US3808119A - Process for refining carbonaceous fuels - Google Patents
Process for refining carbonaceous fuels Download PDFInfo
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- US3808119A US3808119A US00297093A US29709372A US3808119A US 3808119 A US3808119 A US 3808119A US 00297093 A US00297093 A US 00297093A US 29709372 A US29709372 A US 29709372A US 3808119 A US3808119 A US 3808119A
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- carbonaceous
- hydrogen
- fuel
- solvent
- carbon monoxide
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/001—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by thermal treatment
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
- C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation in the presence of a solvent
Definitions
- the solvation be effected within a relatively narrow range of temperatures and pressures and that the period of time at which the carbonaceous material is in contact with the solvent at elevated temperatures and pressures be limited within a relatively narrow range.
- the carbonaceous material to be treated by the method of this invention will be ground and slurried with the solvent prior to treatment.
- the aromatic solvent employed be derived from a carbonaceous material having the same or substantially the same composition as that being treated. Production of a low-ash, lowoxygen, low-sulfur carbonaceous fuel by the method of the present invention results in higher yields of the more valuable products and in products having higher hydrogen contents than when hydrogen alone is present during the solvation step.
- This invention relates to an improved method for refining carbonaceous fuels. More particularly, this invention relates to an improved solvation process for refining carbonaceous fuels.
- a lowash, low-oxygen, low-sulfur carbonaceous fuel is obtained in combination with both liquid and gas by-products by dissolving a substantial portion of the available fraction of a naturally occurring carbonaceous fuel in a suitable solvent.
- the solvent will be derived from the original fuel feed stock.
- the hydrogen content of the liquid product from this process is generally low and it is sometimes necessary or desirable to further hydrogenate this product so as to enhance both its usefulness and value.
- the relatively high yields of gas product when compared to the yield of liquid product detract from the economic attractiveness of the process.
- the total yield of useful product which is, generally, economically acceptable with all feed stocks, is undesirably low with certain feed stocks such as the lignites and subbituminous coals.
- the foregoing and other objects and advantages are accomplished by dissolving all or a substantial portion of the potentially available fuel fraction of a naturaly occurring carbonaceous fuel in a suitable solvent and in the presence of both carbon monoxide and steam or carbon monoxide, steam and hydrogen, then separating the undissolved portion of the carbonaceous fuel from the solution, and thereafter recovering a low-ash, low-oxygen, low-sulfur solid, carbonaceous fuel from the solvent.
- the liquid and gas products will be obtained by flashing and/ or fractionation of the liquid media from the solvation step.
- FIG. 1 is a schematic flow diagram of a process within the scope of the present invention wherein the refining of a carbonaceous fuel is effected continuously.
- the present invention relates to an improved process for refining or upgrading naturally occurring carbonaceous fuels.
- the refining or upgrading is effected by first dissolving so much of the available fuel portion of the carbonaceous material as is consistent with good operation in a suitable solvent.
- the refined or upgraded carbonaceous fuel is then recovered by first separating the ash portion (undissolved portion) of the carbonaceous feed material and thereafter separating the dissolved fuel fraction from'the solvent and any liquid and gas by-products produced during the dissolving step.
- any carbonaceous fuel may be refined or upgraded to a low-ash, low-oxygen, low-sulfur fuel by the method of the present invention.
- the process is, however, most suitable for the upgrading of naturally occurring canbonaceous fuels such as bituminous and subbituminous coals and lignites.
- the carbonaceous material may be treated by the method of the present invention in essentially any shape or size.
- the carbonaceous material will be most easily handled and most readily dissolved when the same is in a relatively small particle size.
- it is, generally, advantageous to grind or otherwise pulverize the coal such that 100 percent will pass through a mesh screen (U.S. Standard) and such that at least 50 wt. percent will pass through a 40 mesh screen (U.S. Standard).
- the particle size of the carbonaceous material treated in accordance with the method of the present invention will range between about 0.006 and 0.008 inch in diameter.
- any of the solvents known in the prior art to be useful for the purpose of dissolving the available fuel portion of a carbonaceous material may be used in the method of the present invention.
- Suitable solvents include the highly hydrogenated aromatic materials, generally, boiling within a range of about 200 to about 900 F. such as anthracene oil or creosote oil.
- a particularly preferred solvent is one obtained by the extraction of the carbonaceous fuel itself.
- a liqu d y-p' is obtained as a result of dissolving the carbonaceous feed material and a portion of this liquid material is suitable for use as a solvent therein.
- a sufi'icient quantity of such a solvent will be produced during the extraction to satisfy the process needs therefor in either a batch or continuous operation.
- the composition of the solvent thus produced will vary with the particular carbonaceous feed material but that portion of the liquid by-product having an initial boiling point within the range of about F. to about 700 F. and a final boiling point within the range of about 700 F. to about 1100 F., a density of about 1.1 and a carbon to hydrogen ratio in the range of about 1.0209 to about 10:03 will be satisfactory for use in the method of the present invention.
