EP0007247A1 - Verfahren zur katalytischen Vergasung von kohlenstoffhaltigen Brennstoffen - Google Patents

Verfahren zur katalytischen Vergasung von kohlenstoffhaltigen Brennstoffen Download PDF

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EP0007247A1
EP0007247A1 EP79301418A EP79301418A EP0007247A1 EP 0007247 A1 EP0007247 A1 EP 0007247A1 EP 79301418 A EP79301418 A EP 79301418A EP 79301418 A EP79301418 A EP 79301418A EP 0007247 A1 EP0007247 A1 EP 0007247A1
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sodium
potassium
gasification
salt
lithium
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French (fr)
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EP0007247B1 (de
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Robert Joseph Lang
Joanne Keel Pabst
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/723—Controlling or regulating the gasification process
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/74—Construction of shells or jackets
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/82—Gas withdrawal means
    • C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • 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
    • C10J2300/0943—Coke
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0959—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0966—Hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0969—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0973—Water
    • C10J2300/0976—Water as steam
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • 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

Definitions

  • the present invention relates to a process for the catalytic gasification of carbonaceous materials such as oils, petroleum residua, coals and the like, and is particularly concerned with the catalytic gasification operations carried out in the presence of alkali metal- containing catalysts.
  • alkali metal compounds can be employed to catalyze the gasification of carbonaceous materials such as coal and other carbonaceous solids.
  • carbonaceous materials such as coal and other carbonaceous solids.
  • potassium carbonate, sodium carbonate, cesium carbonate and lithium carbonate will substantially accelerate the rate at which steam, hydrogen, carbon dioxide, oxygen and the like react with bituminous coal, subbituminous coal, lignite, petroleum coke, organic waste materials and similar carbonaceous solids to form methane, carbon monoxide, hydrogen, carbon dioxide and other gaseous products.
  • Other alkali metal salts such as alkali metal chlorides, however, have a low catalytic activity when compared to that of the corresponding carbonate. Because of the relatively high cost of cesium carbonate and the low effectiveness of lithium and. sodium carbonates, most of the experimental work in this area which has been carried out in the past has been directed toward the use of potassium carbonate.
  • the present invention provides an improved process for the catalytic gasification of a carbonaceous feed material.
  • catalyst costs incurred during the gasification of oils, petroleum residua, bituminous coat, subbituminous coal, lignite, organic waste material, petroleum coke, and other carbonaceous feed materials can be significantly reduced while at the same time obtaining unexpectedly high gasification rates by employing mixtures of inexpensive potassium compounds and sodium compounds as the catalyst.
  • Laboratory tests have shown that when mixtures of coal, potassium chloride or potassium sulfate, and sodium carbonate or sodium sulfate are injected into a reaction zone and the coal is subsequently gasified, surprisingly high gasification rates are obtained.
  • the use of catalysts containing mixtures of inexpensive potassium and sodium compounds reduces the initial catalyst cost and the cost of makeup catalyst and at the same time permits the attainment of high gasification rates.
  • the use of such mixtures also obviates the need for expensive secondary catalyst recovery procedures.
  • the invention makes possible substantial savings in gasification operations and permits the generation of product gases at significantly lower cost than would normally otherwise be the case.
  • the process depicted in Figure 1 is one for the gasification of bituminous coal, subbituminous coal, lignite, organic waste materials or similar carbonaceous solids in the presence of added sodium and potassium compounds. It will be understood that the invention is not restricted to this particular gasification process and instead may be employed in any of a wide variety of fixed bed, moving bed and fluidized bed gasification operations in whick alkali metal compounds are used to promote- the reaction of steam, hydrogen, carbon dioxide, or a similar gasification agent with carbonaceous feed materials and a char, coke or other solid product containing alkali metal residues is recovered. Many such operations have been described in the technical literature and will be familiar to those skilled in the art.
  • a solid carbonaceous feed material such as bituminous coal, subbituminous coal, lignite or the like, which has been crushed and screened to a particle size of about 8 mesh or smaller on the U.S. Sieve Series Scale is fed into the. system through line 10 from a coal preparation plant or storage facility which is not shown in the drawing.
  • the solids introduced through line 10 are fed into a hopper or similar vessel 12 from which they are passed through line 13 into a feed preparation zone 14.
  • the feed preparation zone shown includes a screw conveyor or similar device, not shown in the drawing, which is powered by a motor 16, a series of spray nozzles or the like 17 for the spraying of a solution of soluble alkali metal compounds introduced through line 18 onto the solids as they are moved through the preparation zone by the conveyor, and nozzles or the like 19 for the introduction of steam from line 20 into the preparation zone to heat the solids and drive off moisture.
  • the alkali metal solution fed through line 18 is prepared by introducing soluble sodium and potassium salts or other sodium and potassium compounds into mixing vessel 21 as indicated by lines 22 and 23, respectively and dissolving these in water or other suitable solvent solution admitted through line 24.
