Classifications

• • 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
  • C10J3/54—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
  • C10J3/46—Gasification of granular or pulverulent flues in suspension
  • C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
  • C10J3/56—Apparatus; Plants
• • 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
  • C10J3/78—High-pressure apparatus
• • 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
  • C10J2200/00—Details of gasification apparatus
  • C10J2200/06—Catalysts as integral part of gasifiers
• • 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
  • C10J2300/0953—Gasifying agents
  • C10J2300/0956—Air or oxygen enriched air
• • 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
  • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
  • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
  • C10J2300/1656—Conversion of synthesis gas to chemicals
  • C10J2300/1662—Conversion of synthesis gas to chemicals to methane
• • 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
  • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
  • C10J2300/1671—Integration of gasification processes with another plant or parts within the plant with the production of electricity
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/30—Hydrogen technology
  • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

• This invention relates to new processes for making hydrogen, oxides of carbon, methane, other light hydrocarbons, and mixtures of two or more of these products by reacting carbonaceous materials comprising carbon, ferrous group metal components, and hydrogen with steam. These processes produce commercially attractive product yields in commercially attractive temperature ranges.
• the invention also relates to new carbonaceous materials comprising carbon, hydrogen, and ferrous group metal components, particularly nickel and cobalt.
• new carbonaceous materials comprising carbon, hydrogen, and ferrous group metal components, particularly nickel and cobalt.
• the new carbonaceous materials include a major amount of carbon, and minor amounts of hydrogen, and one or more ferrous group metal components.
• the new carbonaceous materials include from about 55 percent by weight to about 98 percent by weight of carbon, and preferably from about 75 percent by weight to about 95 percent by weight.
• the ferrous group metal components constitute an amount in the range of about one percent to about 44 percent, preferably in the range of about 25 percent to about 5 percent by weight, of the carbonaceous material. At these high carbon-to-metal ratios, the carbonaceous materials react readily with steam to produce large, commercially attractive quantities of hydrogen, methane, and/or other light hydrocarbons in commercially attractive temperature ranges.
• our carbonaceous materials exhibit excellent fluidity in fluid bed reactors, where these carbonaceous materials are reacted with steam.
• These carbonaceous materials also include hydrogen in amounts ranging from about 0.1 to about 1.0 percent by weight.
• the carbonaceous materials have total surface areas in the range of about 100 to about 300 square meters per gram of carbonaceous material, and pore volumes in the range of about 0.3 to about 0.6 milliliters (ml) per gram of carbonaceous material.
• the ferrous group metal components in our new carbonaceous materials are selected from the group consisting of nickel, cobalt, nickel alloys, and cobalt alloys, and mixtures of these metals and alloys. Broadly, iron constitutes no more than about 30 percent by weight, and preferably no more than about 10 percent by weight, of the ferrous group metal component content of our new carbonaceous materials. Nickel and cobalt constitute at least 70 percent by weight of the ferrous group metal component content in our carbonaceous materials.
• Our new carbonaceous materials prepared by the deposition processes referred to hereafter, typically include several phases.
• the major phase includes about 95% to about 99.9% carbon by weight, and hydrogen in an amount of about 0.1 percent to about 1 percent.
• the remainder of the minor phases is principally carbon, but may include some hydrogen.
• FIG. 5 is a scanning electron micrograph of a cobalt-containing carbonaceous fiber.
• This fibrous carbonaceous material contains more than about 90 percent by weight carbon, and includes at least about 5 percent by weight of cobalt-rich minor phases of the kind described above, as indicated at the arrow in FIG. 5.