- the ratio of hydrocarbon solvent to the carbonaceous material being treated be at least 05:1 and ratios of hydrocarbon solvent to dry carbonaceous material within the range of about 0.5:1 to about 5:1 will be operable in the method of the present invention. Higher ratios will, of course, also be operable but such higher ratios provide no functional advantage in the process of the present invention. Moreover, the use of such higher ratios will require additional energy or work for the subsequent separation of solvent from the upgraded carbonaceous product and for recycling in the system. Lower ratios within the broad range are, therefore, preferred.
- the fuel fraction of the carbonaceous material being treated by the method of the present invention will be dissolved at a temperature sufficiently high to facilitate the solvation but not so high as to cause excessive decomposition of the fuel fraction, which is sought to be recovered, or the solvent employed in the extraction or solvation step.
- Temperatures within the range of about 700 to about 950 F. have been found suitable for use in the present invention. In this regard, it should be noted that the rate of solvation below about 700 F. is too slow to permit reasonable recovery of the available fuel fraction. At temperatures above about 950 F., on the other hand, decomposition of the desired products and the solvent become excessive. As will be readily apparent, from the standpoint of economics, the use of the lower temperatures within this range which are consistent with good yields is most desirable.
- the solvation of the available fuel fraction of the carbonaceous material is accomplished at an elevated temperature and in the presence of hydrocarbon materials having a boiling point below these temperatures, it is essential that the extraction or solvation step be accomplished at an elevated pressure. Moreover, since elevated pressure enhances the solvation of the available fuel fraction of the carbonaceous material, it is most desirable to effect the solvation at elevated pressures. In general, pressures within the range of about 500 to about 5000 p.s.i.g. will be effective. In this regard, it should be noted that at pressures below about 500 p.s.i.g., the yield of deashed carbonaceous fuel is unreasonably low.
- the essence of the present invention resides in the discovery of unexpected advantages which are realized when part or all of the available fuel fraction of the carbonaceous material is dissolved in an atmosphere containing both carbon monoxide and steam.
- these advantages will be realized when carbon monoxide is present in an amount ranging between about 1.5 and 40 s.c.f. of CO per pound of dry coal in combination with steam within the range of about 0.2 to 1.5 pounds per pound of dry coal.
- carbon monoxide and steam be the only gaseous components present in the gas phase during the extraction or dissolving step and, in fact, it has been found beneficial in many cases to also have hydrogen available in the gas phase.
- the ratio of hydrogen plus carbon monoxide to dry carbonaceous feed material will range between about 1.5 and 40 s.c.f. per pound of said carbonaceous material and the ratio of steam and/or water to dry carbonaceous material will range from about 0.2:1 to 1.5 :1 on a weight basis.
- the ratio of hydrogen to carbon monoxide will range between about 0.1:1 to 10.011.
- the length of time during which the solvent and carbonaceous fuel will be contacted at the process temperature will vary between about 3 and 180 minutes.
- the optimum holding time for each carbonaceous material will, however, vary with each such material.
- the viscosity of the solu tion obtained during processing of the carbonaceous material will, initially, increase with time, then decrease and then increase again as the holding time is extended.
- separation of the undissolved portion of the carbonaceous material from the solution and the recovery of the dissolved fuel portion from the solution will be most readily accomplished when the viscosity of the mixture from the reactor is at a reasonably low value.
- the viscosity of the solution in the dissolver can be used to provide an accurate guide to determine the optimum holding time in the extraction or solvation step and that this may conveniently be accomplished by reference to the relative viscosity of the solution formed in the dissolver.
- the relative viscosity here referred to is the ratio of the viscosity of the solution in the dissolver to the viscosity of the solvent used therein.
- the relative viscosity will reduce to a value below 10, and, generally, to a value well below 5 before the same again begins to increase.
- mixtures from the dissolver having relative viscosities less than 10 can be processed by the method of the present invention and a low-ash, low-oxygen, lowsulfur carbonaceous fuel recovered therefrom.
- the extraction or solvation will, therefore, be continued at least until the relative viscosity of the solution from the dissolver is less than 10 but the same will be discontinued before the relative viscosity has passed through its minimum and then increased to a value of 10 or more.
- the extraction or solvation step will be continued until the relative viscosity of the solution in the dissolver has reached a value of 5 or less but will be discontinued before the relative viscosity has increased back to a corresponding value of 5. In a most preferred embodiment, the extraction or solvation step will be discontinued when the relative viscosity has reached a value of about 1.5 to 2.
- the solvation of the available fuel portion of the carbonaceous material being treated is effected via a depolymerization of the relatively high molecular weight components thereof, "and that when this depolymerization in accomplished in the presence of a hydrogen ion donor the free radicals thus formed are neutralized by the hydrogen ions, thereby preventing repolymerization of the free radicals.