  • Alkali metal solution recycled from the catalyst recovery zone through line 25 as described hereafter may also be used.
  • Steam is withdrawn from the preparation zone 14 through line 28 and will normally be passed to a condenser or heat exchanger not shown for the recovery of heat and condensate which can be used as makeup water or the like.
  • the potassium compound introduced into mixing vessel 21 through line 23 will normally be an inexpensive compound which has a relatively poor catalytic activity as compared to that of potassium carbonate.
  • "Relatively poor catalytic activity as compared to that of potassium carbonate” as used herein refers to a gasification rate obtained from gasifying a carbonaceous material in the presence of a sufficient amount of potassium compound to yield an atomic ratio of potassium cations-to-carbon atoms of about .03 or greater that is about one-half or less that of the rate obtainable by gasifying the same material in the presence of an equivalent amount of potassium carbonate.
  • Examples of such potassium compounds include potassium chloride, potassium sulfate, and similar potassium salts of a strong acid.
  • “Strong acid” as used herein refers to an organic or inorganic acid having an ionization constant greater than about 1x10 at 25°C.
  • the sodium compound introduced into mixing vessel 21 through line 22 will normally be either a sodium salt of a weak acid or a sodium salt of a strong acid that is converted, either temporarily or permanently, into a weak acid salt of sodium when subjected to gasification conditions in the presence of the potassium compound.
  • "Weak acid” as used herein refers to an organic or inorganic acid having an ionization constant less than about 1 x 10 -3 at 25°C. Examples of suitable sodium compounds that are salts of weak acids in- cluide sodium hydroxide, sodium carbonate, sodium bicarbonate sodium sulfide, sodium oxalate, sodium acetate, and the like.
  • sodium salts of strong acids that may be used in conjunction with potassium sulfate because they are temporarily or permanently converted to weak acid salts include sodium chloride, sodium sulfate and sodium nitrate.
  • the actual sodium compound used will normally depend upon its availability, cost, degree of solubility and the potassium compound utilized.
  • the anion associated with the potassium compound and the anion associated with the sodium compound exchange with one another to produce K 2 CO 3 and Na 2 SO 4 , which is reduced in the presence of carbon, hydrogen or carbon monoxide under gasification conditions to Na 2 S.
  • the Na 2 S then undergoes an anion exchange with the K 2 SO 4 to produce K 2 S and additional Na 2 SO 4 , which also is reduced to Na 2 S.
  • the net results of these reactions is the conversion of the poorly catalytic K 2 S0 4 , a strong acid salt of potassium into catalytically active K 2 CO 3 and K 2 S , weak acid salts of potassium.
  • the Na 2 S that is formed is also catalytically active and is believed to add to the overall resultant catalytic activity of the original combination. It is believed that the weak acid salts, K 2 CO 3 , K2S and Na 2 S, react with the acidic carbonaceous solids to form an alkali metal-char "salt", which is believed to be the active site in gasification. Thus, in the case where the potassium compound is K 2 S0 4 and the sodium compound is Na 2 CO 3 , both the potassium and sodium cations end up catalyzing the gasification of the carbonaceous solids.
  • the potassium compound is potassium sulfate and the sodium compound is sodium sulfate
  • the following equations are believed to represent the reactions that take place.
  • an anion exchange cannot take place between K 2 S0 4 and Na 2 SO 4 since the anions are identical.
  • the strong acid salt Na 2 SO 4 is reduced in the presence of carbon, carbon monoxide or hydrogen under gasification conditions to the weak acid salt Na 2 S, which then undergoes an anion exchange with the K 2 S0 4 to produce K 2 S and Na 2 SO 4 .
  • the Na 2 SO 4 thus formed is also reduced in the presence of carbon, carbon monoxide or hydrogen to Na 2 S .
  • the net result of these reactions is the formation of catalytically active K 2 S and Na 2 S and therefore, like the example illustrated in equations (1) and (2) above, both the potassium and sodium cations end up catalyzing the gasification of the carbonaceous solids.
  • equations (5) and (6) set forth below represent the mechanism by which potassium sulfate is activated by sodium chloride. .
  • the potassium and sodium compounds exchange anions thereby forming KCl and Na 2 SO 4 .
  • the Na 2 SO 4 is then reduced under gasification conditions and in the presence of carbon, hydrogen or carbon monoxide to Na Z S, which undergoes an anion exchange with KC1 to yield catalytically active K 2 S and catalytically inactive NaCl, one of the original reactants.
  • equations (1) through (4) above only the potassium cations end up catalyzing the gasification reactions.
  • any weak acid salt of sodium may be used to activate the relatively noncatalytic potassium ! compound; however, only certain strong acid sodium salts will be effective for this purpose.
  • only strong acid salts of sodium that are either temporarily or permanently converted to weak acid sodium salts under gasification conditions and in the presence of the potassium compound to be activated can be utilized.
  • the examples illustrated by equations (3) through (6) above represent two cases in which relatively noncatalytic K 2 SO 4 is activated by a strong acid sodium salt that is converted into a weak acid salt.
  • the strong acid sodium salt Na 2 SO 4 undergoes reduction and is thereby permanently converted to the weak acid salt Na 2 S.
  • the strong acid salt NaCl is converted to the weak acid salt Na 2 S in a two-step process.
  • the Na 2 S then exchanges anions with KCl to reform the strong acid salt NaCl.
  • This example therefore, represents a case where a strong acid sodium salt is only temporarily converted to a weak acid salt.
