EP1373131A4 - Procede de production d'hydrogene et applications associees - Google Patents

Procede de production d'hydrogene et applications associees

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Publication number
EP1373131A4
EP1373131A4 EP02723316A EP02723316A EP1373131A4 EP 1373131 A4 EP1373131 A4 EP 1373131A4 EP 02723316 A EP02723316 A EP 02723316A EP 02723316 A EP02723316 A EP 02723316A EP 1373131 A4 EP1373131 A4 EP 1373131A4
Authority
EP
European Patent Office
Prior art keywords
recited
molten metal
steam
hydrogen
iron
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP02723316A
Other languages
German (de)
English (en)
Other versions
EP1373131A1 (fr
Inventor
Boyd R Davis
J Kelly Kindig
Robert R Odle
Thomas E Weyand
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Alchemix Corp
Original Assignee
Alchemix Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US09/800,421 external-priority patent/US7232472B2/en
Priority claimed from US09/800,434 external-priority patent/US6620398B2/en
Priority claimed from US09/800,769 external-priority patent/US6682714B2/en
Priority claimed from US09/800,423 external-priority patent/US20020139049A1/en
Priority claimed from US10/085,436 external-priority patent/US6663681B2/en
Application filed by Alchemix Corp filed Critical Alchemix Corp
Publication of EP1373131A1 publication Critical patent/EP1373131A1/fr
Publication of EP1373131A4 publication Critical patent/EP1373131A4/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/10—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/025—Preparation or purification of gas mixtures for ammonia synthesis
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/10—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with metals
    • C01B3/105—Cyclic methods
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B49/00—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
    • C10B49/14—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot liquids, e.g. molten metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/12—Applying additives during coking
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • 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
    • C10J2300/0959—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
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • 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
    • C10J2300/1687—Integration of gasification processes with another plant or parts within the plant with steam generation
    • 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