- the neutralized free radicals, as well as any other decomposition products, are then soluble in the solvent and may be subsequently recovered by flashing or otherwise separating the solvent therefrom.
- materials other than those which are soluble in the solvent are either formed or liberated.
- Such materials include hydrogen sulfide, carbon dioxide, methane, propane, butane, and other higher hydrocarbons and these materials will comprise part of the atmosphere in the dissolver. Generally, however, their presence therein will not adversely affect the extraction or solvation of the carbonaceous material. Care should, however, be exercised so as to prevent a buildup of these materials to the extent that the partial pressures of carbon monoxide and steam (and hydrogen, when used) are reduced to inoperable values. In this regard, it should be noted that these materials may be separated from any recycled gas by conventional means.
- hydrogen is consumed by the extracted or dissolved portion of the carbonaceous material in an amount rang ing between about 0.5 and 4.0 wt. percent of the initial dry coal feed and this amount should be made up if the gas phase is recycled and the presence of hydrogen desired initially.
- about 5 to about 50 mol percent of the carbon monoxide and steam will be converted to hydrogen during the extraction or solvation step and this amount, too, should be made up if gas recycle is employed.
- the upgraded, low-ash, low-oxygen, low-sulfur carbonaceous fuel can then be recovered from solution.
- this recovery will involve: the separation of the undissolved portion of the carbonaceous feed material from the solution; the separation of the carbon monoxide, steam and hydrogen, as well as any other gaseous components present in the system, from the solution; the separation of the low-ash, low-oxygen, low-sulfur carbonaceous fuel from the solvent; and the separation of any gas and liquid by-products from the solvent.
- any suitable means such as filtration and centrifugation, can be employed to effect the separation of the undissolved portion of the carbonaceous feed from the solution.
- it will, generally, be desirable to subject the recovered solids to a drying step so as to recover entrained solvent therefrom.
- the dried solids from a centrifugal separation and/or the dried filter cake from a filter will have a definite fuel value with fuel ratings running as high as 7000 B.t.u./lb.
- the gaseous components may be separated from the slurry containing the undissolved portion of the carbonaceous feed material either prior to or simultaneously with the separation of the solid material. After separation, the gases may then be subjected to any subsequent treatment, such as scrubbing to remove acid gas components, and then recycled or used for other purposes, as desired.
- any subsequent treatment such as scrubbing to remove acid gas components, and then recycled or used for other purposes, as desired.
- gas recycle a buildup in hydrogen gas will, often, occur, initially, due to the formation thereof through the reaction of carbon monoxide with steam. This inital buildup is not, however, detrimental and, at steady-state operation, within the operating ranges heretofore set forth, the concentration of carbon monoxide and steam in the dissolver can easily be maintained within the operable limits set forth, supra.
- the low-ash, lowoxygen, low-sulfur carbonaceous fuel may then be recovered therefrom with any suitable means such as by vacuum distillation or flash evaporation.
- any suitable means such as by vacuum distillation or flash evaporation.
- the solvent and other lower boiling liquids therein will be separated by exposure to temperatures just slightly above the boiling point of the highest boiling component thereof.
- the upgraded, low-ash, low-oxygen, low-sulfur carbonaceous fuel may be recovered as either a liquid or a solid, depending upon the particular method used to separate the same from the solvent, and the same may be used in either form. Moreover, when the upgraded fuel is recovered as a liquid, the same may be solidified simply by cooling.
- the method of the present invention offers several advantages over prior art processes wherein hydrogen alone is used to supply the hydrogen required during the extraction or solvation step.
- the advantages oifered do, however, vary with the particular carbonaceous material subjected to treatment.
- bituminous coal is upgraded by the method of the present invention
- the yield of all products (gas, liquid and upgraded fuel) from the feed is, often, substantially identical to that obtained through the use of hydrogen alone. Separation of the undissolved portion of the carbonaceous feed material from the solution is, however, significantly enhanced, and as a result, smaller filtration equipment is required to effect the desired separation.
- bituminous coal when bituminous coal is treated by the method of this invention, the yield of the more valuable liquid by-product is, generally, increased with a corresponding decrease in the less valuable gas by-product and the hydrogen content of all products is, surprisingly, higher.
- subbituminous coal when subbituminous coal, on the other hand, is treated by the method of this invention, the advantages noted above and associated with the treatment of bituminous coal are again generally realized. In addition, the total yield of the more valuable products is significantly increased over the full range of operating conditions normally employed.
- lignite when lignite is treated by the method of this invention, all of the advantages derived in the treatment of subbituminous ooal are, generally, realized and an upgraded fuel containing less sulfur is, generally, obtained.