  • An example of a strong acid salt of sodium which is neither temporarily nor permanently converted to a weak acid sodium salt under gasification conditions in the presence of K 2 SO 4 and therefore will not activate K 2 SO 4 is Na 3 PO 4
  • the total quantity of the sodium and potassium compounds used should normally be sufficient to provide a combined added alkali metal-to-carbon atomic ratio in excess of about .03:1. Generally speaking, from about 5% to about 50% by weight of sodium and potassium compounds, based on the coal or other carbonaceous feed material will be employed. From about 10% to about 35% by weight is generally preferred. The higher the mineral content of the feed material, the more sodium and potassium compounds that should normally be used.
  • the feed solids which are impregnated with sodium and potassium compounds in feed preparation zone 14 are withdrawn through line 30 and passed to a feed hopper or similar vessel 31. From here they are discharged through a star wheel feeder or a similar device 32 in line 33 at an elevated pressure sufficient to permit their entrainment in a stream of steam, recycle product gas, inert gas or other carrier gas introduced into the system through line 34.
  • the carrier gas and entrained solids are passed through line 35 into manifold 36 and fed through multiple feed lines 37 and nozzles, not shown in the drawing, into gasifier 38.
  • the feed system employed may include parallel lock hoppers, pressurized hoppers, aerated standpipes operated ' in series, or other apparatus for raising the input feed solid stream to the required pressure level.
  • Gasifier 38 comprises a refractory-lined vessel containing afluidized bed of carbonaceous solids extending upward within the vessel above an internal grid or similar distribution device not shown in the drawing.
  • the solids are maintained in the fluidized state within the gasifier by means of a mixture of steam and oxygen injected through bottom inlet line 39 and multiple nozzles 40 connected to manifold 41.
  • Sufficient oxygen is added to the steam through line 42 to maintain the fluidized bed at a temperature within the range between about 1200°F and about 2000°F.
  • the gasifier pressure will normally be between about 100 psig and about 2000 psig.
  • the gas leaving the fluidized bed in gasifier 38 passes through the upper section of the gasifier, which serves as a disengagement zone where particles too heavy to be entrained by the gas leaving the vessell are returned to the bed.
  • this disengagement zone may include oneor 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 43 is passed to cyclone separator or similar device 44 for removal of larger fines.
  • the overhead gas then passes through line 46 into a second separator 47 where smaller particles are removed.
  • the gas from which the solids have been separated is taken overhead from separator 47 through line 48 and the fines are discharged downward through dip legs 45 and 49.
  • the gas stream may be passed through suitable heat exchange equipment for the recovery of heat and subsequently passed downstream for further processing.
  • Char particles containing carbonaceous material, ash and alkali metal residues are continuously withdrawn through line 50 from the bottom of the fluidized bed in gasifier 38.
  • the particles flow downward through line 50 counter. current to a stream of steam or other elutriating gas introduced through line 51.
  • a preliminary separation of solids based on differences in size and density takes place.
  • the lighter particles containing a relatively large amount of carbonaceous material tend to be returned to the gasifier and the heavier particles having a relatively high content of ash and alkali metal residues continue downward through line 52 into fluidized bed withdrawal zone 53.
  • Steam or othe fluidizing gas is introduced into the bottom of the withdrawa zone through line 54 to maintain the bed in the fluidized state.
  • Water may be introduced through line 55 in order to cool the particles and facilitate their further processing.
  • the withdrawal rate is controlled by regulating the pressure within zone 53 by means of throttle valve 56 in overhead line 57.
  • the gases from line 57 may be returned to the gasifier through line 58 or vented through valve 59.
  • From vessel 53 the solid particles are passed through line 60 containing valve 61 into hopper 62.
  • the char fines recovered from the raw product gas through dip legs 45 and 49 may be combined with the char particles withdrawn from the gasifier by passing the fines through line 63 into hopper 62.
  • the particles in hopper 62 will contain sodium and potassium residues composed of water-soluble and water-insoluble sodium and potassium compounds. These particles are passed from hopper 62 through line 64 into catalyst recovery ; unit 65.
  • the catalyst recovery unit will normally comprise a multistage countercurrent extraction system in which the particles containing the sodium and potassium residues are countercurrently contacted with water introduced through line 66.
  • An aqueous solution of sodium and potassium compounds is recovered from the unit and may be recycled through lines 67 and 25 to the catalyst preparation unit or mixing vessel 21. Particles from which substantially all of the soluble sodium and potassium constituents have been extracted are withdrawn from the catalyst recovery unit through line 68.
  • These solids will normally contain substantial quantities of sodium and potassium present in the form of sodium and potassium aluminosilicates and other water-insoluble compounds. These compounds are formed in part by the reaction with the ash in the coal and other feed material of sodium and potassium compounds added to catalyze the gasification reaction. In general, from about 15% to as much as 50% of the added alkali metal constituents will be converted into alkali metal aluminosilicates and other water-insoluble compounds.
  • the feed solids are impregnated with a solution containing a mixture of sodium and potassium compounds prior to their introduction into the gasifier 38.
  • a solution containing a mixture of sodium and potassium compounds prior to their introduction into the gasifier 38.
