US20060102493A1 - Enrichment of oxygen for the production of hydrogen from hydrocarbons with co2 capture - Google Patents

Enrichment of oxygen for the production of hydrogen from hydrocarbons with co2 capture Download PDF

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US20060102493A1
US20060102493A1 US10/534,784 US53478403A US2006102493A1 US 20060102493 A1 US20060102493 A1 US 20060102493A1 US 53478403 A US53478403 A US 53478403A US 2006102493 A1 US2006102493 A1 US 2006102493A1
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hydrogen
conversion
carbon dioxide
conversion product
oxygen
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Didier Grouset
Philippe Marty
Jean-Christopher Hoguet
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N Ghy SA
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    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/382—Multi-step processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
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    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
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    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
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    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00309—Controlling the temperature by indirect heat exchange with two or more reactions in heat exchange with each other, such as an endothermic reaction in heat exchange with an exothermic reaction
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
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    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
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    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
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    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
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    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1288—Evaporation of one or more of the different feed components
    • C01B2203/1294—Evaporation by heat exchange with hot process stream
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    • C01B2203/14—Details of the flowsheet
    • C01B2203/148—Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
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    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
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    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0043—Impurity removed
    • C01B2210/0046—Nitrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D21/00—Heat-exchange apparatus not covered by any of the groups F28D1/00 - F28D20/00
    • F28D21/0001—Recuperative heat exchangers
    • 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
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • 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
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry

Definitions

  • the present invention concerns a method and a device for producing hydrogen from a hydrocarbon with high energy efficiency while releasing low or zero levels of carbon dioxide and pollutants.
  • hydrocarbon generally designates any fossil or renewable fuel, including substances that are oxygenated (alcohol, ester, etc.), gaseous, liquid, or even in powdered solid form (handleable like a fluid), provided that it forms only a small amount of inert solid residue, i.e., an ash content of less than 1% by weight.
  • hydrogen as such does not exist in a natural state and must be produced, for example for use in fuel cells, either in a centralized way in order to be distributed to local retailers and users, or in a decentralized way, locally, just upstream from the fuel cell, for immediate consumption by the latter.
  • Hydrogen can be produced from two separate sources: either by so-called “downstream” means, i.e. by breaking down water thermally at a very high temperature or electrically by electrolysis, or by so-called “upstream” means, by converting a hydrocarbon.
  • downstream means, i.e. by breaking down water thermally at a very high temperature or electrically by electrolysis
  • upstream means, by converting a hydrocarbon.
  • the hydrogen Since the hydrogen is intended to subsequently produce electricity in a fuel cell, the use of “electrolysis” may seem inappropriate, at least in terms of overall energy efficiency. But if this electricity is from a renewable (wind, solar, geothermal) or nuclear source, there is no production of CO 2 or other pollutants in this production-consumption chain. Whether for stationary or mobile applications, the hydrogen in that case seems to be an energy vector, making it possible, through the use of fuel cells, to produce clean electricity in places that are totally or periodically without access to nuclear or renewable energy.
  • the conversion of a fossil or renewable hydrocarbon generates hydrogen but also CO 2 , which may limit the advantage of using fuel cells.
  • this method has the advantage of potentially high energy efficiency, thus conserving fossil fuel resources or biomass products for energy uses.
  • the partial oxygen (POX) reaction corresponds to the reaction of the fuel (C n H m O p ) with oxygen. It results in the formation of gaseous mixture of hydrogen, carbon monoxide, and possibly nitrogen (if the oxygen is drawn from the air): C n H m O p +[( n ⁇ p )/2] (O 2 + ⁇ N 2 ) ⁇ n CO+( m/ 2)H 2 +[( n ⁇ p )/2] ⁇ N 2
  • ⁇ represents the N 2 /O 2 molar ratio of the oxidant mixture (standard air or oxygen-enriched air: ⁇ 3.762).
  • the POX reaction is exothermic; it does not require an external supply of heat. Having extracted the hydrogen from the fuel, it is possible to produce more of it using the so-called water-gas shift or WGS reaction, in which the carbon monoxide reacts with the water vapor to form carbon dioxide and additional hydrogen through the following reaction: CO+H 2 O ⁇ CO 2 +H 2
  • POX being endothermic, produces less hydrogen than the vapor reforming (second family of methods) described below, and moreover, has a tendency to produce solid carbon, which can foul or clog the tubes and exchangers.