- FIG. 1 there is shown a schematic flow diagram of one embodiment of the present invention wherein a carbonaceous feed material is upgraded in a continuous process.
- a finely ground carbonaceous feed material is fed to mixer or slurry tank 1 through line 2 where the same is slurried with a suitable solvent therefor.
- the solvent enters through line 3.
- the carbonaceous material After the carbonaceous material has been slurried, the same is withdrawn from the slurry tank through line 4 and passed through preheater 5 and into dissolver 6 through line 7.
- the slurry is heated to the desired solvation temperature and then held in the dissolver until the desired portion of the available fuel fraction of the carbonaceous material has been dissolved therein.
- the solvation be accomplished in an atmosphere comprising carbon monoxide and steam and it is important that the carbonaceous material be in contact with these components at all times during which the same is exposed to elevated temperatures. For this reason, then, it is important that the slurry be mixed with the desired gas prior to passing the same through the preheater 5.
- the desired gas feed is brought in through line 8 and mixed with the slurry in line 4.
- the gas fed to the preheater may be pure carbon monoxide, when there is suflicient water in the coal to provide the required steam or when sulficient water is added thereto, or the same may be a mixture of carbon monoxide and steam or a mixture of carbon monoxide, steam and hydrogen. It will, of course, be appreciated that other gaseous components could be present in the gas feed and this will, generally, be the case when recycle gas is employed or when impure sources of the gas are used.
- the solution containing any undissolved portion of the carbonaceous feed material is withdrawn from the dissolver through line 9 and passed to filter 10.
- the filter cake may then be processed by any suitable method for the purpose of recovering absorbed solvent or other materials.
- the same may be passed through a rotary drum drier 17 and then withdrawn from the process through line 18.
- the solvent or other recovered material may then be recovered through line 19 and either recycled to the slurry tank or withdrawn from the process as desired.
- the solution containing the dissolved fuel fraction of the carbonaceous feed material is withdrawn from the filter through line 20 and passed through a second preheater 21. In the preheater, the solution is heated to a temperature suitable for vacuum flash separation and is then withdrawn through line 22 and passed to vacuum flash vessel 23.
- the vacuum flash vessel may, of course, be heated as required.
- the solvent and any other liquid materials will be flashed and will pass overhead through line 24.
- the overhead product may then be subjected to distillation in distillation column 25.
- any number of products may then be recovered from the distillation column.
- the recovered solvent is withdrawn through line 26 and may be recycled to the slurry tank through line 3.
- the lighter liquid materials will pass overhead through line 28 and may be withdrawn from the process through this line.
- the upgraded, low-ash, lowoxygen, low-sulfur product will be withdrawn from the vacuum flash vessel as a liquid through line 29.
- the liquid product may then be cooled and solidified and withdrawn from the process by any suitable means such as watercooled conveyor 30.
- the method of the present invention will be employed to upgrade a carbonaceous material selected from the group consisting of the lignites, the subbituminous coals and the bituminous coals and the upgrading will be effected continuously.
- the carbonaceous feed material will first be ground such that approximately 80% thereof will pass through a 200 mesh (U.S. Standard) screen and then slurried with a solvent derived from the carbonaceous material and having an initial boiling point within the range of about 400 to about 600 F. and a final point within the range of about 800 to about 1000 F.
- the ratio of solvent to dry coal in the feed slurry will range from about 1.0:1 to about 25:1.
- the slurry will then be mixed with a gaseous mixture comprising both hydrogen and carbon monoxide.
- a gaseous mixture comprising both hydrogen and carbon monoxide.
- from about -00 to about 5000 standard cubic feet of these gases will be added per barrel of slurry.
- Steam will also be added to the slurry, when required, such that the ratio of water to dry coal ranges between about 0.5:1 to about 1:1.
- the ratio of hydrogen to carbon monoxide will be within the range of about 0.321 to 4:1.
- the slurry will then be heated to a solvation temperature within the range of about 775 to about 875 F. and the solvation will be effected at a pressure within the range of about 1000 to 2500 p.s.i.g.
- the liquid space velocity in the reaction zone will be within the range of about 0.5 to about 3.0.
- Example 1 In this example, a Kentucky No. 11 bituminous coal was ground such that wt. percent thereof passed through a 100 mesh (U.S. Standard) screen and then slurried with amixture of water and a highly aromatic solvent. The solvent to dry coal ratio in the slurry was 2 to 1. The ratio of water to dry coal was 0.25 to 1. The slurry was heated in an atmosphere comprising 50 mol percent carbon monoxide and 50 mol percent hydrogen at an initial pressure of 1500 p.s.i.g. and held at these conditions for 30 minutes (at 425 C., the autogenous produced pressure was 3800 p.s.i.g.).
- Example 2 The run of Example 1 was repeated except that the ground Kentucky No. 11 bituminous coal was heated to a temperature of 425 C. in an atmosphere of pure hydrogen and held for 30 minutes.