  • the compounds may be mixed in the solid state with the carbonaceous feed particles and the mixture may be subse-. quently passed into the gasifier.
  • Other methods for separate introduction of the sodium and potassium compounds into this system will be apparent to those skilled in the art.
  • the gasification rate obtained for each char sample was determined.
  • the char not gasified was ashed to determine the amount of carbon present and the alkali metal cation-to-carbon atomic ratio was then calculated.
  • the results of these tests are set forth in Figures 2 through 10. In all cases the gasification rate is expressed as the conversion weighted average rate in percent of carbon present per hour over the interval of 0-907. carbon conversion.
  • Figure 2 sets forth the steam gasification rate data obtained from char impregnated with various concentrations of potassium carbonate, potassium sulfate, sodium carbonate and a mixture of potassium sulfate and sodium carbonate. It can be seen in Figure 2 that the relatively expensive potassium carbonate yielded much greater gasification rates than did the less expensive potassium sulfate and sodium carbonate and is therefore a much more active gasification catalyst than either of the latter two compounds.
  • the dashed line in Figure 2 represents the gasification rates that one of ordinary skill in the art would expect to observe if a mixture of sodium carbonate :and potassium sulfate which is equimolar in sodium and potassium (moles Na/K " 1.0) was used as a catalyst.
  • the expected gasification rate for such a mixture that yields an atomic ratio of .066 alkali metal cations per carbon atom was calculated as follows.
  • the observed rate of about 51% carbon per hour for a concentration of sodium carbonate that yielded an atomic ratio of .066 sodium cations per carbon atom was added to the observed rate of about 9.0% carbon per hour for a concentration of potassium sulfate that yielded an atomic ratio of .066 potassium cations per carbon atom and the resultant value of 60% carbon per hour was divided by 2 to yield the expected rate of 30% carbon per hour.
  • This rate was then plotted against the atomic ratio of .066 cations per carbon atom where .033 of the cations were potassium cations and the other .033 were sodium cations.
  • the expected gasification rates for mixtures of sodium carbonate and potassium sulfate that are equimolar in sodium and potassium but yield alkali metal cation-to-carbon atomic ratios of other values were calculated in a manner similar to that described above.
  • Figure 4 shows that surprisingly high gasification rates are obtained using mixtures of potassium sulfate and sodium chloride that are equimolar in potassium and.sodium.
  • the gasification rates for potassium sulfate alone and for sodium chloride alone fall on the same line. This line, therefore, also represents the gasification rates that would be expected for mixtures of the two salts that are equimolar in potassium and sodium.
  • Figures 6 and 7 illustrate that catalysts comprised of a mixture of potassium chloride and one of various inexpensive sodium salts will yield higher than expected gasification rates when the catalyst concentration is above a certain value.
  • Figure 6 shows that surprisingly high rates are obtained when a mixture of potassium chloride and sodium carbonate that is equimolar in potassium and sodium is employed in sufficient concentrations to yield an atomic ratio greater than about .08 alkali metal cations per carbon atom.
  • Figure 7 makes a similar showing for a mixture of potassium chloride and sodium sulfate that is equimolar in potassium and sodium.
  • the expected gasification rates are represented by a dashed line and were calculated as described in reference to Figure 2.
  • Figure 8 illustrates that a catalyst comprised of a mixture of a relatively noncatalytic potassium salt and a lithium salt -- in lieu of a sodium salt -- will also yield unexpectedly high gasification rates. It can be seen in Figure 8 that surprisingly high gasification rates are obtained when char is gasified in the presence of a mixture of potassium sulfate and lithium sulfate that is equimolar in potassium and lithium. As in prior Figures, the dashed line represents the gasification rate that would be expected by one of ordinary skill in the art.
  • Figure 9 shows the gasification rates obtained when Illinois No. 6 coal char was gasified in the presence of catalysts comprised of mixtures of potassium sulfate and varying amounts of either sodium carbonate, sodium sulfate or sodium chloride.
  • the potassium sulfate was present in quantities such that the atomic ratio of potassium cations-to-carbon atoms ranged between about .051 and about .057.
  • the amount of the particular sodium salt present was varied over a range such that the ratio of sodium cations to potassium cations present per carbon atoms ranged from .25 to 1.0. This ratio (Na/K) is indicated next to each point plotted in the Figure.
  • the rate of 8% carbon per hour obtained for the use of potassium sulfate alone (Na/K - 0) is also shown in the Figure. It can be seen from the plotted data that for each combination of potassium sulfate and one of the three sodium salts, the presence of only a small amount of the sodium salt (Na/K - .25) resulted in a sharp increase in the gasification rate over that for a zero concentration of the sodium salt. The gasification rate continued to.increase as the amount of the sodium salt in the mixture was increased up to a sodium-to-potassium atomic ratio of 1.0.
  • Figure 10 is a plot similar to that of Figure 9 except that the gasification rates plotted are for a catalyst comprised of a mixture of potassium chloride and varying amounts of sodium carbonate.
  • the invention provides a process for gasifying a carbonaceous material which makes it possible to employ mixtures of inexpensive alkali metal salts as catalysts and at the same time attain gasification rates nearly as high as those obtainable by the use of expensive potassium carbonate. As a result, the overall cost of the product gas may be substantially reduced.
  • Temperatures given herein in °F are convertible to C by subtracting 32 and then dividing by 1.8.