Definitions

  • the present invention is directed to a method for the production of hydrogen gas. More particularly, the present invention is directed to a method for the production of hydrogen gas by steam reduction wherein steam is contacted with molten metal to form a metal oxide and a hydrogen-containing gas stream. The metal oxide can then be reduced back to the metal for further production of hydrogen gas.
  • the hydrogen gas can be used for the generation of energy and in various chemical processes, such as the treatment of coal and the production of ammonia.
  • Hydrogen (H 2 ) is a valuable commodity and specialty chemical that is critical to a number of industrial processes including the production of " ammonia and the refining of oil.
  • hydrogen can be converted directly to electricity in fuel cells at efficiencies approaching 80 percent.
  • Water is the sole by-product of hydrogen conversion in fuel cells, and toxic emissions are eliminated. For these reasons, hydrogen is widely considered the fuel of the future.
  • hydrogen gas can be produced from many different feedstocks such as natural gas, biomass or water using different techniques such as reformation, gasification or electrolysis.
  • the most common methods are steam methane reformation (SMR), coal gasification, steam reduction, biomass gasification and pyrolysis, and electrolysis.
  • Hydrogen produced by SMR is co-mingled with a significant quantity of carbon oxides that can only be partially removed by scrubbing or pressure swing adsorption, both of which are costly.
  • the carbon oxides remaining in SMR hydrogen are detrimental to the catalysts employed in fuel cells and in the production of ammonia (NH 3 ) from hydrogen.
  • Hydrogen production by coal gasification is another established commercial technology, but is only economically competitive when natural gas is prohibitively expensive.
  • steam and oxygen (O 2 ) are utilized in the coal gasifier to produce a hydrogen-containing gas.
  • High purity hydrogen can then be extracted from the synthesis gas by a water-gas shift reaction followed by removal of the carbon dioxide (CO 2 ) by pressure swing adsorption or scrubbing. Impurities such as acid gases must also be separated from the hydrogen.
  • Hydrogen can also be formed by the gasification of other hydrocarbons such as residual oil.
  • the steam reduction method utilizes the oxidation of a metal to strip oxygen from steam (i.e., steam reduction), thereby forming hydrogen gas.
  • This reaction is illustrated by Equation 1. xMe + yH 2 O ⁇ Me x O y + yH 2 (1)
  • the metal oxide must be reduced back to the metal using a reductant.
  • a reductant For example, carbon monoxide (CO) has an oxygen affinity that is similar to the oxygen affinity of hydrogen and they are equal at about 812°C. At temperatures above about 812°C, CO has a greater affinity for oxygen than does hydrogen.
  • the CO will reduce the oxide of Equation 1 back to the metal.
  • the function of the metal/metal oxide couple is to transfer oxygen from the steam to the reducing gas (CO) without allowing the steam/hydrogen of the hydrogen production step to contact the carbon monoxide/carbon dioxide of the metal oxide reduction step.
  • the metal and metal oxide are not consumed by the overall process.
  • Oxygen partial pressure (pO 2 ) relates to the facility with which the metal may be oxidized (e.g., by steam) and the oxide may be reduced (e.g., by CO).
  • a related mathematical expression is pH 2 O/pH 2 , which is proportional to the oxygen partial pressure.
  • an equivalent and inversely related quantity is the hydrogen fraction, expressed as: pH 2 (3) (pH 2 + pH 2 O)
  • Certain metals react strongly with water, releasing hydrogen.
  • metals include: lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), francium (Fr), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra), aluminum (Al), silicon (Si), phosphorus, (P), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), yttrium (Y), zirconium (Zr), niobium (Nb), lanthanum (La), hafnium (Hf), tantalum (Ta) and gallium (Ga).
  • the oxygen partial pressure in equilibrium with these metals and their oxides together is extremely low. Once the oxides are formed, they cannot be effectively reduced back to the metal by carbon monoxide. Conversely, there is another group of metals that produce insignificant quantities of hydrogen when reacted with water. Examples of these metals include: nickel (Ni), copper (Cu), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), mercury, (Hg), lead (Pb), bismuth (Bi), selenium (Se) and tellurium (Te).
  • the oxygen partial pressure in equilibrium with these metals and their oxides together is quite high. The oxides, therefore, can be easily reduced by carbon monoxide.
  • metals characterized by an oxygen affinity that is roughly the same as the oxygen affinity of hydrogen. Included in this intermediate group of metals are: germanium (Ge), iron (Fe), zinc (Zn), tungsten (W), molybdenum (Mo), indium (In), tin (Sn), cobalt (Co) and antimony (Sb). These are elements that readily produce hydrogen from steam wherein the resulting oxide can be reduced by carbon monoxide. That is, these metals have an oxygen affinity such that their equilibrium pH 2 O/pH 2 is low enough to be practical for the production of hydrogen, yet the metal oxide is readily reduced by carbon at normal pyrometallurgical temperatures (e.g., about 1200°C).
  • U.S. Patent No. 1,345,905 by Abbott discloses the production of hydrogen from steam by oxidation of iron using multiple reactors. In a four- reactor configuration, one reactor is used for iron oxidation (hydrogen production), two are used for iron oxide reduction and the fourth is used for preheating the reactants. Gas flows can be switched among the reactors for the continuous production of hydrogen.
  • U.S. Patent No. 4,343,624 by Belke et al. discloses a 3-stage hydrogen production method and apparatus utilizing steam reduction as the hydrogen source.
  • a low BTU gas containing hydrogen and carbon monoxide is formed from a feedstock such as coal.
  • the low BTU gas is then reacted in a second stage with magnetite to form iron, carbon dioxide and steam.
  • the steam and iron are then reacted in a third stage to form hydrogen gas and magnetite.
  • the magnetite can be returned to the second stage for use in the reduction reaction, such as by continuously returning the magnetite to the second stage reactor via a feed conduit. At least one of the stages takes place in a rotating fluidized bed reactor.
  • U.S. Patent No. 4,555,249 by Leas discloses a gas fractionating unit that contains a reagent powder, such as an iron alloy, having a significant weight difference between the reduced form and the oxidized form.
  • the unit includes two zones for containing the reagent powder, an oxidation zone and a reduction zone, wherein hydrogen gas is extracted from the oxidation zone.
  • the weight of the powder increases and the change in weight is utilized to transfer the reduced powder to the oxidation zone while moving the oxidized powder to the reduction zone.
  • the biosyngas which includes H 2 , CO, H 2 O, and CO 2 with traces of N 2 and CH 4 , is used to reduce magnetite to iron.
  • the iron is then cooled and fed to a hydrogen gas generator where the iron is contacted with steam to form hydrogen by steam reduction.
  • the iron oxide is then cooled and returned to the metal oxide reduction reactor for reaction with the biosyngas.
  • Disadvantages of the steam reduction process utilizing iron include that the reaction of solid iron with steam produces an oxide layer, which inhibits additional steam from reacting with iron beneath the oxide layer and therefore the rate of reaction is limited by the rate of gas-diffusion through the oxide layer. Also, the rate of reaction is dependent upon the surface area of the iron available for the reaction. High surface area, however, is equated with small particle size, and small particles are expensive to process. Further, there are difficulties associated with reducing the iron oxide.
  • One method for reducing the iron oxide includes smelting of the oxide and therefore carries the disadvantage of high temperature due to the high melting point of iron (1538°C). In another method, the iron oxide is reduced to the metal in the solid state by carbon and/or reducing gas.
  • U.S. Patent No. 1,050,902 by Acker discloses the use of tin or zinc in a steam reduction process to form hydrogen and the regeneration of the metal by reduction of the metal oxide with coal.
  • U.S. Patent No. 3,821 ,362 by Spacil illustrates the use of Sn/SnO 2 to form hydrogen. Molten tin is atomized and contacted with steam to form SnO 2 and hydrogen gas. The SnO 2 is then contacted with a producer gas composed of H 2 , N 2 and CO, which is formed by contacting powdered coal with air. The SnO 2 is reduced to liquid tin, which is then transferred back to the first reactor.
  • a similar method for hydrogen production is illustrated in U.S. Patent No. 3,979,505 by Seitzer.
  • a dissolved liquid The effect of employing a dissolved liquid is that the oxygen partial pressure is increased (i.e., the hydrogen fraction is decreased) and less hydrogen is produced.
  • suitable solvents for the dissolved liquids may be selected from one or more of the non-reactive metals that have a high oxygen partial pressure, for example copper, lead and nickel. It is also disclosed that tin, a reactive metal, can serve as a solvent for indium.
  • thermodynamics dictate that a large excess of steam is required in order for the reaction to proceed.
  • the need for a large excess of steam creates a number of problems. Heat must be recovered for the process to be economical, including the heat of evaporation of the water to form the steam. Technically, most of this heat recovery is possible, although doing so requires additional capital. Also, a large excess of steam must physically contact the tin, such as by being bubbled through the liquid tin. Practically, such contact is possible only if the steam and reactor are operated under considerable pressure and, generally, processes that operate at very high pressures are quite expensive.
  • the production of one ton of hydrogen requires the reaction of 8.94 tons of steam with 29.4 tons of tin (stoichiometric calculations). Additionally, the production of one ton of hydrogen at 900°C requires 35J tons of steam to satisfy the thermodynamic requirement. If this total steam requirement (44.6 tons) is passed through the stoichiometric quantity of tin at atmospheric pressure, the velocity of the steam through the space that otherwise would be occupied by the tin must be in excess of 100 meters per second. This yields a nominal residence time of less than 1/100 of a second. Even if system pressure is raised to 100 atmospheres, only 0.85 seconds are available for the reaction to approach equilibrium.
  • the steam/tin process fails the economic viability requirement because of poor kinetics at low temperatures (below about 800°C) and poor thermodynamics at higher temperatures.
  • the consequence of poor thermodynamics is the requirement that large amounts of steam be processed through the molten metal, which increases the difficulty and cost of the process. Due to these and other factors, the present inventors are not aware of a commercial facility that is practicing the steam reduction method, despite the high demand for hydrogen gas.
  • a method for the production of a hydrogen-containing gas stream includes the steps of generating steam and contacting the steam with a molten metal mixture having at least about 20 weight percent iron dissolved in a diluent metal, wherein at least a portion of the iron is oxidized to a metal oxide and at least a portion of the steam is reduced to form a hydrogen- containing gas stream.
  • the diluent metal is tin.
  • a method for the production of a hydrogen-containing gas wherein steam is generated and is contacted with a molten metal mixture at a temperature of at least about 1100°C.