- the initial pressure was 1500 of the carbonaceous feed material was dissolved and an upgraded carbonaceous fuel was obtained in a yield of 48.3 wt. percent based on the initial coal feed.
- a liquid product having a boiling range between 100 and 800 F. was obtained in a yield of only 18 wt. percent based on initial coal feed while a gas product containing C -C hydrocarbons was obtained in a yield of 9 wt. percent.
- the hydrogen to carbon ratio in the upgraded fuel was only 0.60:1, while that of the liquid product was 0.82:1.
- separation of the undissolved portion of the carbonaceous feed material from the solution took 4 hours for the same volume in the same laboratory filtration apparatus under identical conditions.
- Example 3 In this example, a Kentucky No. 9 bituminous coal containing 3.58 wt. percent sulfur was ground to a particle size such that 100 wt. percent passed through a 100 mesh (U.S. Standard) screen and then slurried in a highly aromatic solvent having an initial boiling point of 550 F. and a final boiling point of 800 F. The ratio of solvent to available fuel fraction in the carbonaceous feed material was 2.4 to 1. The slurry was then processed in a continuous flow unit at a temperature of 425 C. in an atmosphere containing steam, carbon monoxide and hydrogen at a pressure of 1000 p.s.i.g.
- the hourly liquid space velocity in the reaction zone was 0.8 while the hourly gas space velocity (STP) was 225.
- the weight ratio of steam to coal in the available fuel fraction was 0.3 to 1 and the mol ratio of hydrogen to carbon monoxide in the atmosphere was 1 to 1.
- 87% of the available fuel fraction of the Kentucky No. 9 coal was dissolved in the highly aromatic solvent and an upgraded carbonaceous fuel was obtained in a yield of 54.8 wt. percent based on initial coal feed.
- the sulfur content of the upgraded fuel was 0.8 wt. percent.
- Example 4 The run of Example 3 was repeated except that the sol vation of the available fuel fraction in the carbonaceous feed material was accomplished in an atmosphere of pure hydrogen. In this run, 90% of the available fuel fraction was dissolved in the aromatic solvent and an upgraded carbonaceous fuel was obtained in a yield of 47.1 wt. percent based on initial coal feed. The sulfur content of this product was, however, 1.02 wt. percent.
- Example 5 In this example, a Big Horn, Wyoming subbituminous coal was ground to a particle siZe such that 100 wt. per cent passed through a 65 mesh (U.S. Standard) screen and then slurried in a mixture of water and a highly aromatic solvent having an initial boiling point of 550 F. and a final boiling point of 800 F.
- the solvent to dry coal ratio in the slurry was 2 to 1.
- the water to dry coal weight ratio in the slurry was 0.4 to 1.
- the slurry was then heated to 400 C. in an atmosphere containing 50 mol percent carbon monoxide and 50 mol percent hydrogen and held for 30 minutes.
- the initial pressure in the reactor was 1500 p.s.i.g.
- Example 6 The run of Example 5 was repeated except that the solvation was accomplished at a temperature of 450 C. in an atmosphere of pure hydrogen and the solvation step was allowed to continue for 94 minutes. In this run, only 60% of the available fuel fraction of the Big Horn, Wyoming subbituminous coal dissolved in the solvent and an upgraded carbonaceous fuel was recovered in a yield of only 34.7 wt. percent based on initial coal feed. Moreover, the yield of total liquid product was less than 1 wt. percent based on initial coal feed.
- Example 7 Elkol, Wyoming subbituminous coal was ground to a particle size such that 100 wt. percent passed through a 65 mesh (U.S. Standard) screen and then slurried in a mixture of water and a highly aromatic solvent having an initial boiling point of 550 F. and a final boiling point of 800 F.
- the solvent to dry coal ratio in the slurry was 2 to 1 on a weight basis.
- the water to dry coal ratio was 0.4 to l on a weight basis.
- the slurry was then heated to 400 C. in an atmosphere comprising 50 mol percent carbon monoxide and 50 mol percent hydrogen and held at these conditions for 30 minutes.
- the initial pressure in the dissolver was 1500 p.s.i.g.
- Example 8 The run of Example 7 was repeated except that the solvation was accomplished in an atmosphere of pure hydrogen and at a temperature of 425 C. In this run, only 73% of the available fuel fraction of the carbonaceous feed material was dissolved in the highly aromatic solvent. Moreover, the yield of upgraded carbonaceous fuel was only 53 wt. percent based on initial coal feed while that of the liquid product was less than 1 wt. percent based on initial coal feed.
- Example 9 In this example, a Beulah lignite was ground to a particle size such that 100 wt. percent passed through a 65 mesh (U.S. Standard) screen and then slurried with a mixture of water and a highly aromatic solvent having an initial boiling point of 550 F. and a final boiling point of 800 F.
