EP0032283A1 - Production d'un gaz de synthèse chimique à partir d'une matière d'alimentation carbonée et de vapeur - Google Patents

Production d'un gaz de synthèse chimique à partir d'une matière d'alimentation carbonée et de vapeur Download PDF

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Publication number
EP0032283A1
EP0032283A1 EP80300143A EP80300143A EP0032283A1 EP 0032283 A1 EP0032283 A1 EP 0032283A1 EP 80300143 A EP80300143 A EP 80300143A EP 80300143 A EP80300143 A EP 80300143A EP 0032283 A1 EP0032283 A1 EP 0032283A1
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Prior art keywords
steam
gas
hydrogen
methane
carbon monoxide
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EP80300143A
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German (de)
English (en)
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EP0032283B1 (fr
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James Milton Eakman
Theodore Kalina
Harry Allyn Marshall
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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Priority to DE8080300143T priority patent/DE3063388D1/de
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    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
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    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/48—Apparatus; Plants
    • C10J3/482—Gasifiers with stationary fluidised bed
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    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
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    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • C10J3/60—Processes
    • C10J3/64—Processes with decomposition of the distillation products
    • C10J3/66—Processes with decomposition of the distillation products by introducing them into the gasification zone
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    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
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    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
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    • C10K1/00—Purifying combustible gases containing carbon monoxide
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    • C10K1/12—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors
    • C10K1/122—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors containing only carbonates, bicarbonates, hydroxides or oxides of alkali-metals (including Mg)
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    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
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    • C10K1/12—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors
    • C10K1/14—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors organic
    • C10K1/143—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors organic containing amino groups
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    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • C10K1/12—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors
    • C10K1/14—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors organic
    • C10K1/143—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors organic containing amino groups
    • C10K1/146—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors organic containing amino groups alkali-, earth-alkali- or NH4 salts
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/16—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids
    • C10K1/165—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids at temperatures below zero degrees Celsius
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/093—Coal
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    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0946—Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
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    • C10J2300/0959—Oxygen
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    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
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    • C10J2300/0966—Hydrogen
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    • C10J2300/00—Details of gasification processes
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    • C10J2300/0976—Water as steam
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    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0983—Additives
    • C10J2300/0996—Calcium-containing inorganic materials, e.g. lime
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    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1861—Heat exchange between at least two process streams
    • C10J2300/1884—Heat exchange between at least two process streams with one stream being synthesis gas
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    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1861—Heat exchange between at least two process streams
    • C10J2300/1892—Heat exchange between at least two process streams with one stream being water/steam

