000 volumes of hydrogen per volume of coal per hour. A substantial amount of the organic sulfur is removed from the coal at this stage of the process. Organic sulfur is converted to hydrogen sulfide which is separated from the coal and transported to sulfur removal apparatus. Low sulfur coal is transported through line 45 to storage facilities.

When water is introduced into the system in the absence of an acid, the water and coal are combined in an amount sufficient to form a coal slurry. Normally, the coal and water are combined in a weight ratio of from about 1:20 to about 20:1.

Alternatively, water may be introduced into mixing vessel 6 with coal and transported through line 7, pump 8 and line 10, with hydrogen from line 12, to heating zone 14, line 16 and pressurized reactor 18. The coal slurry, including solids and water, is transferred from high pressure separator 22 through line 26 to filter zone 28, where coal is separated from metals and water. Coal is transferred through line 40 into high temperature reactor 42, where hydrogen is introduced through lines 50 and 52 into heating zone 54 where the hydrogen is heated to a temperature above about 800.degree. F. and introduced through line 55 into high temperature reactor 42 where organic sulfur is removed from the coal. Next, the coal is washed with an aqueous media, introduced through line 45, which maintains the pH level at this step of the process below 4.0, especially from about 1.0 to about 4.0. Low sulfur coal is transported through line 45 to storage facilities.

Approximately 20 percent to about 45 percent by weight of the coal is converted to volatiles which are readily recoverable as synthetic fuels, including gas and liquid products. Synthetic liquid fuels produced from the coal are primarily aromatic and generally have a boiling range of from about 300.degree. F. to about 1,400.degree. F., a density of about 0.1 to about 1.1 and a carbon to hydrogen molecular ratio in the range of from about 1.3:1 to about 0.66:1. A typical example is a solvent oil obtained from a subbituminous coal such as Wyoming-Montana coal, comprising a middle oil having a boiling range of from about 375.degree. F. to about 675.degree. F. Other products derived from the coal or carbonaceous material include unsaturated hydrocarbons such as the C.sub.2.sup.+ mono olefins, for example, ethylene, propylene, isopropylene, etc., and other light hydrocarbon gases, such as, methane, ethane, propane, etc. The synthetic fuels herein may conveniently be upgraded to suitable fuels using conventional apparatus and techniques in the art.

Volatiles produced in high temperature reactor 42 are transferred through line 44 to separation zone 56 where liquid condensates are separated from gases produced in the process. The liquid condensates are transferred through line 58 to upgrading zone 60, including hydrogen introduced via line 62, where the liquid condensate is upgraded to liquid synthetic fuels. Gas volatiles are transported through line 66 to hydrogen sulfide removal unit 67 where trace amounts of hydrogen sulfide are removed using an adsorbent solution such as an amine compound and transported through lines 78 and 74 to sulfur removal unit 76 where sulfur is recovered. Hydrogen and light hydrocarbon gases are transported through line 69 to gas separation zone 68 where light hydrocarbon gases are separated from hydrogen. Light hydrocarbon gases, for example, methane, ethane, propane, etc. are transported through line 70 to storage facilities. Hydrogen is recirculated into the process through lines 72 and 38 into line 10 and heating zone 14 and through line 38 into lines 50, 52 and heating zone 54.

Volatiles produced in the process may be upgraded into useful synthetic fuels using apparatus and techniques known in the art. For example, volatiles may be transported to a separator unit where light hydrocarbon gases and condensible oils are conveniently recovered using condensation techniques and apparatus commonly used in the industry. Oil produced in the process is transported to an atmospheric distillation tower where low boiling oils are separated from high boiling oils using a standard distillation tower. Light synthetic oils, boiling in the range of 200.degree. F. to 700.degree. F., are transported to a reaction unit where the synthetic oils are contacted with hydrogen and a hydrogenation catalyst at a temperature between about 550.degree. F. and 750.degree. F., at a pressure between about 500 p.s.i.g. and 1,500 p.s.i.g., utilizing a weight hourly space velocity (WHSV) between about 0.25 and about 50 kilograms of synthetic oil per kilogram of catalyst per hour, and added hydrogen in amounts between about 5 and about 1000 cubic meters per barrel of synthetic oil. The exact conditions selected will depend, for example, upon the catalyst used, the particular charge stock to be treated, and the degree of conversion desired. It should be noted, that as low a temperature as possible should be used to limit the number of undesirable side reactions, such as coke formation, which are promoted by high temperatures. The low boiling synthetic oils are primarily converted into gasoline, diesel fuel, turbine fuel, naphtha and light fuel oil.