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EP79301418A 1978-07-17 1979-07-17 Verfahren zur katalytischen Vergasung von kohlenstoffhaltigen Brennstoffen Expired EP0007247B1 (de)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0035887A2 (de) * 1980-03-10 1981-09-16 Exxon Research And Engineering Company Verfahren zur katalytischen Vergasung von Kohle
FR2478615A1 (fr) * 1980-03-21 1981-09-25 Haldor Topsoe As Procede de conversion de charbon et/ou de fractions lourdes de petrole en hydrogene ou gaz de synthese de l'ammoniac
FR2549488A1 (fr) * 1983-07-23 1985-01-25 Metallgesellschaft Ag Procede pour l'exploitation d'une installation de gazeification de combustibles solides
US7513260B2 (en) 2006-05-10 2009-04-07 United Technologies Corporation In-situ continuous coke deposit removal by catalytic steam gasification
WO2014134000A1 (en) 2013-02-28 2014-09-04 Corning Incorporated Chemical activation of carbon via an entrained stream method
WO2014160597A1 (en) 2013-03-27 2014-10-02 Corning Incorporated Chemical activation of carbon via a gas atomization method
US9353322B2 (en) 2010-11-01 2016-05-31 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
CN107497467A (zh) * 2017-07-14 2017-12-22 四川雷鸣环保装备有限公司 一种热解气化催化剂及使用该催化剂的造纸垃圾处理工艺
US10344231B1 (en) 2018-10-26 2019-07-09 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with improved carbon utilization
US10435637B1 (en) 2018-12-18 2019-10-08 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with improved carbon utilization and power generation
US10464872B1 (en) 2018-07-31 2019-11-05 Greatpoint Energy, Inc. Catalytic gasification to produce methanol