Definitions

  • This invention relates to the gasification of coal and similar carbonaceous materials and is particularly concerned with a catalytic gasification process carried out in the presence of a carbon-alkali metal catalyst to produce a chemical synthesis gas.
  • the amounts of hydrogen and carbon monoxide produced in the reformer compensate for the amounts of those gases removed in the treated gas that is withdrawn as intermediate Btu product gas.
  • the reformer effluent will normally contain carbon monoxide and hydrogen in amounts equivalent to the equilibrium quantities of those gases present in the raw product gas and will therefore supply the substantially equilibrium quantities of hydrogen and carbon monoxide required in the gasifier along with the carbon-alkali metal catalyst and steam to produce the thermoneutral reaction that results in the formation of essentially methane and carbon dioxide.
  • This invention provides a process for the generation of a high purity chemical synthesis gas by the substantially thermoneutral reaction of steam with coal, petroleum coke, heavy oil, residuum and other carbonaceous feed materials in the presence of carbon-alkali metal catalyst and added hydrogen and carbon monoxide.
  • a chemical synthesis gas can be generated by reacting steam with a carbonaceous feed material in a reaction zone at a temperature between about 1000°F. and about 1500°F.
  • the reforming zone effluent contain carbon monoxide and hydrogen in amounts equivalent to the equilibrium quantities of those gases present in the effluent gas withdrawn from'the reaction zone so that the effluent from the steam reforming zone will supply the substantially equilibrium quantities of hydrogen and carbon monoxide required in the reaction zone along with the carbon-alkali metal catalyst and steam to produce the thermoneutral reaction that results in the formation of essentially methane and carbon dioxide.
  • the reforming zone effluent contains less than the desired amount of carbon monoxide and hydrogen, additional amounts of these gases may be added to the gasifier.
  • a slip stream of the chemical synthesis product gas is used for this purpose. If the reforming zone effluent contains more than the desired amount of carbon monoxide and hydrogen, the excess can be mixed with the reaction zone effluent, passed through the downstream processing scheme, and withdrawn as a portion of the chemical synthesis gas product.
  • a sufficient amount of steam is normally fed to the reforming zone so that enough unreacted steam is present in the steam reforming zone effluent to provide substantially all the steam necessary to supply the reactions taking place in the reaction zone.
  • the reforming zone is normally operated at conditions such that its effluent may also be used to supply the heat needed to preheat the carbonaceous feed material to reaction temperature and compensate for heat losses from the reaction zone. This is normally achieved if the temperature of the reforming zone effluent is between about 100°F. and about 300°F. higher than the temperature in the reaction zone and the effluent is passed without substantial cooling into the reaction zone.
  • the process of the invention unlike similar processes proposed in the past, utilizes the thermoneutral reaction of steam with a carbonaceous feed material to produce a high purity chemical synthesis gas that has wide spread industrial applications.
  • the drawing is a schematic flow diagram of a process carried out in accordance with the invention for the manufacture of a chemical synthesis gas by the gasification of coal or similar carbonaceous solids with steam in the presence of a carbon-alkali metal catalyst and added equilibrium quantities of hydrogen and carbon monoxide.
  • the process depicted in the drawing is one for the production of a chemical synthesis gas by the gasification of bituminous coal, subbituminous coal, lignite, coal char, coke or similar carbonaceous solids with steam at a high temperature in the presence of a carbon-alkali metal catalyst prepared by impregnating the feed solids with a solution of an alkali metal compound or mixture of such compounds and thereafter heating the impregnated material to a temperature sufficient to produce an interaction between the alkali metal and the carbon present.
  • the solid feed material that has been crushed to a particle size of about 8 mesh or smaller on the U.S. Sieve Series Scale is passed into line 10 from a feed preparation plant or storage facility that is not shown in the drawing.
  • the solids introduced into line 10 are fed into a hopper or similar vessel 11 from which they are passed through line 12 into feed preparation zone 14.
  • This zone contains a screw conveyor or similar device, not shown in the drawing, that is powered by a motor 16, a series of spray nozzles or similar devices 17 for the spraying of an alkali metal-containing solution supplied through line 18 onto the solids as they are moved through the preparation zone by the conveyor, and a similar set of nozzles or the like 19 for the introduction of a hot dry gas, such as flue gas, into the preparation zone.
  • the hot gas, supplied through line 20 serves to heat the impregnated solids and drive off the moisture.
  • a mixture of water vapor and gas is withdrawn from zone 14 through line 21 and passed to a condenser, not shown, from which water may be recovered for use as makeup or the like.