  • gasoline it is performed at around 1200° C. without a catalyst and at around 800° C. with a catalyst.
  • diesel fuel it is conducted between 950° C. and 1200° C. (Texaco-ShellTM burners).
  • Vapor reforming is a reaction that is well known in petrochemistry, where the production of hydrogen from natural gas is common. It requires a nickel-based catalyst, adapted to the molecules to be reformed (methane and light hydrocarbons). It is done at a temperature of 850 to 950° C. at pressures of 15 to 25 bar and at H 2 O/F (fuel) ratios between 2 and 4. These reactions, being endothermic, are conducted in large furnaces or banks of parallel tubes filled with catalysts and heated externally (mainly by radiation), which are passed through by the mixture to be reformed. The energy required for the reforming reaction is produced by oxidizing part of the fuel with air (producing CO 2 and H 2 O) and is transmitted to the reagents to be reformed through the walls of these tubes.
  • the conditions and catalysts are different.
  • the temperatures are lower than for methane (850° C.).
  • Methanol is easier to reform; temperatures of 250° C. are sufficient, and the catalyst is Cu/Zn/Al-based.
  • Reforming gasoline requires a temperature higher than 800° C.
  • Hydrocarbons that contain sulfur require pre-desulphurization, as the catalyst would be poisoned by the sulfur.
  • the reforming is therefore done under temperature and pressure conditions that are adapted to the fuel and that can be calculated using the laws of thermodynamics involving chemical equilibrium. It is always a slow reaction, which is why the reforming is necessarily catalytic.
  • the fraction v that should be burned depends solely on the atomic composition of the fuel and its heat-generating power, as well as that of the hydrogen.
  • VRA is a combination of reforming and partial oxidation (with water and air injection). This technology has been adapted for small-scale facilities both in EPYXTM technology and in single-reactor HOTSPOTTM technology, initially developed for methanol.
  • the air is compressed before being introduced into the reforming process.
  • air is also compressed in order to be introduced into the fuel cell.
  • the air compressors represent auxiliary equipment that consumes a significant part of the electric power produced by the fuel cell. To limit this consumption, the tendency is to use low levels of pressurization relative to the atmospheric pressure, both for the fuel cell and for the reforming process when it is performed in direct connection with a fuel cell.
  • the invention concerns a method for producing hydrogen from a hydrocarbon with high energy efficiency while releasing very low or zero levels of carbon dioxide and pollutants.
  • the method comprises a step (a) for using a flow of (pure or nearly pure) oxygen to (i) oxidize a portion of the hydrocarbons and (ii) supply the heat required to convert, using water vapor, at suitable temperatures, nearly all of the other portion of the hydrocarbons into hydrogen, carbon monoxide and carbon dioxide.
  • Suitable temperatures means temperatures like those used in the techniques described above.
  • the method also comprises a step (b) for preheating the hydrocarbons, the flow of oxygen and the water to be vaporized.
  • the hydrocarbons, the flow of oxygen, and the water to be vaporized are hereinafter referred to as the reagents.
  • the mixture formed by the hydrogen, the carbon monoxide, the carbon dioxide and the excess water vapor is hereinafter referred to as the products of the conversion. Nitrogen being absent from the reagents, it does not dilute the conversion products; the subsequent steps (b) through (f) of the method are facilitated, and overall efficiency is increased.
  • the method also comprises steps (c) for cooling (at least one) of the conversion products in order to recover a fraction of the thermal energy of the conversion products for the purpose of preheating the reagents and condensing at least part of the water vapor contained in the conversion products.
  • the method also comprises the following steps:
  • a step (d) for recovering the hydrogen by extracting the hydrogen from the conversion products, either in order to consume it or with a view to storing it for later consumption.
  • Steps (a) through (d) are performed at suitably high pressures, above 30 bar, in order to:
  • the method according to the invention also comprises:
  • steps (e) for the final conversion of the carbon monoxide into carbon dioxide are performed during the step for recovering the hydrogen.
  • the method according to the invention is performed at sufficient pressure to implement:
  • the method according to the invention uses a membrane that is selectively permeable to hydrogen to extract the hydrogen from the conversion products.
  • the method also comprises a step for lowering the partial pressure of the hydrogen downstream from the membrane by diluting the flow of permeated hydrogen in a flow of extraction gas, particularly a condensable gas.
  • the extraction of hydrogen by means of a permeable membrane is performed at the same time as the step for the final conversion of the carbon monoxide into carbon dioxide.