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KR101140530B1 (ko) * 2007-12-28 2012-05-22 그레이트포인트 에너지, 인크. 접촉 기화용 석유 코크스 조성물
KR101468768B1 (ko) * 2009-05-13 2014-12-04 그레이트포인트 에너지, 인크. 탄소질 공급원료의 히드로메탄화 방법
WO2012024369A1 (en) * 2010-08-18 2012-02-23 Greatpoint Energy, Inc. Hydromethanation of carbonaceous feedstock
JP2013537248A (ja) * 2010-09-10 2013-09-30 グレイトポイント・エナジー・インコーポレイテッド 炭素質フィードストックの水添メタン化
JP2013541622A (ja) * 2010-11-01 2013-11-14 グレイトポイント・エナジー・インコーポレイテッド 炭素質フィードストックの水添メタン化
US10618818B1 (en) 2019-03-22 2020-04-14 Sure Champion Investment Limited Catalytic gasification to produce ammonia and urea

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FR1003980A (fr) * 1949-01-03 1952-03-24 Standard Oil Dev Co Catalyseurs
US3252773A (en) * 1962-06-11 1966-05-24 Pullman Inc Gasification of carbonaceous fuels
US3775072A (en) * 1970-12-14 1973-11-27 Chevron Res Gas production
US3850588A (en) * 1970-05-05 1974-11-26 Chevron Res Production of synthesis gas rich in carbon monoxide
US4094650A (en) * 1972-09-08 1978-06-13 Exxon Research & Engineering Co. Integrated catalytic gasification process

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GB191007718A (en) * 1909-07-07 1911-03-30 Otto Dieffenbach Improvements in the Production of Hydrogen.
FR1003980A (fr) * 1949-01-03 1952-03-24 Standard Oil Dev Co Catalyseurs
US3252773A (en) * 1962-06-11 1966-05-24 Pullman Inc Gasification of carbonaceous fuels
US3850588A (en) * 1970-05-05 1974-11-26 Chevron Res Production of synthesis gas rich in carbon monoxide
US3775072A (en) * 1970-12-14 1973-11-27 Chevron Res Gas production
US4094650A (en) * 1972-09-08 1978-06-13 Exxon Research & Engineering Co. Integrated catalytic gasification process

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0035887A3 (en) * 1980-03-10 1981-12-02 Exxon Research And Engineering Company A process for the catalytic gasification of coal
EP0035887A2 (de) * 1980-03-10 1981-09-16 Exxon Research And Engineering Company Verfahren zur katalytischen Vergasung von Kohle
FR2478615A1 (fr) * 1980-03-21 1981-09-25 Haldor Topsoe As Procede de conversion de charbon et/ou de fractions lourdes de petrole en hydrogene ou gaz de synthese de l'ammoniac
FR2549488A1 (fr) * 1983-07-23 1985-01-25 Metallgesellschaft Ag Procede pour l'exploitation d'une installation de gazeification de combustibles solides
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
US9353322B2 (en) 2010-11-01 2016-05-31 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
WO2014134000A1 (en) 2013-02-28 2014-09-04 Corning Incorporated Chemical activation of carbon via an entrained stream method
WO2014160597A1 (en) 2013-03-27 2014-10-02 Corning Incorporated Chemical activation of carbon via a gas atomization method
CN107497467A (zh) * 2017-07-14 2017-12-22 四川雷鸣环保装备有限公司 一种热解气化催化剂及使用该催化剂的造纸垃圾处理工艺
CN107497467B (zh) * 2017-07-14 2020-05-15 四川雷鸣环保装备有限公司 一种热解气化催化剂及使用该催化剂的造纸垃圾处理工艺
US10464872B1 (en) 2018-07-31 2019-11-05 Greatpoint Energy, Inc. Catalytic gasification to produce methanol
US10344231B1 (en) 2018-10-26 2019-07-09 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with improved carbon utilization
US10435637B1 (en) 2018-12-18 2019-10-08 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with improved carbon utilization and power generation

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JPS6349719B2 (de) 1988-10-05
ZA793440B (en) 1980-07-30
EP0007247B1 (de) 1982-11-24
DE2964095D1 (en) 1982-12-30
BR7904521A (pt) 1980-04-15

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