Any hydrogenation catalyst well known to those having ordinary skill in the art may be employed herein, but preferably, the catalyst comprises at least one hydrogenating component selected from the group consisting of metals, metal sulfides and/or metal oxides of Groups VI and VIII of the Periodic Table. Particularly preferred among the hydrogenating metals are nickel, cobalt, molybdenum and tungsten. The hydrogenating metals are preferably composited with a porous support, for example, alumina or silica-alumina. Additionally, these Group VI and Group VIII catalysts may employ promoters selected from the elements of Groups II and IV of the Periodic Table. The most preferred promoters are Ti, Zr, Sr, Mg, Zn, and Sn. The promoters are employed at levels not in excess of about eight percent by weight of the catalyst used.

Particularly desirable catalysts, suitable for use herein, are set forth in U.S. Pat. Nos. 4,113,605 and 4,094,820, which are directed to carbonates and/or hydroxides of one or more of the Group VIII metals, crystalline cobalt and/or nickel molybdate interreacted with gelatinous boehmite alumina. The resulting catalysts are then extruded, dried, calcined and are found to be very active for desulfurization, denitrogenation and other hydrogenation reactions, for example, upgrading synthetic fuels.

The disclosures of the above-described patents are incorporated herein by reference. The catalysts are used in an amount sufficient to upgrade synthetic oil to useful fuel products.

The higher boiling synthetic oils are distilled under vacuum and the overhead is treated in accordance with the procedure and catalysts described above for the low boiling synthetic oils at a temperature of from about 600.degree. F. to about 800.degree. F. and from about 500 p.s.i.g. to about 3,000 p.s.i.g. The products upgraded at this stage of the process include turbine fuel and feedstock for a hydrocracker, fluid catalytic cracker or coker.

The residual from the vacuum distillation is subjected to a hydrocracking reaction using standard equipment and techniques to produce low sulfur synthetic fuels. Any type reaction vessel may be used in this invention which is normally used in the art.

The invention is further described by the following examples which are illustrative of specific modes of practicing the invention as defined by the appended claims.

Indiana #3 coal is desulfurized and synthetic fuels are produced therefrom according to the procedure described below. The coal is analyzed according to the procedure set forth in ASTM Designations: D-1372-73, D-3176-74 and D-2492-77, the results are disclosed in Table II below: ______________________________________ INDIANA #3 COAL ______________________________________ Moisture-Free Basis Proximate Analysis % by Weight ______________________________________ Ash             17.6 Volatile Carbon 40.8 Fixed Carbon    41.6 ______________________________________ Moisture-Free Analysis Ultimate Analysis % by Weight ______________________________________ Carbon          65.20 Hydrogen        4.90 Nitrogen        1.28 Sulfur          4.32 Ash             17.58 Oxygen          6.72 ______________________________________ Moisture-Free Basis Form of Sulfur  % By Weight ______________________________________ Pyritic         1.88 Organic         2.25 Sulfate         0.20 ______________________________________

A one-liter autoclave is loaded with 400 cc of water, 10 cc of 85 percent phosphoric acid, and 23.18 grams of Indiana #3 coal, which has been pulverized to 60/100 standard mesh. The autoclave is pressurized with hydrogen to 500 p.s.i.g. and heated to a temperature of 550.degree. F. for twelve hours with constant agitation. The maximum pressure reached during this stage of the process is 1,400 p.s.i.g.

Upon opening the autoclave, it is noted that the coal has retained its solid form and is easily separated from the aqueous phase. The coal is analyzed for sulfur content and found to contain 2.09 percent by weight sulfur. To a quartz tube is loaded 5.64 grams of the pretreated coal. Hydrogen is introduced into the quartz tube at a flow rate of 1,500 volumes of hydrogen per volume of coal per hour for two hours at 1,400.degree. F. and atmospheric pressure. The recovered solid (3.43 grams) is free flowing, has a sulfur content of 0.08 percent by weight and a BTU value of 12,800.