  • the result of this combination of technical characteristics is that the partial pressure of the hydrogen during the final conversion step is lowered, which promotes the conversion of the carbon monoxide into carbon dioxide.
  • the method also comprises a step for regulating the temperature of the final conversion by adjusting the flow rate and/or the temperature of the flow of extraction gas.
  • the method is such that the preheating and cooling steps are combined in a recovery exchanger so that the reagents and the conversion products circulate continuously through the recovery exchanger.
  • the method according to the invention also comprises a step for lowering the pressure of the conversion products and/or the final conversion products and/or the hydrogen produced while compressing the air required to run the fuel cell.
  • the method according to the invention can also be combined with a hydrogen production method that generates a flow of oxygen, particularly by electrolysis.
  • a hydrogen production method that generates a flow of oxygen, particularly by electrolysis.
  • the method according to the invention can also be combined with a nitrogen production method that generates a flow of oxygen.
  • the result of this combination of technical characteristics is that it thus possible to limit the cost of producing the oxygen consumed in the method according to the invention.
  • the invention concerns a device for producing hydrogen from a hydrocarbon with high energy efficiency while releasing very low or zero levels of carbon dioxide and pollutants.
  • the device comprises a reactor for converting (a) the hydrocarbons using water vapor.
  • the conversion reactor is supplied with pure or nearly pure oxygen in order to (i) oxidize a portion of the hydrocarbons and (ii) supply the heat required to convert into hydrogen, carbon monoxide and carbon dioxide, at suitable temperatures, nearly all of the other portion of the hydrocarbons.
  • the mixture formed by the hydrogen, the carbon monoxide, the carbon dioxide and the excess water vapor is hereinafter referred to as the products of the conversion.
  • the device also comprises means for preheating (b) the hydrocarbons, the flow of oxygen and the water to be vaporized.
  • the hydrocarbons, the flow of oxygen and the water to be vaporized are hereinafter referred to as the reagents.
  • the device also comprises:
  • At least one heat exchanger for (i) cooling the conversion products, for (ii) recovering a fraction of the thermal energy from the conversion products in order to preheat the reagents, and for (iii) condensing at least a part of the water vapor contained in the conversion products.
  • the hydrogen recovery unit comprises an extraction element for extracting the hydrogen from the conversion products in order to consume it in a hydrogen-consuming device (for example in a fuel cell) or store it in a reservoir for later consumption.
  • the conversion reactor, the preheating means, the heat exchanger, and the recovery unit operate at suitably high pressures, above 30 bar, in order to:
  • the device according to the invention also comprises:
  • the pressure inside the device is sufficient to implement:
  • a container for storing the carbon dioxide in liquid form for storing the carbon dioxide in liquid form.
  • the extraction element includes a membrane that is selectively permeable to hydrogen for extracting the hydrogen from the conversion products.
  • the extraction element also includes a feed of extraction gas, particularly an easily condensable gas, located downstream from the membrane, which lowers the partial pressure of the hydrogen downstream from the membrane by diluting the flow of permeated hydrogen.
  • the extraction element with a permeable membrane is disposed in the final conversion reactor.
  • the result of this combination of technical characteristics is that the partial pressure of the hydrogen during the final conversion is lowered, which promotes the conversion of the carbon monoxide into carbon dioxide.
  • the device also comprises means for regulating the temperature of the final conversion by acting on the flow rate and/or the input temperature of the extraction gas.
  • the device is such that the permeable membrane is composed of a plurality of tubes that descend into the extraction element.
  • Each tube is shaped like a glove finger whose open end opens to the outside of the extraction element. The open end makes it possible to introduce the extraction gas into the tube.
  • the device according to the invention is such that the preheating means and the cooling heat exchanger are combined in a recovery exchanger so that the reagents and the conversion products circulate continuously through the recovery exchanger.
  • the device in the case where the device is more specifically intended to produce hydrogen for the purpose of supplying a fuel cell running with air, the device according to the invention also comprises an element for reducing the pressure of the conversion products and/or the final conversion products and/or the hydrogen produced, making it possible to compress the air required to run the fuel cell.
  • the device according to the invention can also be combined with a hydrogen production unit that generates a flow of oxygen, particularly by means of an electrolyzer.
  • a hydrogen production unit that generates a flow of oxygen, particularly by means of an electrolyzer.
  • the device according to the invention can also be combined with a nitrogen production unit that generates a flow of oxygen.
  • a nitrogen production unit that generates a flow of oxygen.