  • the majority of the alkali metal-containing solution is recycled through line 49 from the alkali metal recovery portion of the process, which is described hereafter. Any makeup alkali metal solution required may be introduced into line 18 via line 13.
  • alkali metal-containing solution be introduced into preparation zone 14 to provide from about 1 to about 50 weight percent of an alkali metal compound or mixture of such compounds on the coal or other carbonaceous solids. From about 5 to about 30 percent is generally adequate.
  • the dried impregnated solid particles prepared in zone 14 are withdrawn through line 24 and passed to a closed hopper or similar vessel 25 from which they are discharged through a star wheel feeder or equivalent device 26 in line 27 at an elevated pressure sufficient to permit their entrainment into a stream of high pressure steam, recycle product gas, inert gas or other carrier gas introduced into line 29 via line 28.
  • the carrier gas and entrained solids are passed through line 29 into manifold 30 and fed from the manifold through feed lines 31 and nozzles, not shown in the drawing, into gasifier 32.
  • the feed system may employ parallel lock hoppers, pressurized hoppers, aerated standpipes operated in series, or other apparatus to raise the input feed solids stream to the required pressure level.
  • the gasifier 32 It is generally preferred to operate the gasifier 32 at a pressure between about 100 and 1500 psia, the most preferred range of operation being between about 200 and 800 psia.
  • the carrier gas and entrained solids will normally be introduced at a pressure somewhat in excess of the gasifier operating pressure.
  • the carrier gas may be preheated to a temperature in excess of about 300°F., but below the initial softening point of the coal or other feed material employed. Feed particles may be suspended in the carrier gas in a concentration between about 0.2 and about 5.0 pounds of solid feed material per pound of carrier gas.
  • ratios between about 0.5 and about 4.0 pounds of solid feed material per pound of carrier gas are preferred.
  • Gasifier 32 contains a fluidized bed of carbonaceous solids extending upward within the vessel above an internal grid or similar distribution device not shown in the drawing.
  • the bed is maintained in the fluidized state by means of steam, hydrogen and carbon monoxide introduced through line 33, manifold 34 and peripherally spaced injection lines and nozzles 35 and through bottom inlet line 36.
  • the particular injection-system shown in the drawing is not critical and hence other methodsfor:injecting the steam, hydrogen and carbon monoxide may be employed. In some instances, for example, it may be preferred to introduce the gases through multiple nozzles to obtain more uniform distribution of the injected fluid and reduce the possibility of channeling and related problems.
  • the space velocity of the rising gases within the fluidized bed will normally be between about 2 and about 300 actual volumes of steam, hydrogen and carbon monoxide per hour per volume of fluidized solids.
  • the carbonaceous solids impregnated with the alkali metal compound or mixture of such compounds are subjected to a temperature within the range between about 1000°F. and about 1500°F., preferably between about 1200°F. and 1400°F. At such a temperature the alkali metal constituents interact with the carbon in the carbonaceous solids to form a carbon-alkali metal catalyst, which will under proper reaction conditions equilibrate the gas phase reactions occurring during gasification to produce additional methane and at the same time supply substantial amounts of additional exothermic heatin situ.
  • the gasifier is therefore largely in heat balance.
  • the heat employed to preheat the feed coal to the reaction temperature and compensate for heat losses from the gasifier is supplied for the most part by excess heat in the gases introduced into the gasifier through lines 35 and 36. In the absence of the exothermic heat provided by the catalyzed gas phase reactions, these gases would have to be heated to substantially higher temperatures than those employed here.
  • the carbon-alkali metal catalyst utilized in the process of the invention is prepared by heating an intimate mixture of carbon and an alkali metal constitu- tent to an elevated temperature, preferably above 800°F.
  • the intimate mixture is prepared by impregnating the carbonaceous feed material with an alkali metal-containing solution and then subjecting the impregnated solids to a temperature above 800°F in the gasifier itself.
  • the alkali metal catalyst utilized in the process of this invention can be prepared without impregnation onto the carbonaceous solids to be gasified, and without heating in the gasifier.
  • the heating step may be carried out in a solid feed preparation zone or in an external heater.
  • the carbonaceous solids used will in most instances be the ones which are to be gasified but in some variations of the process carbonaceous materials other than the feed solids may be used.
  • inert carriers having carbon deposited on their outer surface may be used. Suitable inert carriers include silica, alumia, silica-alumina, zeolites, and the like.