  • the molten metal mixture includes a reactive metal dissolved in a diluent metal wherein the reactive metal is oxidized and the steam is reduced to form hydrogen.
  • the use of temperatures of at least about 1100°C for the molten metal mixture enables the production of hydrogen under favorable thermodynamic and kinetic conditions.
  • a method for the production of a hydrogen-containing gas stream includes the steps of generating steam, contacting the steam with a molten metal mixture in a reactor, wherein reactive metal-containing particles are dispersed in the molten metal mixture.
  • the reactive-metal containing particles advantageously supply additional reactive metal to the molten metal mixture as the reactive metal is oxidized by the steam.
  • a method for the production of a hydrogen-containing gas stream includes the steps of contacting steam with a molten metal mixture in a reactor, the molten metal mixture including a reactive metal dissolved in a diluent metal.
  • the reactive metal is oxidized to a metal oxide by the steam.
  • the metal oxide is then reduced back to the reactive metal within the reactor.
  • the hydrogen-containing gas stream produced in according with the foregoing can be used in a variety of processes and is particularly suited to the treatment of carbon-bearing substances such as coal or waste products and to the manufacture of chemicals such as ammonia.
  • Fig. 1 illustrates a binary phase diagram for a tin-iron metal mixture that is useful in accordance with the present invention.
  • Fig. 2 illustrates the production rate of hydrogen as a function of iron content in the reactor according to an embodiment of the present invention.
  • Fig. 3 illustrates the production rate of hydrogen as a function of iron content and reaction temperature according to an embodiment of the present invention.
  • Fig. 4 illustrates a reactor operating in steam reduction mode according to an embodiment of the present invention.
  • Fig. 5 illustrates a reactor operating in metal oxide reduction mode according to an embodiment of the present invention.
  • Fig. 6 illustrates a process flow for continuous hydrogen production according to the present invention.
  • Fig. 7 illustrates a process flow for the treatment of coal or other organic-containing feed material according to the present invention.
  • Fig. 8 illustrates a process flow for the production of ammonia according to the present invention.
  • hydrogen gas (H 2 ) is formed by contacting steam (H 2 O) with a molten metal mixture that includes at least a first reactive metal that is at least partially dissolved in at least one diluent metal.
  • the diluent metal may also be reactive with the steam, but is, by definition, less reactive with steam than the reactive metal.
  • the oxygen from the steam preferentially reacts with the reactive metal to oxidize the reactive metal to a metal oxide and reduce a portion of the steam to form a hydrogen-containing gas stream that will also include excess steam.
  • hydrogen production continues until the concentration of the dissolved reactive metal in the molten metal mixture is reduced to a minimum concentration that is dictated by economics, at which point the injection of steam is terminated. Then, a reductant is introduced into the reactor under conditions of intense mixing, such as by using a top-submerged lance. Under these conditions, the metal oxide is chemically reduced back to the reactive metal, which re-dissolves into the molten metal mixture.
  • a molten metal mixture that includes at least a first reactive metal and at least a first diluent metal.
  • the reactive metal is, by definition, more reactive with steam than the diluent metal.
  • the reactive metal preferably has an oxygen affinity that is similar to the oxygen affinity of hydrogen and reacts with the steam to form a metal oxide.
  • the reactive metal can be selected from germanium (Ge), iron (Fe), zinc (Zn), tungsten (W), molybdenum (Mo), indium (In), tin (Sn), cobalt (Co) and antimony (Sb).
  • the molten metal mixture can include one or more reactive metals.
  • the reactive metal preferably should: (1) be soluble in the diluent metal(s); (2) have a very low vapor pressure at the oxidation/reduction temperature(s); and (3) produce one or more oxides when reacted with steam that also has a very low vapor pressure at the oxidation/reduction temperature(s).
  • a particularly preferred reactive metal according to the present invention is iron and according to one embodiment the reactive metal in the molten metal mixture consists essentially of iron.
  • the reactive metal is at least partially dissolved within a second metal, or mixture of metals.
  • the metal into which the reactive metal is dissolved is referred to herein as the diluent metal.
  • the diluent metal may also be reactive with steam, in which case it can be selected from the group of reactive metals disclosed hereinabove, provided that the diluent metal is less reactive than the reactive metal.
  • the diluent metal may be selected from the metals wherein the oxygen partial pressure (pO 2 ) in equilibrium with the metal and oxides together is relatively high.
  • diluent metal More than one diluent metal can be utilized in the molten metal mixture.
  • the diluent metal should not be a metal wherein the oxygen partial pressure in equilibrium with the metal and metal oxide together is extremely low.
  • the diluent metal should: (1) combine with the reactive metal to be liquid in the temperature range of 400°C to 1300°C; (2) have a very low vapor pressure over this temperature range; and (3) have the capacity to hold the reactive metal in solution.
  • the diluent metal is tin and in one embodiment, the diluent metal consists essentially of tin.
  • the molten metal mixture can also include additional diluent metals, particularly copper and nickel.
  • a particularly preferred molten metal mixture for steam reduction according to the present invention includes iron as the reactive metal and tin as the diluent metal.
  • Iron has a high solubility in molten tin at elevated temperatures and the melting temperature of the mixture is substantially lower than the melting temperature of pure iron (1538°C). Although tin is also reactive with steam, it is less reactive than iron.
  • thermodynamic steam requirement for tin at 660°C is approximately equal to the thermodynamic steam requirement for iron at 1200°C.
  • the production of hydrogen using tin as a reactive metal at 660°C is not practical since the kinetics (i.e., the reaction rate) are very poor and therefore very long residence times (i.e., the time that the steam is in contact with the tin) are required.
  • Table 2 illustrates the nominal residence times of the steam at a production rate of 4.439 tons of hydrogen per hour.
  • a reactive metal dissolved in a diluent metal in accordance with the present invention is that the residence time of the steam within the reactor is increased with respect to the mass of the reactive metal. That is, a given mass of iron will occupy a first volume as pure iron, but the same mass of iron will be distributed over about twice the volume if the iron is in a 50 weight percent mixture with a diluent metal such as tin.
  • Fig. 1 illustrates a phase diagram for iron and tin adapted from Hari Kumar, K.C., et al., Calphad. 20, 2, 139-149 (1996). It can be seen from Fig.
  • one effect of adding iron (the reactive metal) to tin (the diluent metal) is to substantially lower the melting temperature of the iron.
  • the liquidus of the metal mixture decreases from 1538°C (pure iron) to about 1134°C at a melt composition of about 48.7 weight percent tin and 51.3 weight percent iron.
  • the metal mixture be maintained at a temperature above the liquidus line AC of Fig. 1 (e.g., above 1134°C).
  • a metal-steam reaction temperature that is too high, however, adds significantly to the operating costs.
  • the melt should be maintained at a temperature above the liquidus temperature of about 1134°C, more preferably at a temperature of at least about 1200°C.
  • the temperature should not be greater than about 1500°C and more preferably is not greater than about 1400°C.
  • a particularly preferred temperature range for the completely molten tin/iron metal mixture is from about 1200°C to 1300°C.
  • the metal mixture initially include at least about 3 weight percent iron in the molten metal mixture, more preferably at least about 10 weight percent iron, even more preferably at least about 20 weight percent iron and even more preferably at least about 50 weight percent iron in the molten metal mixture.
  • the amount of iron in the molten metal mixture should preferably not exceed about 85 weight percent and more preferably should not exceed about 80 weight percent.
  • the balance of the metal mixture in a preferred embodiment consists essentially of tin. Accordingly, the amount of tin in the system is preferably not greater than about 97 weight percent, more preferably is not greater than about 90 weight percent and even more preferably is not greater than about 80 weight percent.
  • the molten metal mixture preferably includes at least about 15 weight percent tin and more preferably at least about 20 weight percent tin.
  • insoluble phases such as in the form of particles can be dispersed within the molten metal mixture.
  • This assembly of a molten metal mixture and insoluble phase is termed a slurry.
  • the steam is contacted with a slurry that includes a molten metal mixture and a solid second phase, wherein the solid second phase includes reactive metal-containing particles and is adapted to supply additional reactive metal to the molten metal mixture.
  • the particles are metallic particles (e.g, not oxide particles).
  • the slurry could include iron-rich metallic particles within an iron/tin melt that is saturated with iron.
  • dissolved iron is removed from the molten metal mixture by oxidation of the iron and additional iron from the iron-rich particles dissolves in the molten metal to keep the molten metal portion of the slurry saturated with iron.
  • the composition within the two-phase region defined by point A (83.3 wt.% Fe at 1134°C), point B (84 wt.% Fe at 1134°C), point C (12 wt.% Fe at 895°C) and point D (3 wt.% Fe at 895°C) includes an iron/tin melt with about 3 wt.% to 84 wt.% total iron, with a portion of the iron as iron-rich metallic particles dispersed in the melt.
  • the molten metal mixture will include about 4 wt.% dissolved iron in the system. As the dissolved iron is oxidized, additional iron metal from the iron- rich particles will dissolve to maintain 4 wt.% dissolved iron in the melt. The activity of the iron, therefore, remains unchanged as a consequence of dissolution of iron-rich particles.
  • the slurry comprised of the molten metal mixture and iron-containing particles, is maintained at a temperature below the liquidus temperature of 1134°C and is at least about 895°C, more preferably from about 900°C to about 1134°C.
  • One advantage of such a method is that the activity of the iron remains constant and in fact is close to one, and therefore the production rate of hydrogen remains constant and maximized throughout the steam reduction process.
  • thermodynamic relationship exists between the partial pressure of hydrogen in the off-gas, the reaction temperature and the weight percent iron in the molten metal composition.
  • the thermodynamic quantity referred to as the "activity" of iron, varies as a function of iron concentration and strongly influences the ratio of hydrogen to water in the off-gas.
  • the production of hydrogen is maximized by operating within phase regions that establish a high iron activity over a wide composition range through the use of a second phase in equilibrium with the reacting phase. This applies both to the liquid-liquid region, above the line AC in Figure 1 , as well as the solid-liquid region, below the line AC and to the right of the line AB.
  • the present invention does not exclude operation in the iron-rich liquid phase.
  • Fig. 2 illustrates the relationship between the level of hydrogen in the off-gas as a function of iron content in the molten metal mixture.