  • FIG. 1 which illustrates the variation in the fraction (fa) of hydrocarbon oxidized with pure oxygen as a function of the reagent preheating temperature in the case of diesel fuel
  • FIG. 2 which illustrates the variation in the fraction (fa) of hydrocarbon oxidized with air as a function of the reagent preheating temperature in the case of diesel fuel
  • FIG. 3 which illustrates, in block diagram form, a variant of embodiment of a unit for producing pure hydrogen stored under pressure
  • FIG. 4 which illustrates, in block diagram form, another variant of embodiment of a unit for producing pure hydrogen, intended to be used immediately in a low-temperature, low-pressure PEMFC-type fuel cell,
  • FIG. 5 which illustrates, in block diagram form, another variant of embodiment of a unit for producing a mixture of hydrogen and carbon dioxide, intended to be used immediately in a low-temperature, medium-pressure PEMFC-type fuel cell,
  • FIG. 6 which illustrates in block diagram form, another variant of embodiment of a unit for producing a mixture of hydrogen and carbon dioxide, intended to be used immediately in a high-temperature, medium-pressure SOFC-type fuel cell,
  • FIG. 7 which illustrates a variant of embodiment of a means for preheating the reagents and a heat exchanger for cooling the associated products, constituting a regeneration system, the regeneration system being combined with a conversion reactor,
  • FIG. 8 which illustrates another variant of embodiment of a means for preheating the reagents and a heat exchanger for cooling the associated products, constituting a recovery exchanger, the recovery exchanger being combined with a conversion reactor,
  • FIG. 9 which illustrates in a graph the increase in the efficiency of the hydrogen permeation as a function of the ratio between the molar flow rate of the extraction gas downstream from the membrane and the molar flow rate of the hydrogen to be extracted upstream from the membrane,
  • FIGS. 10 a and 10 b which illustrate a reactor for converting CO into CO 2 equipped with a hydrogen-permeable membrane, supplied with extraction water vapor on the downstream end
  • FIG. 11 which illustrates a reactor for converting CO into CO 2 , equipped with a series of closed-end tubes that descend into the core of the reactor, each of which supports a hydrogen-permeable membrane.
  • FIG. 1 This figure illustrates the variation in the fraction (fa) of hydrocarbon oxidized with pure oxygen as a function of the reagent preheating temperature in the case of diesel fuel.
  • the fraction (fa) of hydrocarbon oxidized depends on the desired conversion temperature.
  • the curves shown respectively correspond to the following conversion temperatures (Tconv): 1000° C., 1200° C., 1400° C. They have been plotted for water factor (fe) values equal to 1.5 and a pressure of 5 bar.
  • water factor (fe) means the ratio between the flow of water actually made available by injection into the conversion reactor and the stoichiometric flow of water required for a complete conversion of the fraction of hydrocarbon to be converted: C n H m O p +fa ( n+m/ 4 ⁇ p/ 2)(O 2 + ⁇ N 2 +[fe (1 ⁇ fa )(2 n ⁇ p ) ⁇ fa ( m/ 2)]H 2 O ⁇ n CO 2 +(1 ⁇ fa )(2 n+m/ 2 ⁇ p )H 2 +fa ⁇ ( n+m/ 4 ⁇ p/ 2)N 2 +( fe ⁇ 1)(1 ⁇ fa )(2 n ⁇ p )H 2 O
  • FIG. 1 shows that fa diminishes when the preheating temperature of the reagents increases.
  • the amount of energy supplied with preheated reagents makes it possible to reduce the fraction of fuel to be burned in order to reach the desired temperature level and to promote the endothermic conversion reactions.
  • the fraction fa and the flow of oxygen can be determined, as shown in FIG. 1 .
  • the three reagent flows to be placed in contact inside the conversion reactor are identified.
  • the hydrogen conversion reaction being endothermic, no matter how high the preheating temperature, it will be necessary in all cases to oxidize a fraction of the hydrocarbon in order to compensate for the heat of the conversion reaction.
  • This minimum fraction to be burned can be determined as a function of the fuel's enthalpy of formation and its composition.
  • This particular value of fa is marked v. This value is characteristic of the fuel. It is equal to 0.2565 in the case of diesel fuel.
  • the flows of oxygen and diesel fuel to be used are therefore in a ratio of 1.27.
  • FIG. 2 illustrates, in the case of diesel fuel, the variation in the fraction (fa) of hydrocarbon oxidized with air as a function of the reagent preheating temperature.