- the solvent to dry coal ratio in the slurry was 2 to l on a weight basis, and the water to dry coal ratio was 1 to l on a weight basis.
- the slurry was then heated to a temperature of 410 C. in an atmosphere of pure carbon monoxide and held at these conditions for 10 minutes.
- the initial pressure in the dissolver was 1000 p.s.i.g.
- Example 10 The run of Example 9 was repeated except that the solvation was accomplished at a temperature of 425 C.
- Example 11 In this example, a Baukol-Noonan lignite containing 31 wt. percent water was ground to a particle sizesuch that 100 wt. percent thereof passed through a 65 mesh (US. Standard) screen and then slurried with a highly aromatic solvent having an initial boiling point of 550 F. and a final boiling point of 800 F. The slurry was then mixed with a gas stream consisting of pure carbon monoxide and heated to a temperature of 425 C. for 30 minutes. Sufiicient gas was added to make the initial pressure in the dissolver 1000 p.s.i.g. During the 30 minute holding time, more than 90% of the available fuel fraction of the Baukol-Noonan lignite feed was dissolved in the solvent.
- the undissolved portion of the carbonaceous feed material was separated from the solution by filtration.
- An upgraded carbonaceous fuel was then recovered by vacuum distillation to remove the solvent and other liquids associated therewith.
- the upgraded carbonaceous fuel was recovered in a yield of 31.8 wt. percent based on dry coal feed.
- a liquid product having an initial boiling point of 100 F. and a final boiling point of 800 F. was obtained in a yield of 32.8 wt. percent based on initial coal feed and a gas product containing C C hydrocarbons was obtained in a 7 wt. percent yield based on feed coal.
- Example 12 The run of Example 1 was repeated except that the slurry was mixed with a gas stream comprising 50 mol percent hydrogen and 50 mol percent carbon monoxide. In this run, again more than 90% of the available fuel fraction in the lignite feed was dissolved in the highly aromatic solvent. Moreover, the yield of upgraded carbonaceous fuel, liquid by-product and gas by-product were substantially identical with those of the previous run and the hydrogen to carbon ratios were not significantly changed. The ash content of the upgraded carbonaceous fuel was, however, significantly lower; viz., 0.12 wt. percent versus 0.45 wt. percent.
- Example 13 The run of Example 11 was again repeated except that the slurry was mixed with a gas stream comprising pure hydrogen rather than pure carbon monoxide. In this run, only 59% of the available fuel fraction of the lignite feed was dissolved in the aromatic solvent and the yield of all products was significantly reduced and the hydrogen content thereof was significantly lower. Moreover, the undissolved portion of the lignite feed was separated from the solution at a much slower rate. 1
- the ratio of solvent to dry coal is within the range of about 0.5 to 1 to'about 5 to 1 5.
- said solvent has an initial boiling point within the range of about to about 700 F. and a final boiling point within the range from about 700 F. to about 1100 F.
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Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00297093A US3808119A (en) | 1972-10-12 | 1972-10-12 | Process for refining carbonaceous fuels |
CA169,473A CA990675A (en) | 1972-10-12 | 1973-04-17 | Process for refining carbonaceous fuels |
ZA733362A ZA733362B (en) | 1972-10-12 | 1973-05-18 | Improved process for refining carbonaceous fuels |
AU56002/73A AU466761B2 (en) | 1972-10-12 | 1973-05-23 | Improved process for refining carbonaceous fuels |
DE2326707A DE2326707A1 (de) | 1972-10-12 | 1973-05-25 | Verfahren zur herstellung von vergueteten, praktisch aschefreien, sauerstoffarmen und schwefelarmen kohlenstoffhaltigen brennstoffen |
JP5785573A JPS5438601B2 (zh) | 1972-10-12 | 1973-05-25 | |
KR7300855A KR780000159B1 (en) | 1972-10-12 | 1973-05-28 | Process for refining carbonaceous fuels |
IN826/CAL/74A IN139155B (zh) | 1972-10-12 | 1974-04-11 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00297093A US3808119A (en) | 1972-10-12 | 1972-10-12 | Process for refining carbonaceous fuels |
Publications (1)
Publication Number | Publication Date |
---|---|
US3808119A true US3808119A (en) | 1974-04-30 |