  • the catalyst particles whether composed substantially of carbon and an alkali metal constituent or made up of carbon and an alkali metal constituent deposited on an inert carrier, may range from fine powders to coarse lumps, particles between about 4 and about 100 mesh on the U.S. Sieve Series Scale generally being preferred.
  • the size selected for use in a particular operation will normally depend in part on the gas velocities and other conditions within the system in which the catalyst is to be used. In fluidized bed systems, the particle size is in part dependent upon the conditions under which the bed is to be operated. In fixed or moving bed systems, the catalyst particle size is generally of less importance.
  • alkali metal constituents can be used in preparing the carbon-alkali metal catalyst.
  • Suitable constituents include alkali metals themselves and alkali metal compounds such as alkali metal carbonates, bicarbonates, formates, biphosphates, oxalates, amides, hydroxides, acetates, sulfates, hydrosulfates, sulfides, and mixtures of these and other similar compounds. All of these are not equally effective and hence a catalyst prepared from certain alkali metal constituents can be expected to give somewhat better results under certain conditions than do others.
  • cesium, potassium, sodium and lithium salts derived from organic or inorganic acids having ionization constants less than about 1 x 10 and alkali metal hydroxides are preferred.
  • the cesium compounds are the most effective, followed by the potassium, sodium and lithium compounds in that order. Because of their high activity, relatively low cost compared to cesium compounds, and ready availability, potassium compounds or sodium compounds are generally employed.
  • Potassium carbonate and potassium hydroxide are especially effective.
  • the alkali metal constituent and the carbonaceous solids are combined to form an intimate mixture by dissolving a water soluble alkali metal compound in an aqueous carrier, impregnating the carbonaceous solid with the resulting aqueous solution by soaking or spraying the solution onto the particles, and thereafter drying the solids.
  • a water soluble alkali metal compound in an aqueous carrier
  • the carbonaceous material can be impregnated by suspending a finely divided alkali metal or alkali metal compound in a hydrocarbon solvent or other inert liquid carrier of suitably low viscosity and high volatility and thereafter treating the solids with the liquid containing the alkali metal constituent.
  • the gas leaving the fluidized bed in gasifier 32 passes through upper section of the gasifier, which serves as a disengagement zone where the particles too heavy to be entrained by the gas leaving the vessel are returned to the bed.
  • this disengagement zone may include one or more cyclone separators or the like for removing relatively large particles from the gas.
  • the gas withdrawn from the upper part of the gasifier through line 37 will normally contain an equilibrium mixture at reaction temperature and pressure of methane, carbon dioxide, hydrogen, carbon monoxide, and unreacted steam. Also present in this gas are hydrogen sulfide, ammonia and other contaminants formed from the sulfur and nitrogen contained in the feed material, and entrained fines.
  • This raw product gas is introduced into cyclone separator or similar device 38 for removal of the larger fines.
  • the overhead gas then passes through line 39 into a second separator 41 where small particles are removed.
  • the gas from which the solids have been separated is taken overhead from separator 41 through line 42 and the fines are discharged downward thrcugh dip legs 40 and 43. These fines may be returned to the gasifier or passed to the alkali metal recovery portion of the process.
  • a stream of high ash content char particles is withdrawn through line 44 from gasifier 32.in order to control the ash content of the system and permit the recovery and recycle of alkali metal constituents of the catalyst.
  • the solids in line 44 which may be combined with fines recovered from the gasifier overhead gas through dip legs 40 and 43 and line 45, are passed to alkali metal recovery unit 46.
  • the recovery unit will normally comprise a multistage countercurrent leaching system in which the high ash content particles are countercurrently contacted with water introduced through line 47.
  • An aqueous solution of alkali metal compounds is withdrawn from the unit through line 48 and recycled through lines 49 and 18 to feed preparation zone 14.
  • Ash residues from which soluble alkali metal compounds have been leached are withdrawn from the recovery unit through line 50 and may be disposed of as land fill or further treated to recover added alkali metal constituents.
  • the gas leaving separator 41 is passed through line 42 to gas-gas heat exchanger 51 where it is cooled by indirect heat exchange with a gaseous mixture of methane and steam introduced through line 77.
  • the cooled gas is then passed through line 53 into waste heat boiler 54 where it is further cooled by indirect heat exchange with water introduced through line 55. Sufficient heat is transferred from the gas to the water to convert it into steam, which is withdrawn through line 56.
  • unreacted steam in the gas from exchanger 51 is condensed out and withdrawn as condensate through line 57.