  • Fig. 2 was calculated based on thermodynamics of the reaction at 1225°C. It is evident that the hydrogen production rate rapidly decreases as the iron content drops from 20 weight percent to 10 weight percent.
  • Fig. 3 illustrates the hydrogen production as a function of temperature and iron content.
  • the production capacity for hydrogen is impaired since: (1) the pH 2 /pH 2 O drops significantly; and (2) only short periods of time are available before gas flows (i.e., steam and metal oxide reductant) have to be switched.
  • steam is contacted with the molten metal mixture to generate hydrogen and to convert the reactive metal to a metal oxide.
  • the steam is contacted with the molten metal mixture in a manner that promotes good mixing and contact with the molten metal mixture.
  • the steam can be contacted with the molten metal mixture by injection through a top- submerged lance or through a porous ceramic diffuser disposed at the bottom of a reactor. Preferred reactor systems in this regard are discussed below.
  • the reactor temperature can be controlled to maintain a substantially constant temperature by controlling the incoming steam temperature and quantity and/or by adding oxygen to the reactor.
  • the steam reduction reactor can be maintained at an elevated pressure if necessary for adequate residence time in the reactor, as is discussed above. For example, it may be desirable to maintain an elevated pressure, such as at least about 15.3 atmospheres (225 psi). .A slightly elevated pressure can also be beneficial for providing a hydrogen gas stream with sufficient pressure for transmission (e.g., a line pressure of about 200 psi). However, significantly increased pressure adds to capital cost and therefore the pressure in the steam reduction reactor is preferably not greater than about 600 psi and more preferably is not greater than about 225 psi. According to the present invention, a slag layer is maintained over the molten metal mixture. A slag layer provides a number of advantages, including preventing the iron oxide from exiting the reactor.
  • the temperature in the steam reduction reactor should be sufficient to maintain the slag layer that forms over the metal mixture in the molten state over a range of compositions.
  • a decrease will occur in the concentration of the reactive metal in the metal mixture and the metal mixture should remain molten as the reactive metal is oxidized.
  • the range of preferred slag compositions required to ensure adequate slag fluidity and reactivity, and prevent foaming can be adjusted, as necessary, for a given temperature.
  • fluxes can be added to the reactor to adjust the properties of the slag.
  • One flux system is indicated by the liquid surface of SiO 2 , FeO, CaO, MgO, Na 2 O and K 2 O.
  • sulfur and other cations may be incorporated in this or other slags to secure satisfactory slag chemistry.
  • the metal oxide (e.g., wustite and/or magnetite) that is generated by the steam reduction can advantageously be trapped (dissolved or suspended) in the slag layer within the reactor.
  • the iron oxide is incorporated into the slag, which is lighter than the metal mixture. Therefore, as the dissolved iron is depleted from the molten metal mixture, the iron oxide rises through the molten metal and contributes to the slag layer on top of the molten metal. It is an advantage of this embodiment of the present invention that the oxide formed upon reaction of the reactive metal with the steam has a density that is less than the density of the molten metal mixture, whereby the oxide rises to the slag layer.
  • the metal oxide is at least about 10 percent less dense than the molten metal mixture. This also enables the metal to sink from the slag layer to the molten metal mixture upon reduction of the metal oxide. As is discussed above, this accumulation of iron oxide in the slag may require the addition of a flux such as SiO 2 , FeO, CaO, MgO, Na 2 O, K 2 O or mixtures thereof to maintain the slag in the preferred condition with respect to viscosity, reactivity, foaming, and the like.
  • a flux such as SiO 2 , FeO, CaO, MgO, Na 2 O, K 2 O or mixtures thereof to maintain the slag in the preferred condition with respect to viscosity, reactivity, foaming, and the like.
  • the molten metal mixture must be contained within a suitable reactor to maintain suitable reaction conditions. Further, the reactants should be provided in a manner conducive to good mixing and high contact surface area. High-temperature reactors suitable for establishing good gas/liquid contact are utilized in the chemical, and especially metallurgical industries.
  • a preferred reactor system according to the present invention utilizes a top-submerged lance to inject the steam into the molten metal.
  • Such reactors have been used in the commercial production of tin from tin ore (cassiterite).
  • Examples of reactors utilizing a top-submerged lance to inject reactants are disclosed in U.S. Patent No. 3,905,807 by Floyd, U.S. Patent No. 4,251 ,271 by Floyd, U.S. Patent No. 5,251,879 by Floyd, U.S. Patent No. 5,282,881 by Baldock et al., U.S. Patent No. 5,308,043 by Floyd et al. and U.S. Patent No. 6,066,771 by Floyd et al. Each of these U.S.
  • Such reactors are capable of injecting reactants (e.g., steam) into the molten metal at extremely high velocities, approaching Mach 1 , thereby promoting good mixing of the reactants.
  • reactants e.g., steam
  • a reactor incorporating a lance for injection of steam is illustrated in Fig. 4.
  • the reactor 400 includes refractory sidewalls 402 that are adapted to contain the molten metal mixture 404. Heating means (not illustrated) can be provided, if necessary, to maintain the temperature within the reactor 400.
  • a top-submerged lance 408 is disposed through the reactor top wall 412 and is adapted to inject steam into the metal mixture 404 at a high velocity.
  • the top-submerged lance 408 terminates and injects steam below the surface of the slag layer 406 and near the interface of the molten metal mixture 404 and the slag layer 406.
  • steam is introduced through the lance 408
  • iron from the metal mixture 404 oxidizes to iron oxide.
  • the iron oxide rises and accumulates in a slag layer 406.
  • a gas product 416 including hydrogen gas co-mingled with steam is extracted from outlet port 410, after which the excess steam can be condensed to form a substantially pure hydrogen gas stream.
  • the steam reduction process is continued until the rate of hydrogen production decreases to a sufficiently low level.
  • a reductant is introduced into the reactor containing the molten metal mixture and the slag to reduce the iron oxide back to the metal.
  • the point at which the steam reduction process is terminated and the metal oxide reduction process is begun can readily be determined based on economic considerations. That is, at some point the hydrogen production rate in the steam reduction reactor will decrease to a point that is economically advantageous to terminate the steam reduction and begin regeneration of the metal from the metal oxide.
  • the iron oxide in the slag is reduced and returned to the melt as iron.
  • This is achieved by lowering the oxidation potential of the system by introducing a reductant to the reactor.
  • the reductant lowers the oxidation potential of the system thereby driving the iron back into the melt.
  • the reductant can be carbon monoxide, coal and/or other carbon source.
  • the oxidation potential of the system is lowered by injecting particulate carbon, hydrocarbon or liquid hydrocarbon into the slag with an oxygen-containing gas under conditions of intense mixing.
  • the particulate carbon or hydrocarbon can include coke, coal or other organic material.
  • a liquid hydrocarbon, such as #6 or other oil can also be used. Waste materials such as scrap tires can also be used. Scrap tires can advantageously supply additional iron to the reactor to make up for incidental losses of the iron.
  • a top-submerged lance is preferred for introducing the air or other oxygen-containing gas into the reactor in a manner that insures good mixing.
  • the reactor Prior to injection of a reducing composition, the reactor may be purged, such as with steam, to remove any hydrogen from the reactor. After the reductive cleaning of the slag is complete, the reactor may again be purged, with air or steam, for the purpose of removing any carbon that may be dissolved in the iron and/or for the purpose of removing any other tramp elements that may be in either the melt or slag, that otherwise would contaminate the hydrogen produced when steam is re-introduced into the reactor.
  • a reductant derived from a carbon source such as coal and an oxygen source such as air or oxygen-enriched air is injected into the molten metal mixture and slag layer.
  • the coal can be injected through the top-submerged lance with the air, or can be added separately. It is an advantage to use coal as the reductant source, because, compared to oil and gas, it is both abundant and relatively inexpensive.
  • Coal can also supply iron to the reactor to make-up for iron that is lost during processing. Scrap tires and other waste materials can also supply some iron.
  • the metal oxide reduction process is continued until a sufficient amount of iron metal has been re-dissolved in the molten metal mixture.
  • the reaction conditions when operating in the mode to reduce the metal oxide to metal are substantially identical to the conditions during steam reduction. That is, it is preferred that the temperature and pressure of the metal oxide reduction reactor are the same or very similar to the temperature and pressure of the steam reduction reactor.
  • the temperature is preferably at least above the liquidus (e.g., about 1134°C for the tin/iron system) and more preferably is at least about 1200°C.
  • the temperature does not exceed about 1400°C and more preferably does not exceed about 1300°C.
  • the temperature is about 1200°C in both reactors and the pressure is slightly above atmospheric pressure in the steam-reduction reactor and slightly below atmospheric pressure in the metal oxide reduction reactor.
  • a reactor 500 operating in metal oxide reduction mode is illustrated.
  • the reactor is physically identical to the steam reduction reactor illustrated in Fig. 4, and includes insulated side- walls 502.
  • the metal mixture 504 initially includes predominantly tin, although some iron will still be present.
  • the slag layer 506 includes the iron oxide that was formed during the steam reduction process described above.
  • Carbon 514 such as in the form of coal, can be injected through the lance 508 that is disposed through the reactor top wall 512, along with an oxygen source such as oxygen-enriched air.
  • an oxygen source such as oxygen-enriched air.
  • carbon can be added to the reactor separately and the gaseous oxygen source can be injected through the lance.
  • ash formed from coal will also be incorporated into the slag.
  • the slag which can be pozzolanic when CaO is added as a flux, can be periodically or continuously withdrawn, ground and can be used as a replacement for Portland cement.
  • the slag may be partially granulated by quenching with water. The granulated slag can then be drained and disposed to waste.
  • Impurities in the coal for example sulfur, chlorine and fluorine
  • gaseous species such as sulfur dioxide, hydrogen chloride and hydrogen fluoride
  • the sulfur can be converted into ammonium sulfate, which is useful as a fertilizer compound, and the remaining impurities reacted to render them solid so that they can be directed to waste.
  • Carbon dioxide and nitrogen from the air and fuel are the only gaseous effluents from the metal oxide reduction process.
  • Controlling the oxidation potential of the slag controls the amount of iron oxide in the slag that is reduced to iron that subsequently reports to the melt during metal oxide reduction. This can be achieved by controlling the relative amount of coal (or other carbonaceous fuel) and oxygen that is injected into the slag system.