Volatile hydrocarbons released during the high temperature reaction of the process amounted to 39.18 percent by weight of the coal or carbonaceous material introduced into the high temperature reactor. The volatile hydrocarbons produced in the quartz tube are first separated into light hydrocarbon gases and liquid synthetic oils using standard condensation apparatus. The hydrocarbon gases contain methane, ethane, propane, etc. The synthetic oils are introduced into a standard atmospheric distillation column where low boiling oils are separated from high boiling oils.

The low boiling oils are introduced into a pressurized reactor and contacted at 650.degree. F. and 500 p.s.i.g. with hydrogen and a hydrogenation catalyst as described above at a weight hourly space velocity of 1.0 kilogram of low boiling synthetic oil per kilogram of catalyst per hour and added hydrogen in an amount of 1,000 cubic meters per cubic meter of oil. Fuels produced from the low boiling oils include gasoline, turbine fuel, diesel fuel and light fuel oil.

High boiling synthetic oils are vacuum distilled in a vacuum distillation tower and the overhead is hydrotreated according to the procedure disclosed for the low boiling synthetic oils to produce heavy fuel oils and feedstock for hydrocrackers, fluid catalytic crackers or cokers. Vacuum distillation residuals are blended to produce low sulfur fuel oil or sent to a coker.

Indiana #3 coal, as described in Example I, is desulfurized and synthetic fuels are produced therefrom by loading a one-liter autoclave with 250 cc of water and 18.56 grams of said coal, which has been pulverized to 60/100 standard mesh. The autoclave is pressurized to 500 p.s.i.g. with hydrogen and heated to 550.degree. F. for six hours with agitation. A maximum pressure of 1,100 p.s.i.g. is recorded during the run and the final pressure is 495 p.s.i.g. Upon opening the autoclave, it is noted that the coal is free flowing and is easily separated from the solution. The coal is washed with 200 cc of 20 percent hydrochloric acid and analyzed for sulfur content. The analysis indicates that the coal contains 2.1 percent by weight of sulfur.

A quartz tube is loaded with 6.40 grams of the recovered coal and heated for two hours in contact with hydrogen at a temperature of 1,400.degree. F. and a hydrogen flow rate of 1,500 volumes of hydrogen per volume of coal per hour at atmospheric pressure. The recovered coal is analyzed for sulfur content and is found to contain 0.5 percent by weight of sulfur and, additionally, has a BTU value of 12,800.

The procedure of Example I is followed to prepare useful low-sulfur fuels from the volatiles (23.43 percent by weight of the original coal).

Indiana #3 coal substantially as described in Example I is desulfurized and synthetic fuels are prepared therefrom according to the below-described procedure.

Into a one-liter autoclave is loaded 400 cc of water and 23.18 grams of coal, which has been pulverized to 60/100 standard mesh. The autoclave is pressurized with hydrogen to 500 p.s.i.g. and heated to 550.degree. F. for twelve hours with constant agitation. It is noted, upon opening the autoclave, that the coal is easily separated from the solution by filtration. Analysis of the coal indicates that it contains 2.62 percent by weight of sulfur.

A quartz tube is loaded with 9.22 grams of the pretreated coal and heated to 1400.degree. F. for two hours in contact with hydrogen at a hydrogen flow rate of 1,500 volumes of hydrogen per volume of coal per hour under atmospheric pressure conditions. The recovered solid (5.61 grams) is free flowing, has a sulfur content of 0.95 percent by weight and a BTU value of 12,800. The recovered coal is washed with 200 cc of 20 percent hydrochloric acid and reanalyzed for sulfur content. The analysis indicates that the coal contains 0.41 percent by weight of sulfur.

The volatiles (39.15 percent by weight) produced in the process are treated in accordance with the procedure of Example I to prepare usable low sulfur synthetic fuels.

Obviously, many modifications and variations of the invention, as hereinabove set forth, can be made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the appended claims.

## Claims

1. A process for sequentially reducing the amount of pyritic, organic and sulfate sulfur in coal and other carbonaceous materials and producing synthetic fuels which comprises (a) forming a slurry by contacting said coal or carbonaceous material with hydrogen and an acidic-aqueous media in an amount sufficient to maintain the pH level below 6.0, at a temperature from about 300.degree. F. to about 650.degree. F. and a pressure from about 100 p.s.i.g., to about 4,000 p.s.i.g., and (b) contacting the coal or carbonaceous material with hydrogen at a temperature from about 800.degree. F. to about 1,700.degree. F., at a minimum hydrogen flow rate of from about 100 to about 5,000 volumes of hydrogen per volume of coal or carbonaceous material per hour.