  • the oxidation of the fraction of the fuel and the conversion of the remaining fraction are less sudden than with oxygen.
  • the maximum temperatures reached are lower, and there may remain larger contents of light hydrocarbons such as methane, ethylene and ethane as well as polyaromatic hydrocarbons. These contents are on the order of a few per thousand to a few percent, depending on the family of conversion methods used and the temperature applied.
  • Reforming units on petrochemical sites commonly operate at high pressures of several tens of bar.
  • a small-scale unit that feeds, for example, a low-pressure fuel cell using a partial oxidation or autothermal vapor reforming unit at high pressure is detrimental to the overall efficiency of the system since it is necessary to compress the air to be injected into the conversion reactor, which is energy-expensive. It is therefore preferable to operate at a pressure close to the atmospheric pressure.
  • a hydrogen production unit according to the invention can be embodied in various ways. Four variants of embodiment are shown as examples in FIGS. 3 through 6 .
  • FIG. 3 illustrates, in block diagram form, a variant of embodiment of a unit for producing pure hydrogen stored under pressure.
  • the production unit also called the device 1 , is composed of the following elements:
  • the production unit 1 is used to produce pure hydrogen.
  • the latter is stored under high pressure (200 to 350 bar or more) for later use.
  • the pressure in the conversion reactors 4 of this unit is on the order of 50 to 60 bar. Downstream from the membrane 7 , the pressure of the flow of hydrogen extracted is still significant (20 to 30 bar); the compression effort required to reach the storage pressure is thus considerably reduced.
  • FIG. 4 illustrates, in block diagram form, another variant of embodiment of a unit for producing pure hydrogen, intended to be used immediately in a low-temperature, low-pressure PEMFC-type fuel cell.
  • the production unit also called the device 1 , is composed of the following elements:
  • the production unit 1 produces pure hydrogen, which is immediately put to use in another system, for example a PEMFC (Proton Exchange Membrane Fuel Cell) type fuel cell 17 , running at a relatively low temperature (60 to 120° C.) and low pressure (between 1 and 5 bar).
  • the production unit is identical to the one in FIG. 3 until just downstream from the membrane 7 , where the pressure of the flow of hydrogen extracted is still significant (20 to 30 bar) and its temperature is high (350° C.).
  • the release of pressure from the hydrogen downstream from the membrane 7 by means of a turbo compressor 18 , 19 supplies the energy for compressing the air that feeds the cell 17 , which normally requires a piece of auxiliary equipment that is costly in terms of the overall efficiency of the method.
  • FIG. 5 represents, in block diagram form, another variant of embodiment of a unit for producing a mixture of hydrogen and carbon dioxide, intended to be used immediately in a low-temperature, medium-pressure PEMFC-type fuel cell.
  • the production unit also called the device 2 , is composed of the following elements:
  • the production unit 1 produces hydrogen for immediate use in a mixture with CO 2 in a fuel cell 17 at a relatively low temperature and medium pressure.
  • the production unit 1 does not include a hydrogen permeation membrane 7 , but includes an additional cooling 6 b of the products during the final conversion of the CO into CO 2 .
  • the hydrogen production unit 1 operates at a high level of pressure (30 to 60 bar).
  • the energy recovered during the release of pressure 18 , 19 from the H 2 /CO 2 mixture makes it possible to compress the air admitted into the fuel cell 17 .
  • the recoverable energy is substantial since the mass and volume rate of the H 2 +CO 2 mixture whose pressure is to be reduced is higher than in the case of the production unit represented in FIG. 4 . It is possible to have the cell 17 run at a higher pressure (5 or 7 absolute bar rather than 1 bar), which promotes the recycling of the water leaving the cell 17 in order to feed the conversion reactor 4 , and which also promotes the compactness of the equipment.
  • FIG. 6 illustrates, in block diagram form, another variant of embodiment of a unit for producing a mixture of hydrogen and carbon dioxide, intended to be used immediately in a high-temperature, medium-pressure SOFC-type fuel cell.
  • the production unit also called the device 1 , is composed of the following elements:
  • the production unit 1 produces hydrogen in a mixture with CO and CO 2 for use in an SOFC (Solid Oxide Fuel Cell) type fuel cell running at a high temperature (600 to 900° C.) and relatively medium pressure (between 1 and 7 bar).
  • the production unit 1 does not include a hydrogen-permeable membrane 8 either; nor does it include the final conversion 11 of the CO into CO 2 since the CO can be used by the SOFC.