  • the cool gas exiting waste heat boiler 54 through line 58 is passed to water scrubber 59. Here the gas stream passes upward through the scrubber where it comes in contact with water injected into the top of the scrubber through line 60.
  • the . water absorbs ammonia and a portion of the hydrogen sulfide in the gas stream and is withdrawn from the bottom of the scrubber through line 61 and passed to downstream units for further processing.
  • the water scrubbed gas stream is withdrawn from the scrubber through line 62 and is now ready for treatment to remove bulk amounts of hydrogen sulfide and other acid gases.
  • the gas stream is passed from water scrubber 59 through line 62 into the bottom of solvent scrubber 63.
  • the gas passes upward through the contacting zone in the scrubber where it comes in contact with a down-flowing stream of solvent such as monoethanolamine, dLethanolamine, a solution of sodium salts of amino acids, methanol, hot potassium carbonate or the like introduced into the upper part of the solvent scrubber through line 64.
  • the solvent scrubber may be provided with spray nozzles, perforated plates, bubble cap plates, packing or other means for promoting intimate contact between the gas and the solvent.
  • hydrogen sulfide, carbon dioxide and other acid gases are absorbed by the solvent, which exits the scrubber through line 65.
  • the spent solvent containing carbon dioxide, hydrogen sulfide and other contaminants is passed through line 65 to a stripper, not shown in the drawing, where it is contacted with steam or other stripping gas to remove the absorbed contaminants and thereby regenerate the solvent.
  • the regenerated solvent may then be reused by injecting it back into the top of the scrubber via line 64.
  • a clean gas containing essentially methane, hydrogen, and carbon monoxide in amounts substantially equivalent to the equilibrium quantities of those gases in the raw product gas withdrawn from gasifier 32 through line 37 is withdrawn overhead from the solvent scrubber via line 66.
  • the methane content of the gas will normally range between about 20 and about 60 mole percent and the gas will be of an intermediate Btu heating value, normally containing between about 400 and about 750 Btu's per standard cubic foot.
  • the intermediate Btu gas withdrawn overhead from solvent scrubber 63 through line 66 is introduced into heat transfer unit 67 where it passes in indirect heat exchange with liquid methane introduced through line 68.
  • the methane vaporizes within the heat transfer unit and is discharged as methane gas through line 69.
  • the vaporizing methane chills the intermediate Btu gas, which is primarily composed of methane hydrogen and carbon monoxide, to a low temperature approaching that required for liquefaction of the methane contained in the gas, after which the chilled gas is passed through line 70 into cryogenic unit 71.
  • the gas is further cooled by conventional means until the temperature reaches a value sufficiently low to liquefy the methane under the pressure conditions existing in the unit.
  • cryogenic unit Compressors and other auxiliaries associated with the cryogenic unit are now shown.
  • the amount of pressure required for the liquifaction step will depend in part upon the pressure at which the gasifier is operated and the pressure losses which are incurred in the various portions of the system.
  • a substantially pure stream of liquefied methane is taken off through-line 72 and passed through line 68 into heat transfer unit 67 as described earlier.
  • Hydrogen and carbon monoxide are withdrawn overhead from cryogenic unit 71 through line 80 and recovered as a chemical synthesis product gas.
  • the cryogenic unit is operated and designed in such a manner that less than about 10 mole .percent of methane, preferably less than about 5 mole percent, remains in the product gas removed through line 80.
  • the chemical synthesis gas produced in the process is one of extremely high purity and therefore has many industrial applications.
  • the recycle methane gas removed from heat transfer unit 67 through line 69 is passed to compressor 73 where its pressure is increased to a value from about 25 psi to about 150 psi above the operating pressure in gasifier 32.
  • the pressurized gas is withdrawn from compressor 73 through line 74 and passed through tubes 75 located in the convection section of steam reforming furnace 76.
  • the high pressure gas picks up heat via indirect heat exchange with the hot flue gases generated in the furnace.
  • the methane gas is removed from the tubes 75 through line 77 and mixed with steam, which is generated in waste heat boiler 54 and injected into line 77 via line 56.
  • the mixture of methane gas and steam is then passed through line 77 into gas-gas heat exchanger 51 where it is heated by indirect heat exchange with the raw product gas removed from separator 41.
  • the heated mixture is removed from exchanger 51 and passed through line 78 to steam reforming furnace 76.
  • the preheated mixture of steam and methane gas in line 78 is introduced into the internal tubes 79 of the steam reforming furnace where the methane and steam react with one another in the presence of a conventional steam reforming catalyst.
  • the catalyst will normally consist of metallic constituents supported on an inert carrier.