2. The process according to claim 1 wherein the coal or carbonaceous material in step (a) is first contacted with hydrogen and water; and wherein said coal or carbonaceous material is thereafter contacted with said acidic-aqueous media in an amount sufficient to maintain the pH level below about 4.0.

3. The process according to claims 1 or 2 wherein the acidic aqueous media comprises water and an acid selected from the group consisting essentially of hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid or acetic acid and mixtures thereof.

4. The process of claim 1 wherein the coal or carbonaceous material is contacted with the acidic aqueous media in a weight ratio of from about 1:20 to about 20:1 in step (a).

5. The process according to claim 1 having a pH level of from about 1.0 to about 6.0 in step (a).

6. The process according to claim 1 wherein the coal or carbonaceous material in step (a) is contacted with hydrogen and the acidic aqueous media at a temperature of from about 350.degree. F. to about 650.degree. F. and a pressure of from about 200 p.s.i.g. to about 4,000 p.s.i.g., for about 0.5 hour to about 30 hours.

7. The process according to claim 2 wherein the coal or carbonaceous material in step (a) is first contacted with said hydrogen and said water at a temperature of from about 350.degree. F. to about 650.degree. F. and a pressure of from about 100 p.s.i.g. to about 4,000 p.s.i.g. for about 0.5 hour to about 30 hours.

8. The process according to claim 2 wherein the coal or carbonaceous material is contacted with the acidic-aqueous media in a weight ratio of from about 1:20 to about 20:1.

9. The process according to claim 2 wherein a pH level of from about 1.0 to about 4.0 is maintained.

10. The process according to claim 1 wherein the coal or carbonaceous material in step (b) is contacted with hydrogen at a temperature of from about 800.degree. F. to about 1,700.degree. F., a pressure of from atmospheric pressure to about 500 p.s.i.g., at a hydrogen flow rate of from about 100 to about 5,000 volumes of hydrogen per volume of coal or carbonaceous material per hour, for about 0.1 hour to about 50 hours.

11. The process according to claim 1 including collecting and upgrading the coal or carbonaceous material volatile products to produce synthetic fuels.

12. A process for reducing the amount of pyritic, organic and sulfate sulfur in coal and other carbonaceous materials and producing synthetic fuels which comprises (a) forming a slurry by contacting coal or a carbonaceous material with hydrogen and water at a temperature from about 300.degree. F. to 650.degree. F. and a pressure from about 100 p.s.i.g. to about 4,000 p.s.i.g.; (b) next, contacting the coal or carbonaceous material with hydrogen from about 800.degree. F. to about 1,700.degree. F., at a minimum hydrogen flow rate from about 100 to about 5,000 volumes of hydrogen per volume of coal or carbonaceous material per hour; and (c) thereafter, contacting the coal or carbonaceous material with an acidic-aqueous media in an amount sufficient to maintain the ph level of said slurry below about 4.0.

13. The process of claim 12 wherein the coal or carbonaceous material in step (a) is contacted with hydrogen and water at a temperature of from about 350.degree. F. to about 650.degree. F. and a pressure of from about 200 p.s.i.g. to about 4,000 p.s.i.g. for about 0.5 hour to about 30 hours.

14. The process of claim 12 wherein the coal or carbonaceous material is contacted with water in a weight ratio of from about 1:20 to about 20:1 in step (a).

15. The process of claim 12 wherein the coal or carbonaceous material in step (b) is contacted with hydrogen at a temperature of from about 800.degree. F. to about 1,700.degree. F., a pressure of from atmospheric pressure to about 500 p.s.i.g., at a hydrogen flow rate of from about 100 to about 5,000 volumes of hydrogen per volume of coal or carbonaceous material per hour, for about 0.1 hour to about 50 hours.

16. The process of claim 12 wherein the acidic aqueous media in step (c) comprises water and an acid selected from the group consisting essentially of hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid or acetic acid and mixtures thereof.

17. The process of claim 16 wherein the coal or carbonaceous material is contacted with the aqueous media in a weight ratio of from about 1:20 to about 20:1 in step (c).

18. The process of claim 17 having a pH level of from about 1.0 to about 4.0 in step (c).

19. The process of claim 17 including collecting and upgrading the coal or carbonaceous material volatile products to produce synthetic fuels.