  • Some iron oxide will be dissolved in the slag, the amount determined by the slag chemistry. Another portion of the iron oxide may be present in the slag as slurried particulate solids if the slag is saturated in iron oxide.
  • reactors can be operated in parallel for the production of hydrogen in a continuous manner.
  • iron is depleted from the molten metal mixture in the steam reduction reactor, and as the iron oxide is reduced to metal in the metal oxide reduction reactor, their functions can be reversed by switching the flows into and out of the reactors.
  • the functionality of the reactors is reversed, there is no movement of metal or metal oxide into or out of the reactors. This has a significant and favorable impact on cost.
  • the reactors can utilize a single top-submerged lance for the injection of steam or the injection of carbon and oxygen to form carbon monoxide.
  • a reactor with two lances one for steam and another for carbon/oxygen
  • Additional ports for the injection of steam can also be provided, such as on the sides of the reactor.
  • FIG. 6 A flowsheet illustrating the continuous generation of hydrogen using two reactors in accordance with the present invention is illustrated in Fig. 6.
  • the hydrogen generation process employs two reactors 602 and 604 wherein one of the reactors operates in steam reduction mode while the other operates in metal oxide reduction mode. As illustrated in Fig. 6, reactor 602 is operating in steam reduction mode and generates hydrogen and reactor 604 is operating in metal oxide reduction mode.
  • Steam is provided by heating water in waste heat boilers 606 and 610. Prior to heating in the boilers, the water should be subjected to purification 612 such as by using reverse osmosis and de-ionization to remove contaminants that can affect boiler operation or introduce impurities into the hydrogen product gas. Steam is produced in the boilers and is provided to the reactor 602 at a super-heated temperature that is sufficient to maintain isothermal conditions within the steam reduction reactor 602 at the operating temperature, e.g., about 1200°C.
  • the steam is injected into the reactor 602 through a through a top- submerged lance 608.
  • the top-submerged lance provides good mixing and a high contact surface area between the steam and the molten metal mixture to promote the steam reduction/metal oxidation reaction.
  • the reactor 602 is sealed to prevent egress of hydrogen and steam from the reactor. Also, the reactor may be placed under modest pressure to provide a sufficient contact time for the steam and to deliver the hydrogen under pressure. Other materials can be added to the reactor if necessary. For example, fluxes 614 can be added to control the properties of the slag layer that forms above the molten metal mixture as the steam reduction reaction oxidizes the metal.
  • Possible fluxes include SiO 2 , FeO, CaO, MgO, Na 2 O or K 2 O. Additionally, other materials such as tin compounds, cassiterite ore or other materials such as iron compounds or ore may be added to make-up for losses of metal values. According to a particularly preferred embodiment, cassiterite ore (SnO 2 ) is injected into the reactor to make-up for tin losses.
  • a hydrogen-containing gas that includes hydrogen and excess steam is removed from the reactor 602.
  • the hydrogen-containing gas can be passed through the waste heat boiler 606 to provide heat for additional steam, thereby conserving heat values.
  • the hydrogen-containing gas stream gas can also include some contaminants, such as the sub-oxide of tin oxide (SnO), the hydrated sub-oxide of tin (SnO 2 H 2 ), and entrained particulates of (frozen) slag which volatilize or are ejected from the molten metal bath and slag, and such contaminants can be removed in a baghouse 616.
  • the volatile tin compounds can be condensed from the gas stream and, along with particulate slag, captured either in the waste heat boiler or in the baghouse.
  • these materials can be pelletized 618 and optionally provided to either reactor 602 operating in steam reduction mode or reactor 604 operating in the metal oxide reduction mode for recovery of metal values and control of the slag chemistry.
  • the hydrogen gas stream is treated in a condenser 620 and/or chiller (not shown) to condense the excess steam from the hydrogen gas stream and form a high purity hydrogen gas stream 622. Water condensed from the hydrogen gas stream can be recycled for additional steam production.
  • metal oxides are reduced in reactor 604.
  • the metal oxides are reduced by a reductant such as CO, which can be formed by injecting coal 624 (or other carbonaceous material) and oxygen 626 through a top-submerged lance 628.
  • a reductant such as CO
  • the top-submerged lance 628 provides good mixing and contact surface area between the reactants.
  • the oxygen-containing gas should also be injected using a top-submerged lance or similar device. It is possible to add the particulate coal to the reactor 604 by other means, such as by simply dropping the coal into the reactor.
  • the slag layer can be a salable pozzolanic by-product.
  • other materials such as fluxes can be injected into the reactor 604, for example to control the properties of the slag such as slag fluidity or tendency to foam.
  • the off-gas from the metal oxide reduction reactor 604 can include carbon dioxide, nitrogen and some contaminants from the coal such as sulfur. Heat from the off-gas can be conserved in the waste heat boiler 610 where steam is generated. The gas stream can then be treated in a bag-house 630 to remove particulate contaminants. The remaining gases can be treated in a limestone scrubber 632 to form environmentally benign stack gases and gypsum from the sulfur that originates from the coal. Alternatively, the sulfur can be treated with anhydrous ammonia to form ammonium sulfate, a useful compound for fertilizing soil.
  • the reactors can be purged to remove residual gases and contaminates, if any. Accordingly, hydrogen gas can be produced in a substantially continuous manner.
  • the hydrogen gas that is produced according to the present invention preferably can have a high purity.
  • the gas stream includes at least about 30 volume percent hydrogen with the remainder composed primarily of water in the form of steam.
  • the purity of the hydrogen is greater than about 99% or more preferably greater than about 99.9% after removal of the residual water in a condenser.
  • the hydrogen gas does not require separation from other gas species such as carbon monoxide and carbon dioxide as is the case for hydrogen produced by either steam reformation of methane or coal gasification, which two methods cover the bulk of hydrogen currently produced.
  • carbon species e.g., CO
  • the gas can be extracted and burned for fuel value until the hydrogen purity reaches a sufficient level. That is, any dissolved carbon will preferentially react with the steam to form CO before large amounts of hydrogen are produced by oxidation of the reactive metal.
  • the method and apparatus of the present invention enable the production of high volumes of pure hydrogen gas at a low cost.
  • Hydrogen gas has a fuel value of about 51 ,623 BTU/lb and is useful as a component of a combustion gas. Hydrogen can also be used for hydrogenation processes and in semiconductor fabrication. Further, hydrogen is used directly as a fuel in a fuel cell, such as a proton exchange membrane fuel cell (PEMFC).
  • a fuel cell such as a proton exchange membrane fuel cell (PEMFC).
  • One aspect of the present invention is directed to the treatment of coal to produce energy value from the coal while minimizing the discharge into the atmosphere of harmful by-products that are typically associated with the conversion of coal to energy.
  • the method enables the extraction of the available energy content from the coal in the form of a medium BTU gas while reducing the atmospheric discharge of harmful by-products.
  • One of the problems associated with the use of coal is that the coal must typically be cleaned or purged of its mineral matter content, including sulfur; notwithstanding, there usually is an additional need for post- combustion gas scrubbing to meet environmental standards.
  • the coal feedstock can include low-grade coal including high-sulfur coal and other low-grade coals.
  • low-grade coals are readily available and are available at low cost.
  • the term low-grade coal refers to coal having a sulfur content in excess of 2 weight percent and an ash content in excess of about 10 weight percent.
  • the method of the present invention includes providing the coal feedstock to a hydrogenation unit and contacting the coal feedstock with a treatment gas that includes H 2 produced in accordance with the foregoing.
  • the hydrocarbons in the coal that are volatile will react with hydrogen to form methane (CH ).
  • the exit gases from the hydrogenation unit can be scrubbed if necessary to produce a clean, high BTU gas product.
  • this gas product can be burned in a combined cycle generator taking advantage of the generator's high thermal-to-electric conversion efficiency.
  • Another portion of the gas product can be combusted in a conventional boiler with the non- volatile carbon that is formed in the hydrogenation unit.
  • the carbon will be essentially free of sulfur because the hydrogen treatment gas is a strong desulfurizing agent.
  • another portion of the carbon that is produced in the hydrogenation unit can be recycled back to the metal oxide reduction step where the metal oxide is reduced back to the reactive metal.
  • the coal is advantageously partitioned into the volatiles (treated with hydrogen) and fixed carbon (reacted with oxygen).
  • coal 702 is first conveyed to a pre-heater 704 where the temperature of the coal is raised.
  • the heated coal is then conveyed to a hydrogenation unit 706 where the coal is contacted with hydrogen gas 705 that has been formed in accordance with the method described above.
  • the hydrogenation unit 706 can be a fluidized bed reactor or other reactor that is suitable for the treatment of particulate coal.
  • the unit is preferably operated at ambient or near ambient pressure, such as a pressure of not greater than about 5 psi.
  • the hydrogenation unit 706 is not operated at a substantial elevated pressure. Grossly elevated pressures do produce additional methane, a gas with a very high BTU content. For the purpose of converting coal to clean energy, however, it is more cost effective to produce the combustible gases carbon monoxide and hydrogen from the coke, a residue from the hydrogenation step. Gases derived from the reaction between coke and steam (CO & H 2 ) are combined with the methane from hydrogenation to produce a valuable medium BTU gas.
  • the reaction in the hydrogenation unit 706 is preferably carried out at a temperature of at least about 700°C and preferably not greater than about 1100°C, such as from about 800°C to about 900°C.
  • Coal is a complex mixture of chemical compounds that are primarily organic compounds. While coal is predominately a hydrocarbon, impurities such as sulfur and nitrogen are trapped in the coal. These impurities, released as the coal is combusted, lead to the formation of sulfuric acid and nitric acid if released into atmosphere and must be scrubbed from the off-gas in a typical coal-based power plant. Further, when the coal is burned, the carbon combines with oxygen from the atmosphere and forms CO 2 , a well- known greenhouse gas that traps the earth's heat.
  • the coal 702 when the coal 702 is treated in the hydrogenation unit 706 with the hydrogen treatment gas 705, the coal is not burned. Rather, it is heated to remove the volatile components in the coal.
  • These volatile components advantageously form a high BTU product gas comprised largely of methane.