• the methods for making our new carbonaceous materials comprise depositing carbon from carbon monoxide-containing gas mixtures over one or more ferrous group metal initiators.
• ferrous metal is transferred from the inititor to our carbonaceous material and becomes an integral part of these materials as described above.
• the ferrous group metal starting materials, called initiators in the deposition reaction to distinguish them from ferro.us group metal components in our new carbonaceous materials can be supported or unsupported ferrous group metals, ores, alloys or mixtures of such species.
• the deposition processes take place at pressures in the range of about 1 to about 100 atmospheres or more, and at temperatures in the range of about 300oC to about 700oc.
• the ferrous group metal component includes more than about 70 percent by weight nickel
• the carbon deposition temperature is in the range of about 300oC to about 500oC
• the carbonaceous material is especially suitable for making methane fay reaction with steam.
• the carbonaceous material is especially suitable for making hydrogen by reaction with steam.
• Our new carbonaceous materials are highly reactive with steam at pressures in the range from about 1 to about 100 atmospheres or more and at temperatures in the range of about 500oC to about 750oC. From these steaming reactions, we obtain product gas mixtures that include hydrogen, carbon monoxide, carbon dioxide, methane and other light hydrocarbons. The quantities of each gas produced in the steaming reactions depend on the nature of the carbonaceous material and the temperature and pressure at which the steam gasification takes place. In particular, carbonaceous materials formed at temperatures in the range of about 300oC to about 500oC, especially those formed in this temperature range from nickel alone or from ferrous group metal components containing at least about 70 percent by weight nickel, tend to produce substantial quantities of methane in the steam gasification reactions of this invention.
• carbonaceous materials formed at temperatures above about 550oC especially those carbonaceous materials formed above this temperature from cobalt alone or from ferrous group metai components containing at least about 70 percent by weight cobalt, tend to produce substantial quantities of hydrogen in the steam gasification reactions of this invention.
• the gasification reaction tends to produce hydrogen in large quantities, especially where the carbonaceous material is cobalt-based.
• the molar ratio of steam fed to carbon gasified is less than about 3, and the steam gasification pressure is in the range of about 10 to about 100 atmospheres, (and therefore nearly equals the amount required for thermodynamic equilibrium)
• the gasification reaction tends to produce methane in large quantities, especially where the carbonaceous material is nickel-based.
• the gaseous products initially formed in the steaming reactions of this invention can be converted to gas mixtures richer in hydrocarbons, hydrogen, or both, by lowering the temperature of the gaseous products and contacting these products with either fresh or partially reacted carbonaceous material in the range of about 300°C to about 500oC, and by adjusting the pressure and steam feed rate to produce the desired gases, as explained below.
• Our new carbonaceous materials serve distinctly different purposes in the initial steam gasification process of this invention and in the subsequent, lower temperature conversion reaction of the gasification products from the steaming reactions.
• our new carbonaceous materials participate as reactants.
• our carbonaceous materials serve as a catalyst.
• the carbon monoxide-containing gas mixtures used in the deposition processes for making our new carbonaceous materials can be low pressure or high pressure producer or synthesis gases. Such gas mixtures may include substantial quantities of nitrogen and carbon dioxide, but must contain little or no sulfur compounds such as hydrogen sulfide, carbon disulfide or sulfur dioxide. If necessary, carbon monoxide-containing gas mixtures are pretreateo by known methods for removing sulfur-containing gases before carbon deposition begins. Carbon deposition removes some of the carbon from the carbon monoxide-containing gas mixtures at nearly 100 percent thermal efficiency since the heat of reaction may remain as sensible heat in the carbon monoxide- depleted fuel gas stream. The reaction heated, carbon monoxide-depleted gas mixture from the carbon deposition reaction is a good fuel source for generating combined cycle electric power.