  • the hydrogen production unit 1 operates at a high level of pressure (30 to 60 bar).
  • the energy recovered during the release of pressure 18 from the H 2 /CO/CO 2 mixture makes it possible to compress the air 19 admitted into the fuel cell 17 . It is possible to have the SOFC run at a medium pressure (5 or 7 absolute bar instead of 1), which promotes the recycling of the water leaving the cell in order to feed the conversion reactor 4 , as well as the compactness of the equipment.
  • the means for preheating the reagents 5 and the heat exchanger for cooling 6 the products in the case of the variants of embodiment illustrated in FIGS. 3 through 6 may advantageously be combined so that the energy recovered from the products is transferred to the reagents. Both capabilities of the combination, regeneration or recovery, can be implemented in the variants of embodiment described above.
  • FIG. 7 illustrates a variant of embodiment of a means for preheating the reagents 5 and a heat exchanger for cooling the associated products 6 , constituting a regenerative system.
  • the reagent preheating means previously referenced 5 is referenced 22
  • the cooling heat exchanger previously referenced 6 is referenced 23 .
  • the heat is stored in the elements made of ceramic material placed in the reagent preheating means 22 and in the cooling heat exchanger 23 .
  • the reagent preheating means 22 and the cooling heat exchanger 23 are disposed on either side of the conversion reactor 4 .
  • the flows are periodically alternated.
  • the cold reagents enter the reagent preheating means 22 , wherein the ceramic elements are hot, heat up on contact with it and cool it, while the hot products enter the cooling heat exchanger 23 , which is relatively cold, cool off in contact with the ceramic elements and reheat them.
  • the flows are reversed by means of valves 21 , and the roles of the reagent preheating means 22 and the cooling heat exchanger 23 are reversed.
  • the reagents flow into the cooling heat exchanger 23 , which has become hot enough to serve as the reagent preheating means 22 , then pass through the conversion reactor 4 in the opposite direction.
  • the conversion products leave the conversion reactor 4 in the direction of the reagent preheating means 22 . The latter has become cold enough to serve as the cooling heat exchanger.
  • the ceramic elements have the advantage of being able to be used at a very high temperature.
  • FIG. 8 represents a variant of embodiment of a means for preheating the reagents 5 and a heat exchanger for cooling the associated products 6 , constituting a recovery system 24 .
  • the means for preheating the reagents 5 and the heat exchanger for cooling the products 6 form two sides of the same piece of equipment, and the heat is transferred from one to the other through the impermeable surface that separates them.
  • This configuration has the advantage of continuous operation and does not require a system of flow-reversing and control valves.
  • the thermal inertia is also much lower.
  • the hydrocarbons, the oxygen and the water or vapor enter the recovery system 24 , where they are heated, cooling the hot products of the conversion. They are then injected into the conversion reactor 4 on the opposite side of the recovery system 24 through feed circuits 25 . The hot conversion products then enter the recovery system 24 .
  • the gas after the extraction of the hydrogen or its use by the fuel cell, the gas may still contain a small amount of residual hydrogen.
  • the gas is then subjected to a post-combustion 12 of these residues, which transforms them into H 2 O and CO 2 .
  • the gas under high pressure (50 or 60 bar in the case of the variants of embodiment in FIGS. 3 and 4 ) or medium pressure (5 to 7 bar in the case of the variants of embodiment in FIGS. 5 and 6 ), no longer contains anything other than water vapor and carbon dioxide (with small traces of CO, H 2 if the post-combustion is incomplete, and nitrogen if the oxygen used is not pure). Cooling it to a temperature on the order of 40° C. will result in the condensation 13 of nearly all of the water, which can be recycled back to the beginning of the hydrocarbon conversion process via a reservoir of water under pressure 15 .
  • the residual gas is then nothing but nearly pure CO 2 (with traces of CO, H 2 , N 2 , H 2 O).
  • the CO 2 can be easily condensed by cooling in contact with a wall at ambient temperature.
  • the effective rate of condensation of the CO 2 will depend on the temperature of the cold wall and the level of residual impurities in the gas: for example, at 60 bar and with a wall at 110° C., a 92% to 99.2% condensation of the CO 2 will be obtained if the traces of CO, H 2 and N 2 represent 2% to 0.2%, respectively, in the products leaving the post-combustion chamber.
  • the CO 2 can then be stored in dense liquid form.