  • the residue from the removal of the volatiles is purified by the action of the hydrogen, including removal of sulfur and nitrogen, and the resulting purified carbon (i.e., coke 707) can: (a) be combusted in a conventional boiler with methane and without excessive formation of detrimental by-products; (b) be converted to carbon monoxide and hydrogen which gases are added to the methane from the hydrogenation reactor 706 to produce a medium BTU gas for combustion; (c) be activated by oxygen and steam to form an activated carbon 716; or (d) some combination of the above.
  • the methane-containing gas stream that is produced by the hydrogenation reaction can be passed through a waste heat boiler 708 to conserve heat value from the gas stream. Thereafter, a limestone, lime or ammonia scrubber 710 can be used to remove contaminants from the methane-containing gas stream such as sulfur, thereby producing a high purity methane-containing gas 712. Sulfur in the coal will form hydrogen sulfide (H 2 S) that can be scrubbed from the methane gas stream. It is advantageous to scrub the methane gas stream prior to combustion, if any, since combustion creates a higher volume gas stream.
  • the methane gas can be combusted on-site to generate electricity, or can be treated to remove CO (if any) and provided to end-users as a pipeline gas. Further, a portion of the CH can be cycled back to the other unit operations to provide process heat. For example, a portion of the CH 4 can be diverted to the steam superheater 714.
  • the hydrogenation treatment advantageously removes the impurities in the coal 702 forming a clean coke product 707.
  • the coke product 707 can be treated in an activation/oxidation unit 718 if necessary, to form: (a) clean activated carbon 716, (b) a clean coke (c) a mixed gas comprised of hydrogen and carbon monoxide or (d) some combination of the foregoing.
  • a portion of the coke 707 can be cycled back to the metal oxide reduction reactor (Fig. 5) for the reduction of the metal oxide.
  • the carbon will be converted to CO and the ash incorporated into the slag that can be withdrawn periodically.
  • the remaining coke from the hydrogenation unit 706 can be burned in a conventional boiler with methane for additional energy production.
  • a portion of the hydrogen gas 705 that is produced by the reduction of steam can be diverted from the hydrogenation unit 706 and used directly as a fuel source, either alone or in combination with the methane gas.
  • the hydrogen can be directly fired in a boiler, internal combustion engine or fuel cell.
  • the primary feedstock to the hydrogenation unit of the present invention can be a low-grade coal as well as a high-grade coal.
  • low-grade coal feedstock can be advantageous since they are generally available at a low cost.
  • the coal feedstock is a low-grade coal having at least 1 weight percent sulfur, more preferably at least about 2 weight percent sulfur.
  • the coal can be pre-treated such as to comminute the coal and remove moisture. For example, it is desirable to comminute the coal to reduce the maximum particle size to not greater than about 1 mm.
  • the hydrogenation process results in a highly purified and finely divided carbon product.
  • the hydrogenation treatment according to the present invention converts the volatiles (e.g., hydrocarbons) in the coal to methane.
  • the volatiles e.g., hydrocarbons
  • at least about 90 weight percent, more preferably at least about 95 weight percent and even more preferably at least about 99 weight percent of the volatile matter is converted to methane.
  • the coal frequently includes contaminants, including high levels of sulfur.
  • the method of the present invention advantageously and simultaneously strips contaminants from the volatile matter fraction of the coal as well as the residual coke.
  • the sulfur for example, reacts with the hydrogen gas and form hydrogen sulfide, which can be easily removed from the waste stream.
  • the method of the present invention enables the production of energy from the coal feedstock while producing significantly less carbon dioxide per kilowatt-hour of energy produced than is typically produced in a conventional coal-fired power plant.
  • This lower ratio of carbon dioxide to kilowatt-hours of electricity produced accrues because the method of the present invention converts coal, a solid fuel, to a medium BTU gaseous fuel.
  • the thermal to electric efficiency (expressed as a percentage) for a solid fuel ranges from the mid twenties to the low thirties whereas for a gaseous fuel, the thermal to electric conversion is 55 to 60 percent.
  • the reduction in carbon dioxide emission is an important environmental factor and adds further value to the method.
  • the carbon that is produced in the hydrogenation unit can be an activated carbon.
  • Activated carbon is an amorphous form of carbon characterized by high adsorptivity for many gases, vapors and colloidal solids. The internal surface area of the activated carbon exceeds several hundred m 2 /gram and the density is not greater than about 0.85 g/cm 3 .
  • Activated carbon has a high value and can be used for air and water purification, waste treatment, removal of mercury (Hg) and SO x from stack gases and the like.
  • Hg mercury
  • SO x sulfur oxide
  • hydrocarbon-bearing feedstocks can similarly be treated to produce a valuable product gas that includes methane (CH 4 ).
  • the feedstock is supplied to a hydrogenation unit where it is contacted with large volumes of a gas composition including H 2 at an elevated temperature such that a portion of the feedstock converts to CH 4 .
  • One advantage of the present invention is that the feedstock can be virtually any hydrocarbon bearing feedstock, including those that are available at a very low or even a negative net cost.
  • the feedstock is municipal waste.
  • the municipal waste can include normal household and commercial refuse, hazardous waste, animal waste, sewer sludge, automobile shredder refuse (ASR), scrap rubber tires and the like.
  • ASR automobile shredder refuse
  • Municipal waste is commonly available at a net negative cost since municipalities will typically pay a "tipping" fee for removal and destruction of the waste.
  • the feedstock When the feedstock is municipal waste, the feedstock can be treated and separated if necessary.
  • magnetic metals such as iron and steel can be easily removed and sold for scrap.
  • the cellulose- based materials e.g., paper and wood
  • air separation can be used to separate this light, relatively dry fraction of the waste that includes, for example, paper and paperboard, yard trimmings and wood.
  • the remaining material which includes food wastes, plastics, rubber, leather, non-ferrous metals and glass, can be separated by hydraulic classification. The non-ferrous metals and glass can be recycled off-site.
  • municipal solid waste can include not only residential and general commercial wastes, but specific wastes such as automobile shredder refuse (ASR) or "fluff'.
  • ASR essentially the non-metal components of a recycled automobile, is a heterogeneous mixture of plastics, glass, rubber, fiber, non-recovered metals and dirt.
  • the plastics content of ASR is typically about 20 weight percent and is increasing as the amount of plastic used in automobile construction increases.
  • ASR is presently land-filled and legislation has been proposed in some regions to classify the ASR as a hazardous waste, dramatically increasing the disposal cost.
  • ASR is presently land-filled and legislation has been proposed in some regions to classify the ASR as a hazardous waste, dramatically increasing the disposal cost.
  • ASR can be partitioned into volatiles and fixed carbon by the application of heat.
  • a large volume of combustible gas is produced from the waste and in accordance with the method of the present invention.
  • About 48,550 cubic feet of gas containing about 19.9 million BTU can be generated from 1 ton of municipal waste.
  • the gas is comprised of about 82 percent carbon monoxide, 16 percent methane and 2 percent hydrogen and contains about 410 BTU per cubic foot.
  • the feedstock can be a hydrocarbon bearing substance such as crude oil, tar sand or a similar substance.
  • Crude oil is a mixture of liquid hydrocarbons that is extracted from the earth's crust for use as fuel and various petroleum products. Because crude oil is a mixture of widely varying constituents and proportions, the physical properties vary widely and many crude oils have a very low value due to contaminants in the oil. The present invention advantageously enables the treatment of such low-grade crude oils to produce a useful gas product.
  • Tar sand also called bituminous sand, is a deposit of loose sand or partially consolidated sandstone that is saturated with highly viscous bitumen.
  • Oil recovered from tar sands is commonly referred to as synthetic crude and is a potentially significant form of fossil fuel. The recovery of oil from the tar sand, however, is difficult and costly.
  • the present invention advantageously enables the production of a useful gas product from otherwise low-value tar sand.
  • a combination of two or more of the above-described components can be used as the feedstock.
  • a separated municipal waste stream can be supplemented with pulverized coal.
  • Yet another aspect of the present invention is directed to the production of ammonia using hydrogen gas and nitrogen gas as reactants.
  • One of the important aspects of the method according to the present invention is the in-situ manufacture of large quantities of H 2 at a relatively low cost. It is believed that one of the primary hindrances to the methods disclosed in the prior art for the production of ammonia is the need for high volumes of hydrogen gas and the high cost associated with the hydrogen gas. According to the present invention, high volumes of hydrogen gas can be economically generated in-situ.
  • the nitrogen and hydrogen are combined in a H 2 :N 2 molar ratio of about 3:1 in order to maximize the production of ammonia (NH 3 ).
  • a gas including hydrogen and nitrogen is compressed to about 200 atmospheres of pressure and passed over an iron catalyst at a temperature of from about 380°C to about 450°C.
  • FIG. 8 A method for producing ammonia incorporating the foregoing hydrogen and nitrogen gas production methods is illustrated in Fig. 8.
  • water 801 is provided to a boiler 802 and steam is provided to one of reactors 810 or 812.
  • the hydrogen gas is then passed to a condenser 820 to remove water and is then supplied to an ammonia synthesis loop 848.
  • air 800 is supplied to an oxidation reactor 811 to strip oxygen from the air to provide a nitrogen gas stream 825.
  • the reactor 811 is the metal oxidation reactor whereas the reactor 813 is the metal oxide reduction reactor.
  • a single reactor can be used to provide reduction gas to both the hydrogen production and nitrogen production unit operations.
  • hydrogen gas 824 and nitrogen gas 825 are provided to an ammonia synthesis loop 848.
  • the ammonia synthesis loop preferably operates an elevated pressure, such as up to about 200 atmospheres.
  • the ammonia synthesis loop 848 operates at an elevated temperature and can include a catalyst.
  • the production of ammonia from hydrogen and nitrogen is illustrated in: U.S. Patent No. 4,600,571 by McCarroll et al.; U.S. Patent No. 4,298,588 by Pinto; and U.S. Patent No.
  • the resulting ammonia can be used in a number of applications.
  • the ammonia can be converted to urea for use in fertilizers.
  • the ammonia can also be used to reduce NO x emissions from coal-fired power plants and for the manufacture of various ammonium-containing compounds. While various embodiments of the present invention have been described in detail, it is apparent that modifications and adaptations of those embodiments will occur to those skilled in the art. However, it is to be expressly understood that such modifications and adaptations are within the spirit and scope of the present invention.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • General Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