• a surprising and unexpected aspect of our methods for steam gasification of the new carbonaceous materials is that where such carbonaceous materials contain iron as the chief ferrous metal component, such carbonaceous materials have quite low rates of reactivity with steam at temperatures in the range of about 500oC to about 600oC. Steam gasification, of such carbonaceous materials at temperatures above about 700oC is adversely affected by the side reaction of the iron component with steam, ano gasification ceases long before all of the carbon is gasified.
• our new carbonaceous materials which contain substantial amounts of nickel, cobalt, nickel alloys, cobalt alloys and mixtures thereof, have high reaction rates with steam, and do not suffer from deactivating side reactions.
• Figure 1 illustrates the range of steam reactivities with several different carbonaceous materials, including those of our invention.
• Tables 1 and 2 show differences in final product gas composition where the products of steam-carbon gasification of carbonaceous reactants containing different ferrous group metals further react at temperatures below the carbon gasification point of about 500oC.
• a carbonaceous material comprising about 90 percent carbon and about 9 percent nickel, prepared by carbon deposition on nickel powder, at about 450oC, catalyzed the further conversion of a typical steam-carbon gasification mixture of carbon monoxide, hydrogen and steam at 400oC and about 1 atmosphere pressure in a steady flow reactor.
• Table 1 shows, nearly ail of the carbon monoxide was converted to methane and carbon dioxide, with very little additional gasification of solid carbon (0.04 gram out of 0.83 gram in 203 minutes).
• Table 2 relates to an identical run, with one exception: The carbonaceous material contained cobalt instead of nickel (about 90 percent carbon, and about 9 percent cobalt). These data show that cobalt-based carbonaceous material is less effective in converting the gas mixture to methane than the nickel-based material (27.2 percent methane for nickel-based; 9.5 percent, for cobalt-based), but more effective in shifting to hydrogen (49.8 percent hydrogen from cobalt-based material; 27.0 percent for nickel-based material). TABLE 1. FURTHER CONVERSION OF STEAM-CARBON GASIFICATION PRODUCTS
• FIG. 3 and Table 3 set forth data obtained from steaming a nickel-based carbonaceous material at 650oC at three different pressures, namely one atmosphere, 4.4 atmospheres, and 7.8, atmospheres. We conducted all these runs in small, fluidized bed, steady flow reactors at a constant steam feed rate of 23 standard cubic centimeters per minute per gram of car ⁇ on initially in the reactor. Figure 3 shows that the carbon gasification rate was nearly linear until substantially ail the carbon was gasified. Moreover, this rate did not vary appreciably with pressure. By contrast, the product composition set forth in Table 3 did change substantially depending on the pressure. As the pressure rose from one atmosphere to 7.8 atmospheres, the methane concentration tripled, the carbon monoxide concentration decreased by a factor of two, the hydrogen concentration decreased from about 53 percent to about 43 percent, and the carbon dioxide concentration rose from about 21 percent to about 31 percent.
• Figure 4 shows that our new carbonaceous materials can cycle many times between the carbon-rich states entering the steam gasification process of our invention, and the carbon-lean states resulting from the steam gasification processes of our invention.
• a carbonaceous material comprising about 90 percent carbon and about 9 percent cobalt by depositing carbon from a gas mixture comprising about 85 percent carbon monoxide and about 15 percent hydrogen at 450oC and one atmosphere pressure.
• Figure 4 shows that the rate of steam gasification did not vary significantly from one cycle to the other.
• Figure 6 plots the percent carbon gasified as a function of time at each temperature.
• the carbon gasification rates shown by the slopes of the lines in FIG. 6, were nearly constant until nearly all the carbon in the samples gasified.
• the gasification rates increased slightly with temperature, primarily because of equilibrium considerations.
• reaction temperature increased, the amount of carbon gasified per mole of steam fed to the reactor rose at equilibrium.
• Table 7 and FIG. 7 show, these runs operated at near- equilibrium conditions.
• the run represented by Table 7 occurred at 550oC and the run represented by FIG. 7 occurred at 600oC.
• FIG. 9 is a block diagram showing some of the advantages of a preferred embodiment of our new processes for producing methane, or other synthetic natural gas, and electric power, from coal.