  • Pressures as low as 30 bar are acceptable for condensing the CO 2 ; in that case, it is necessary to use a refrigerant at negative temperatures such as ⁇ 20° C. in order to obtain substantial levels of CO 2 condensation, commensurate with the level of residual impurities in the gas.
  • the flow of CO 2 generated can be stored at a pressure of 7 bar, or possibly recompressed in order to be condensed.
  • FIGS. 3 and 4 show two variants of embodiment comprising two successive steps.
  • the purpose of one step is to convert CO in to CO 2 using the gas's catalytic reaction to water: CO+H 2 O ⁇ CO 2 +H 2 .
  • the purpose of the other step is to extract the hydrogen formed by means of a membrane 7 .
  • the use of oxygen in place of air promotes the extraction by the membrane 7 since the partial pressure of the hydrogen, which is not diluted in nitrogen, is higher.
  • FIG. 9 shows the increase in the efficiency of the hydrogen extraction as a function of the ratio between the molar flow rate of the hydrogen to be extracted and the molar flow rate of the flow of extraction gas.
  • the total pressure upstream from the membrane 7 is 45 bar
  • the molar fraction of the hydrogen upstream is 50.9%
  • the total pressure downstream from the membrane 7 is 5 bar.
  • Extraction efficiencies of 90 to 100% may be obtained, even with back pressures of 5 bar downstream from the membrane 7 .
  • the flow of extraction gas may be condensed by cooling so as to be recycled to the extraction membrane, leaving behind a flow of pure hydrogen to be used or stored.
  • Any gas that is inert with respect to hydrogen and the membrane such as nitrogen, argon, water vapor, ammonia, etc., may be used to lower the partial pressure of the hydrogen downstream from the membrane and thus extract the hydrogen more easily.
  • an easily condensable extraction gas such as water vapor or ammonia; a step for cooling and condensing the vector gas/hydrogen mixture will make it possible to separate them and to recover pure hydrogen.
  • FIGS. 10 a and 10 b two variants of embodiment according to the invention of a reactor for the final conversion of CO into CO 2 11 , comprising a hydrogen-permeable membrane 7 that makes it possible to extract the hydrogen.
  • a reactor for the final conversion of CO into CO 2 11 comprising a hydrogen-permeable membrane 7 that makes it possible to extract the hydrogen.
  • the hydrogen is extracted at the center of the final conversion reactor 11 .
  • the membrane tube 26 is placed on the axis of the chamber 27 and is fed with extraction water vapor.
  • the conversion catalyst is placed in the ring-shaped chamber around the membrane tube 26 and is passed through by the gasses to be converted, generally in the opposite direction from the extraction water vapor.
  • the hydrogen is extracted at the periphery of the final conversion reactor 11 .
  • the water vapor for extracting the hydrogen circulates at the periphery of the final conversion reactor 11 .
  • the conversion catalyst is placed in the center.
  • FIG. 11 another variant of embodiment according to the invention of a reactor for the final conversion of CO into CO 2 11 , equipped with a series of closed-end tubes that descend into the core of the reactor, each of which supports a hydrogen-permeable membrane that makes it possible to extract hydrogen.
  • the membrane surface to be installed would result in an excessive diameter and length if the configuration represented in FIG. 10 a or 10 b were retained.
  • the quantity of catalyst required would result in a ring that is too thick. For this reason, the compositions and temperatures in each section would not be homogeneous. It is preferable to divide up the catalyst thickness using a number of membrane tubes 26 shaped like the fingers of a glove. The tubes 26 , of small diameter and length, descend from the external wall right into the core of the conversion reactor 11 .
  • Reactors like those described in reference to FIGS. 10 a and 10 b make it possible not to separate the steps for the final CO/CO 2 conversion and for the extraction of the hydrogen. They are performed in the same chamber. It is thus possible to reduce the partial pressure of the hydrogen during the final CO/CO 2 conversion and thereby shift the equilibrium toward the formation of CO 2 and H 2 O; the conversion reaction is accelerated. A smaller quantity of catalyst or a smaller size chamber may be used to achieve equivalent performance. This configuration is possible because the conversion of the CO into CO 2 and the extraction through a hydrogen-permeable membrane are done at the same temperature level: on the order of 250 to 400° C. The reaction of the gas to water is exothermic, and heat must be extracted in order to maintain the gas within the optimal operating temperature range of the catalyst.
  • the flow of extraction water vapor can advantageously be used to cool the CO/CO 2 conversion chamber.