L'invention concerne un procédé de production de gaz hydrogène. Ce gaz hydrogène est formé par réduction à la vapeur en utilisant un couple métal / oxyde de métal pour extraire l'oxygène de l'eau. La vapeur est mise en contact avec un mélange de métaux fondus comprenant un premier métal réactif, tel que le fer, dissous dans un métal diluant, tel que l'étain. Le métal réactif s'oxyde en oxyde de métal, formant un gaz hydrogène, et l'oxyde de métal peut être réduit à nouveau en métal pour permettre une nouvelle production d'hydrogène sans transfert majeur du métal ou de l'oxyde de métal dans un second réacteur. Le réacteur (400) comprend des parois latérales réfractaires (402) conçues pour contenir le mélange de métaux fondus (404). Lorsque la vapeur est introduite par la lance (408), le fer présent dans le mélange de métaux (404) s'oxyde en oxyde de fer. Cet oxyde de fer s'élève et s'accumule pour former une couche de laitier (406). Un produit gazeux (416) comprenant du gaz hydrogène mélangé à de la vapeur est extrait par l'orifice de sortie (410).
EP02723316A 2001-03-06 2002-03-05 Procede de production d'hydrogene et applications associees Pending EP1373131A4 (fr)

Applications Claiming Priority (11)

Application Number Priority Date Filing Date Title
US85436 1993-06-30
US800769 2001-03-06
US800423 2001-03-06
US09/800,421 US7232472B2 (en) 2001-03-06 2001-03-06 Method for the treatment of coal
US800421 2001-03-06
US09/800,434 US6620398B2 (en) 2001-03-06 2001-03-06 Method for the production of ammonia
US09/800,769 US6682714B2 (en) 2001-03-06 2001-03-06 Method for the production of hydrogen gas
US09/800,423 US20020139049A1 (en) 2001-03-06 2001-03-06 Method for the production of a methane-containing gas
US10/085,436 US6663681B2 (en) 2001-03-06 2002-02-28 Method for the production of hydrogen and applications thereof
PCT/US2002/006549 WO2002070403A1 (fr) 2001-03-06 2002-03-05 Procede de production d'hydrogene et applications associees
US800434 2007-05-03