Family
ID=23144833
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00297093A Expired - Lifetime US3808119A (en) | 1972-10-12 | 1972-10-12 | Process for refining carbonaceous fuels |
Country Status (8)
Country | Link |
---|---|
US (1) | US3808119A (zh) |
JP (1) | JPS5438601B2 (zh) |
KR (1) | KR780000159B1 (zh) |
AU (1) | AU466761B2 (zh) |
CA (1) | CA990675A (zh) |
DE (1) | DE2326707A1 (zh) |
IN (1) | IN139155B (zh) |
ZA (1) | ZA733362B (zh) |
Cited By (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3850738A (en) * | 1973-12-06 | 1974-11-26 | Bechtel Int Corp | Bituminous coal liquefaction process |
US3884794A (en) * | 1974-03-04 | 1975-05-20 | Us Interior | Solvent refined coal process including recycle of coal minerals |
US3884795A (en) * | 1974-03-04 | 1975-05-20 | Us Interior | Solvent refined coal process with zones of increasing hydrogen pressure |
US3884796A (en) * | 1974-03-04 | 1975-05-20 | Us Interior | Solvent refined coal process with retention of coal minerals |
US3892654A (en) * | 1974-03-04 | 1975-07-01 | Us Interior | Dual temperature coal solvation process |
US3954595A (en) * | 1974-03-18 | 1976-05-04 | The Lummus Company | Coal liquefaction |
US3997424A (en) * | 1973-11-27 | 1976-12-14 | Coal Industry (Patents) Limited | Hydrogenative treatment of coal |
US4011153A (en) * | 1975-04-01 | 1977-03-08 | The United States Of America As Represented By The United States Energy Research And Development Administration | Liquefaction and desulfurization of coal using synthesis gas |
US4128471A (en) * | 1976-11-30 | 1978-12-05 | Gulf Research & Development Company | Coal liquefaction process employing carbon monoxide |
US4144033A (en) * | 1976-09-20 | 1979-03-13 | Kobe Steel, Ltd. | Process for manufacturing metallurgical cabonaceous materials from coals |
US4146459A (en) * | 1976-09-08 | 1979-03-27 | Continental Oil Company | Treatment of coal liquefaction effluent |
US4157305A (en) * | 1975-06-20 | 1979-06-05 | Chemap Ag | Method of filtering molten coal |
US4242102A (en) * | 1978-12-15 | 1980-12-30 | The Lummus Company | Production of gasified products from ash containing bitumen produced in coal liquefaction |
US4332667A (en) * | 1978-07-10 | 1982-06-01 | Exxon Research & Engineering Co. | Liquefaction process for solid carbonaceous materials containing alkaline earth metal humates |
US4425219A (en) | 1981-07-31 | 1984-01-10 | Tatabanyai Szenbanyak | Method for the production of liquid carbon compounds from coal |
US4448665A (en) * | 1982-12-30 | 1984-05-15 | Exxon Research And Engineering Co. | Use of ammonia to reduce the viscosity of bottoms streams produced in hydroconversion processes |
US4778585A (en) * | 1983-07-14 | 1988-10-18 | Research Foundation Of The City Univ. Of Ny | Two-stage pyrolysis of coal for producing liquid hydrocarbon fuels |
US5026475A (en) * | 1989-12-21 | 1991-06-25 | Exxon Research & Engineering Company | Coal hydroconversion process comprising solvent extraction (OP-3472) |
US5071540A (en) * | 1989-12-21 | 1991-12-10 | Exxon Research & Engineering Company | Coal hydroconversion process comprising solvent extraction and combined hydroconversion and upgrading |
US5110450A (en) * | 1989-12-21 | 1992-05-05 | Exxon Research And Engineering Company | Coal extract hydroconversion process comprising solvent enhanced carbon monoxide pretreatment |
US5151173A (en) * | 1989-12-21 | 1992-09-29 | Exxon Research And Engineering Company | Conversion of coal with promoted carbon monoxide pretreatment |
US5336395A (en) * | 1989-12-21 | 1994-08-09 | Exxon Research And Engineering Company | Liquefaction of coal with aqueous carbon monoxide pretreatment |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5344184B2 (zh) * | 1974-10-16 | 1978-11-27 | ||
GB1490078A (en) * | 1974-11-19 | 1977-10-26 | Coal Ind | Gas extraction of coal |
JPS56501205A (zh) * | 1979-09-27 | 1981-08-27 | ||
JPS633094A (ja) * | 1986-06-23 | 1988-01-08 | Ube Ind Ltd | アッシュスラリ−からの熱の回収方法 |
JP2013006907A (ja) * | 2011-06-22 | 2013-01-10 | Kobe Steel Ltd | 無灰炭製造方法 |
CN107207967A (zh) * | 2014-12-05 | 2017-09-26 | 株式会社Posco | 炼焦添加剂制造方法及制造装置 |
-
1972
- 1972-10-12 US US00297093A patent/US3808119A/en not_active Expired - Lifetime
-
1973
- 1973-04-17 CA CA169,473A patent/CA990675A/en not_active Expired
- 1973-05-18 ZA ZA733362A patent/ZA733362B/xx unknown