  • the metallic constituent will normally be selected from Group VI-B and the iron group of the Periodic Table and may be chromium, molybdenum, tungsten, nickel, iron, and cobalt, and may include small amounts of potassium carbonate or a similar compound as a promoter.
  • Suitable inert carriers include silica, alumina, silica-alumina, zeolites, and the like.
  • the reforming furnace is operated under conditions such that the methane in the feed gas will react with steam in the tubes 79 to produce hydrogen and carbon monoxide according to the following equation:
  • the temperature in the reforming furnace will normally be maintained between about 1200°F and about 1800°F, preferably between about 100°F and about 300°F above the temperature in gasifier 32.
  • the pressure will range between about 10 and about 30 psi above the pressure in the gasifier.
  • the mole ratio of steam to methane introduced into the reactor will range between about 2:1 and about 15:1, preferably between about 3:1 and about 7:1.
  • the reforming furnace may be fired by a portion of the methane gas removed from heat transfer unit 67 via line 69, a portion of the intermediate Btu gas removed from solvent scrubber 63 through line 66, or a similar fuel gas.
  • the gaseous effluent stream from the steam reforming furnace which will normally be a mixture consisting primarily of hydrogen, carbon monoxide, and unreacted steam, is passed, preferably without substantial cooling, through lines 81, 36, and 33 into gasifier 32.
  • This stream is the primary source of the hydrogen, carbon monoxide, and steam required in the gasifier in addition to the carbon-alkali metal catalyst to produce the thermoneutral reaction that results in the formation of essentially carbon dioxide and methane. It is therefore desirable that the reforming furnace effluent contain sufficient carbon monoxide and hydrogen to supply the substantially equilibrium quantities of those gases required in the gasifier and sufficient unreacted steam to provide substantially all of the steam required by the reactions taking place in the gasifier.
  • the carbon monoxide and hydrogen in the reformer effluent stream comprises a substantial portion of the heat input into the gasifier.
  • sufficient methane should normally be present in the feed to the reforming furnace so that enough carbon monoxide and hydrogen is produced by steam reforming the methane to compensate for the amount of hydrogen and carbon monoxide removed in the chemical synthesis product gas withdrawn from the process overhead of cryogenic unit 71 through line 80.
  • the conditions in the gasifier may be altered so that additional methane is produced in the raw product gas.
  • a slip stream of the chemical synthesis product gas may be used to make up any deficiency in the amounts of carbon monoxide and hydrogen required.
  • the conditions in the gasifier may be altered to decrease the amount of methane produced in the raw product gas, the excess methane may be withdrawn as a byproduct stream from line 74 prior to subjecting it to steam reforming, or the excess methane may be reformed to produce additional carbon monoxide and hydrogen that can be passed from line 81 into line 42 and recycled through the downstream portion of the process. If the amount of steam added via line 56 to the reforming furnace feed stream in line 78 is not sufficiently in excess of the amount consumed in the furnace so as to provide the desired quantity of unreacted steam in the reformer effluent, additional steam may be injected into line 78 through line 82.
  • the steam reforming step of the process be utilized in such a manner as to obviate the need for a separate preheat step.
  • This may be achieved by operating the reforming furnace so that the heat content of the effluent is sufficient to preheat the carbonaceous feed material to reaction temperature and maintain all of the reactants at such temperature by compensating for heat losses during gasification. Normally, this may be accomplished if the temperature of the effluent is between about 100°F and about 300°F higher than the operating temperature in the gasifier.
  • heat content refers to the sum of the heats of formation plus the sum of the sensible heats for each component in the reforming furnace effluent.
  • the effluent from the reforming furnace 76 will supply substantially all of the heat required in gasifier 32.
  • the effluent will not only contain sufficient sensible heat to preheat the carbonaceous feed material to reaction temperature and maintain all the reactants at such temperature by compensating for heat losses during gasification, but it will also contain sufficient amounts of carbon monoxide and hydrogen which react in the gasifier to produce enough exothermic heat to substantially balance the endothermic heat consumed by the reaction of the steam with carbon.
  • the invention provides a process for producing a high purity chemical synthesis gas from the steam gasification of a carbonaceous material such as coal in the presence of a carbon-alkali metal catalyst and substantially equilibrium quantities of added hydrogen and carbon monoxide.
  • the process of the invention has advantages over existing coal gasification processes that may be used to generate a chemical synthesis gas in that its gasifier operates at lower temperature, it is more energy efficient, and it does not require the injection of oxygen to supply heat, thereby obviating the need for an expensive oxygen plant.