Publications (2)

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EP1373131A1 EP1373131A1 (fr) 2004-01-02
EP1373131A4 true EP1373131A4 (fr) 2007-10-03

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CN (1) CN1254433C (fr)
AU (1) AU2002254101B2 (fr)
CA (1) CA2440137A1 (fr)
EA (1) EA005832B1 (fr)
MX (1) MXPA03008037A (fr)
PL (1) PL364600A1 (fr)
WO (1) WO2002070403A1 (fr)

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EP1462170A1 (fr) * 2003-03-28 2004-09-29 European Community Réactions chimiques en phase vapeur catalysées par un métal fondu
US20050042150A1 (en) * 2003-08-19 2005-02-24 Linnard Griffin Apparatus and method for the production of hydrogen
BRPI0612895B1 (pt) * 2006-04-28 2020-12-22 Tata Steel Limited método para produzir gás hidrogênio a partir de água
JP4949795B2 (ja) * 2006-10-10 2012-06-13 ウチヤ・サーモスタット株式会社 水素発生媒体の製造方法
DE102008021562B4 (de) * 2008-04-30 2012-06-21 Voestalpine Stahl Gmbh Verfahren zur Herstellung von Wasserstoffgas mit Hilfe von Hüttenreststoffen und Verwendung von Hüttenreststoffen
CN101665240A (zh) * 2008-09-03 2010-03-10 李�杰 工业法制氢气及装置
JP5373410B2 (ja) * 2009-01-09 2013-12-18 トヨタ自動車株式会社 アンモニア合成方法
CN103112821A (zh) * 2013-01-15 2013-05-22 上海交通大学 一种碱性硫化氢溶液催化铁水热还原水产氢的方法
KR101529692B1 (ko) * 2013-09-05 2015-07-01 한국과학기술연구원 물과 메탄을 연속적으로 분해하여 수소를 제조하는 방법
CN106220461B (zh) * 2016-07-19 2018-11-30 青岛科技大学 一种基于煤化学链气化直接制备甲烷的装置及方法
DE112016007162A5 (de) * 2016-09-25 2019-05-16 Peter Paul Smolka Treibstoff-Produktionsanlage für Kraftwerke
GB201811785D0 (en) * 2018-07-19 2018-09-05 Univ Surrey A continuous process for sustainable production of hydrogen
RU2701936C1 (ru) * 2018-12-13 2019-10-02 Владимир Владимирович Сербиненко Способ непрерывного производства ценных химических продуктов и энергии из углеродсодержащего сырья
MY192817A (en) * 2019-04-22 2022-09-12 Univ Kebangsaan Malaysia A catalyst composition and method of making thereof for pure hydrogen production
CN111252735B (zh) * 2020-03-19 2023-04-07 上海交通大学 复合金属协同水热分解水制备氢气的方法
WO2024069211A1 (fr) * 2022-09-28 2024-04-04 Volvo Truck Corporation Réacteur d'oxydation pour véhicule à pile à combustible à hydrogène

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JPH06157003A (ja) * 1992-11-19 1994-06-03 Sumitomo Metal Ind Ltd 鉄分を利用した水素製造法

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JPH06157003A (ja) * 1992-11-19 1994-06-03 Sumitomo Metal Ind Ltd 鉄分を利用した水素製造法

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JP2004529056A (ja) 2004-09-24
EP1373131A1 (fr) 2004-01-02
CA2440137A1 (fr) 2002-09-12
EA200300977A1 (ru) 2004-04-29
PL364600A1 (en) 2004-12-13
AU2002254101B2 (en) 2008-03-20
EA005832B1 (ru) 2005-06-30
CN1505591A (zh) 2004-06-16
CN1254433C (zh) 2006-05-03
MXPA03008037A (es) 2004-10-15

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