• coal from source 1 passes on path 2 to coal gasification and clean-up zone 3. There, the coal is converted to a gaseous mixture of nitrogen, carbon monoxide, carbon dioxide and hydrogen, and the ash, sulfur and water content of the mixture is reduced to acceptable levels by known methods.
• One advantage of our processes is that we can make synthetic natural gas by reacting coal with air instead of oxygen. Unlike other synthetic gas manufacturing processes, our processes are compatible with feed stocks containing substantial amounts of nitrogen ana carbon dioxide.
• the cold, clean product gas then passes along path 4 to carbon deposition zone 5 where formation of our carbonaceous materials Dy deposition over one or more ferrous group metal initiators takes place.
• Some of the fuel gas may pass along path 6 directly to power generation zone 7, if desired, for combustion with air to generate base load and/or peaking power.
• Depleted fuel gas passes on path 8 to zone 7 for conversion to power in the same way.
• Catalytically-active carbon rich carbonaceous material passes on path 9 to steam gasification zone 10 for reaction with steam to produce carbon monoxide, carbon dioxide, hydrogen, methane or possibly other light hydrocarbons, as desired.
• Carbon lean carbonaceous material is returned on path 11 to carbon deposition zone 5. Nearly all of the heating value of the carbonaceous material can be converted to methane or hydrogen in our steam gasification processes.
• withdrawn carbon which is embodied in our new carbonaceous materials, can be steam gasified to convert from about 40 percent to about 80 percent of the carbon to hydrogen, carbon oxides, methane, and other light hydrocarbons.
• the carbon-depleted carbonaceous materials can be enriched in carbon by further carbon deposition from carDon monoxide/hydrogen gas mixtures such as the fuel gas referred to above, using the carbon-lean carbonaceous material from the steam gasification.
• Figure .10 shows one embodiment of a reactor for gasifying our carbonaceous materials under fluid bed conditions with steam.
• Our carbonaceous materials enter reactor 101, which has a high length-to-diameter ratio, on path
• Product gasses exit reactor 101 on path 105 are cooled in cooling means 106, and then passed through bag house 107, where unreacted carbon is captured for return to reactor 101.
• Methane-rich gas passes from bag house 107 on path 108 for removal of carbon dioxide and other conventional polishing steps.
• Ferrous group metal component-rich material exits reactor 101 at the bottom, on path 108, and may be returned, if desired, to a carbon deposition reactor.
• Figure 11 shows, in block diagram, a material and heat balanced system for the conversion of our carbonaceous materials to methane, assuming steam-carbon equilibrium at 550oC and 200 psig.
• Carbonaceous material passes from storage zone 201 on path 202 to reactor 203.
• Steam enters reactor 203 on path 204 and contacts the carbonaceous materials for production of methane, carbon monoxide, hydrogen and other gases.
• This gas mixture exits the reactor zone on path 205, passes through superheater 206, and then, on path 207, to zone 208 where carbon dioxide and water are removed. From zone 208, product gas passes on path 209 to polishing methanator 210, from which the product methane gas emerges on path 211.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Combustion & Propulsion (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Catalysts (AREA)
• Carbon And Carbon Compounds (AREA)
• Hydrogen, Water And Hydrids (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (2)

Publications (2)

Family

ID=22939799

Family Applications (1)

Country Status (10)

Families Citing this family (6)

Citations (1)

Family Cites Families (8)

• 1982
  • 1982-03-11 JP JP57501336A patent/JPS58500445A/ja active Granted
  • 1982-03-11 NL NL8220132A patent/NL8220132A/nl unknown
  • 1982-03-11 WO PCT/US1982/000310 patent/WO1982003380A1/en not_active Application Discontinuation
  • 1982-03-11 BR BR8207244A patent/BR8207244A/pt unknown
  • 1982-03-11 IL IL65225A patent/IL65225A/xx unknown
  • 1982-03-11 EP EP19820901238 patent/EP0074394A4/de not_active Withdrawn
  • 1982-03-12 ZA ZA821679A patent/ZA821679B/xx unknown
  • 1982-03-15 CA CA000398346A patent/CA1197098A/en not_active Expired
  • 1982-03-26 PL PL23565882A patent/PL235658A1/xx unknown
  • 1982-03-26 IT IT67385/82A patent/IT1191176B/it active

Patent Citations (1)

Also Published As

Similar Documents

Legal Events