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  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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EP80300143A 1980-01-15 1980-01-15 Production d'un gaz de synthèse chimique à partir d'une matière d'alimentation carbonée et de vapeur Expired EP0032283B1 (fr)

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EP80300143A EP0032283B1 (fr) 1980-01-15 1980-01-15 Production d'un gaz de synthèse chimique à partir d'une matière d'alimentation carbonée et de vapeur
DE8080300143T DE3063388D1 (en) 1980-01-15 1980-01-15 Production of a chemical synthesis product gas from a carbonaceous feed material and steam

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0073552A1 (fr) * 1981-08-27 1983-03-09 Exxon Research And Engineering Company Production de méthanol par gazéification d'houille
US7513260B2 (en) 2006-05-10 2009-04-07 United Technologies Corporation In-situ continuous coke deposit removal by catalytic steam gasification
WO2009104972A1 (fr) * 2008-02-21 2009-08-27 Co2Co Procédé d'utilisation d'un métal alcalin ou d'un métal alcalino-terreux contenant des composites organiques dans la décomposition plasmatique par micro-ondes du dioxyde de carbone pour la production de carbone

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2652319A (en) * 1949-01-03 1953-09-15 Standard Oil Dev Co Process for water-gas generation
US3775072A (en) * 1970-12-14 1973-11-27 Chevron Res Gas production
US3929431A (en) * 1972-09-08 1975-12-30 Exxon Research Engineering Co Catalytic reforming process
US4094650A (en) * 1972-09-08 1978-06-13 Exxon Research & Engineering Co. Integrated catalytic gasification process
FR2381820A1 (fr) * 1977-02-25 1978-09-22 Exxon Research Engineering Co Procede de gazeification catalytique pour l'obtention d'un gaz a pouvoir calorifique intermediaire
FR2393052A1 (fr) * 1977-06-02 1978-12-29 Ght Hochtemperaturreak Tech Gazeification du charbon avec energie nucleaire
FR2416255A1 (fr) * 1978-02-06 1979-08-31 Hochtemperaturreaktor Technik Production de gaz de synthese a partir du charbon

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4095650A (en) * 1977-08-10 1978-06-20 The United States Of America As Represented By The United States Department Of Energy Method for increasing the calorific value of gas produced by the in situ combustion of coal

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2652319A (en) * 1949-01-03 1953-09-15 Standard Oil Dev Co Process for water-gas generation
US3775072A (en) * 1970-12-14 1973-11-27 Chevron Res Gas production
US3929431A (en) * 1972-09-08 1975-12-30 Exxon Research Engineering Co Catalytic reforming process
US4094650A (en) * 1972-09-08 1978-06-13 Exxon Research & Engineering Co. Integrated catalytic gasification process
FR2381820A1 (fr) * 1977-02-25 1978-09-22 Exxon Research Engineering Co Procede de gazeification catalytique pour l'obtention d'un gaz a pouvoir calorifique intermediaire
US4118204A (en) * 1977-02-25 1978-10-03 Exxon Research & Engineering Co. Process for the production of an intermediate Btu gas
FR2393052A1 (fr) * 1977-06-02 1978-12-29 Ght Hochtemperaturreak Tech Gazeification du charbon avec energie nucleaire
FR2416255A1 (fr) * 1978-02-06 1979-08-31 Hochtemperaturreaktor Technik Production de gaz de synthese a partir du charbon

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0073552A1 (fr) * 1981-08-27 1983-03-09 Exxon Research And Engineering Company Production de méthanol par gazéification d'houille
US7513260B2 (en) 2006-05-10 2009-04-07 United Technologies Corporation In-situ continuous coke deposit removal by catalytic steam gasification
US7883674B2 (en) 2006-05-10 2011-02-08 United Technologies Corporation In-situ continuous coke deposit removal by catalytic steam gasification
WO2009104972A1 (fr) * 2008-02-21 2009-08-27 Co2Co Procédé d'utilisation d'un métal alcalin ou d'un métal alcalino-terreux contenant des composites organiques dans la décomposition plasmatique par micro-ondes du dioxyde de carbone pour la production de carbone
WO2009116868A1 (fr) * 2008-02-21 2009-09-24 Co2Co Procédé pour l’utilisation de matières organiques et composites contenant un métal alcalin ou un métal alcalinoterreux dans la décomposition par plasma assistée par micro-ondes desdits composés pour la production de gaz de synthèse

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DE3063388D1 (en) 1983-07-07

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