- 1973-05-23 AU AU56002/73A patent/AU466761B2/en not_active Expired
- 1973-05-25 DE DE2326707A patent/DE2326707A1/de not_active Ceased
- 1973-05-25 JP JP5785573A patent/JPS5438601B2/ja not_active Expired
- 1973-05-28 KR KR7300855A patent/KR780000159B1/ko active
-
1974
- 1974-04-11 IN IN826/CAL/74A patent/IN139155B/en unknown
Cited By (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3997424A (en) * | 1973-11-27 | 1976-12-14 | Coal Industry (Patents) Limited | Hydrogenative treatment of coal |
US3850738A (en) * | 1973-12-06 | 1974-11-26 | Bechtel Int Corp | Bituminous coal liquefaction process |
US3884794A (en) * | 1974-03-04 | 1975-05-20 | Us Interior | Solvent refined coal process including recycle of coal minerals |
US3884795A (en) * | 1974-03-04 | 1975-05-20 | Us Interior | Solvent refined coal process with zones of increasing hydrogen pressure |
US3884796A (en) * | 1974-03-04 | 1975-05-20 | Us Interior | Solvent refined coal process with retention of coal minerals |
US3892654A (en) * | 1974-03-04 | 1975-07-01 | Us Interior | Dual temperature coal solvation process |
US3954595A (en) * | 1974-03-18 | 1976-05-04 | The Lummus Company | Coal liquefaction |
US4011153A (en) * | 1975-04-01 | 1977-03-08 | The United States Of America As Represented By The United States Energy Research And Development Administration | Liquefaction and desulfurization of coal using synthesis gas |
US4157305A (en) * | 1975-06-20 | 1979-06-05 | Chemap Ag | Method of filtering molten coal |
US4146459A (en) * | 1976-09-08 | 1979-03-27 | Continental Oil Company | Treatment of coal liquefaction effluent |
US4144033A (en) * | 1976-09-20 | 1979-03-13 | Kobe Steel, Ltd. | Process for manufacturing metallurgical cabonaceous materials from coals |
US4128471A (en) * | 1976-11-30 | 1978-12-05 | Gulf Research & Development Company | Coal liquefaction process employing carbon monoxide |
US4332667A (en) * | 1978-07-10 | 1982-06-01 | Exxon Research & Engineering Co. | Liquefaction process for solid carbonaceous materials containing alkaline earth metal humates |
US4242102A (en) * | 1978-12-15 | 1980-12-30 | The Lummus Company | Production of gasified products from ash containing bitumen produced in coal liquefaction |
US4425219A (en) | 1981-07-31 | 1984-01-10 | Tatabanyai Szenbanyak | Method for the production of liquid carbon compounds from coal |
US4448665A (en) * | 1982-12-30 | 1984-05-15 | Exxon Research And Engineering Co. | Use of ammonia to reduce the viscosity of bottoms streams produced in hydroconversion processes |
US4778585A (en) * | 1983-07-14 | 1988-10-18 | Research Foundation Of The City Univ. Of Ny | Two-stage pyrolysis of coal for producing liquid hydrocarbon fuels |
US5026475A (en) * | 1989-12-21 | 1991-06-25 | Exxon Research & Engineering Company | Coal hydroconversion process comprising solvent extraction (OP-3472) |
US5071540A (en) * | 1989-12-21 | 1991-12-10 | Exxon Research & Engineering Company | Coal hydroconversion process comprising solvent extraction and combined hydroconversion and upgrading |
US5110450A (en) * | 1989-12-21 | 1992-05-05 | Exxon Research And Engineering Company | Coal extract hydroconversion process comprising solvent enhanced carbon monoxide pretreatment |
US5151173A (en) * | 1989-12-21 | 1992-09-29 | Exxon Research And Engineering Company | Conversion of coal with promoted carbon monoxide pretreatment |
US5336395A (en) * | 1989-12-21 | 1994-08-09 | Exxon Research And Engineering Company | Liquefaction of coal with aqueous carbon monoxide pretreatment |
Also Published As
Publication number | Publication date |
---|---|
DE2326707A1 (de) | 1974-04-18 |
KR780000159B1 (en) | 1978-05-02 |
JPS4974201A (zh) | 1974-07-17 |
AU466761B2 (en) | 1975-11-06 |
CA990675A (en) | 1976-06-08 |
IN139155B (zh) | 1976-05-15 |
ZA733362B (en) | 1974-04-24 |
AU5600273A (en) | 1974-11-28 |
JPS5438601B2 (zh) | 1979-11-22 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: CHEVRON RESEARCH COMPANY, SAN FRANCISCO, CA. A COR Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:PITTSBURG AND MIDWAY COAL MINING COMPANY;REEL/FRAME:004593/0664 Effective date: 19860428 Owner name: CHEVRON RESEARCH COMPANY, A CORP. OF DE.,CALIFORNI Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:PITTSBURG AND MIDWAY COAL MINING COMPANY;REEL/FRAME:004593/0664 Effective date: 19860428 |