  • the flow of extraction water vapor may be used to supply heat to this conversion reactor.
  • the tube or tubes that support the permeation membrane 26 and are passed through by the extraction water vapor can advantageously serve as heat exchangers, thus avoiding the use of specific equipment for this heat exchange function.
  • the temperature of the conversion chamber can thus be regulated by varying the flow rate and the temperature of the flow of extraction water vapor.
  • Nitrogen may be produced by distilling air under cryogenic conditions. The production of one kg of nitrogen is accompanied by the production of 0.30 kg of oxygen. This oxygen, in liquid form, may be used onsite to produce hydrogen using the method according to the invention described in reference to FIGS. 3 through 6 . It may also be transported in order to be used at another site using the method according to the invention described in reference to FIGS. 3 through 6 .
  • the consumption of diesel fuel is respectively equal to 0.21 kg/kg of nitrogen and 0.26 kg/kg of nitrogen for a quantity of captured CO 2 respectively equal to 0.67 kg per kg of nitrogen and 0.82 kg per kg of nitrogen.
  • the quantity of hydrogen generated is respectively equal to 0.054 kg of H 2 per kg of nitrogen produced and 0.073 kg of H 2 per kg of nitrogen produced, representing a chemical energy of 7.7 to 10 MJ and an electrical energy of 1.1 to 1.45 kWh after use in a fuel cell.
  • Hydrogen can also be produced by water electrolysis.
  • the production of one kg of electrolytic hydrogen is accompanied by the production of 8 kg of oxygen.
  • the electrolyzers operate under medium pressure, from a few bar to several tens of bar.
  • the oxygen produced may be put to use according to any of the variants of embodiment represented in FIGS. 3 through 6 .
  • the variant of embodiment represented in FIG. 3 has the advantage of using the oxygen onsite to produce hydrogen.
  • the method according to the invention makes it possible to obtain a flow of chemical hydrogen in addition to the electrolytic hydrogen, while contributing to CO 2 capture and to the amortization of all the utilities for conditioning the hydrogen produced.
  • the leverage is considerable, since with 8 kg of oxygen produced, for an 80 to 90% energy efficiency of the chemical method for producing hydrogen, the consumption of diesel fuel is respectively equal to 5.75 to 6.9 kg/kg of electrolytic hydrogen for a quantity of captured CO 2 respectively equal to 19.1 kg per kg of electrolytic hydrogen and 21.8 kg per kg of electrolytic hydrogen.
  • the quantity of hydrogen generated is respectively equal to 1.45 kg of chemical hydrogen per kg of electrolytic hydrogen and 1.96 kg of chemical hydrogen per kg of electrolytic hydrogen.
US10/534,784 2002-11-13 2003-10-29 Enrichment of oxygen for the production of hydrogen from hydrocarbons with co2 capture Abandoned US20060102493A1 (en)

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FR0214187A FR2846958B1 (fr) 2002-11-13 2002-11-13 Valorisation de l'oxygene pour la production d'hydrogene a partir d'hydrocarbures avec sequestration de co2
FR02/14187 2002-11-13
PCT/FR2003/050109 WO2004046029A2 (fr) 2002-11-13 2003-10-29 Production d'hydrogene a partir d'hydrocarbures

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US20080245660A1 (en) * 2007-04-03 2008-10-09 New Sky Energy, Inc. Renewable energy system for hydrogen production and carbon dioxide capture
GB2456169A (en) * 2008-01-04 2009-07-08 Nebb Technology As A method and associated apparatus for the production of hydrogen and/or electric energy
US20090293360A1 (en) * 2004-04-09 2009-12-03 Hyun Yong Kim High temperature reformer
US10464014B2 (en) * 2016-11-16 2019-11-05 Membrane Technology And Research, Inc. Integrated gas separation-turbine CO2 capture processes
WO2023230121A1 (fr) * 2022-05-27 2023-11-30 Blue Planet Systems Corporation Procédés et systèmes de synthèse de h2 avec une très faible empreinte co2

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US20040265158A1 (en) * 2003-06-30 2004-12-30 Boyapati Krishna Rao Co-producing hydrogen and power by biomass gasification

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WO2004046029A3 (fr) 2004-07-01
CA2505700A1 (fr) 2004-06-03
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AU2003288383A1 (en) 2004-06-15
EP1562854A2 (fr) 2005-08-17
FR2846958B1 (fr) 2005-08-26

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