WO2005033003A1 - Production d'hydrogene a partir de methanol - Google Patents

Production d'hydrogene a partir de methanol Download PDF

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Publication number
WO2005033003A1
WO2005033003A1 PCT/NO2004/000299 NO2004000299W WO2005033003A1 WO 2005033003 A1 WO2005033003 A1 WO 2005033003A1 NO 2004000299 W NO2004000299 W NO 2004000299W WO 2005033003 A1 WO2005033003 A1 WO 2005033003A1
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Prior art keywords
hydrogen
gas
reformer
oxygen
methanol
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PCT/NO2004/000299
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English (en)
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Erling Rytter
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Statoil Asa
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Priority to EP04775080A priority Critical patent/EP1680354A1/fr
Publication of WO2005033003A1 publication Critical patent/WO2005033003A1/fr

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    • 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
    • B01J8/02—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
    • B01J8/0278—Feeding reactive fluids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0229—Purification or separation processes
    • C01B13/0248—Physical processing only
    • C01B13/0251—Physical processing only by making use of membranes
    • 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
    • C01B3/32—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
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • 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
    • C01B3/32—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
    • C01B3/48—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 followed by reaction of water vapour with carbon monoxide
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00004—Scale aspects
    • B01J2219/00006—Large-scale industrial plants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • 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
    • C01B2203/0244—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0405—Purification by membrane separation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/042—Purification by adsorption on solids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
    • C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1217—Alcohols
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1217—Alcohols
    • C01B2203/1223—Methanol
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1217—Alcohols
    • C01B2203/1229—Ethanol
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/82—Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0043—Impurity removed
    • C01B2210/0046—Nitrogen

Definitions

  • the present invention relates to a method and a device for the production of hydrogen from an oxygenated hydrocarbon such as methanol, ethanol and the like.
  • the present method and device is inter alia useful for distributed production of hydrogen.
  • Hydrogen is expected to become an important energy carrier in the future both for heat and power generation and as a fuel. Hydrogen as such is an environmental friendly energy carrier. The use of hydrogen as a source of energy does not contribute to the emission of environmentally harmful gases.
  • Reforming of hydrocarbons is normally carried out at a high temperature to give maximum conversion of the feed to the desired products.
  • the temperature usually is in the range 800 - 1000 °C to avoid excessive so-called methane slip.
  • the reforming temperature is lower, both due to somewhat relaxed equilibrium constraints for the reaction, and also because coking of the catalyst becomes more important.
  • a naphtha feed often contemplated as the feed for hydrogen production coupled to fuel cells for CHP (combined heat and power) applications or in vehicles
  • the temperature in steam reforming usually is in 700 -800 °C range, at least above 650 °C. Methane formation is significant at all these temperatures, and becomes excessive in the low temperature range.
  • Using a hydrocarbon for generating hydrogen by reforming requires the availability of a separate source or storage of water and transfer lines for the water.
  • the source or storage of water and the transfer lines are exposed to freezing at temperatures below 0°C. Additionally a special device is needed for mixing the gaseous fed with water.
  • a simple system for distributed generation of hydrogen based on a hydrocarbon as feed is therefore difficult to achieve.
  • oxygenated hydrocarbons such as methanol, or ethanol or another oxygenate means two times reforming, first the reforming of natural gas (or other hydrocarbon feed) to syngas (CO + H 2 ) prior to synthesis of methanol or another oxygenate, and then reforming of methanol to give hydrogen.
  • large scale methanol plants are efficient and therefore provides methanol at an adequate price, e.g. below 120 USD/ton.
  • methanol as the feed provides several advantages and is therefore in many aspects an alternative feed for generation of hydrogen by reformation. Firstly, distribution of liquid methanol is easier than distribution of gas. Additionally, a specific advantage of using methanol instead of a hydrocarbon as feed for producing hydrogen by reforming is that the handling of water as co-feed is simplified.
  • the desired amount of water is simply included in the storage tank together with the methanol, either directly mixed in the tank, or premixed with the methanol supply.
  • the freezing point of methanol is as low as -93.9 °C, whereas a 1:1 molar mixture with water freezes at - 84.4 °C and a 2: 1 ratio (wate ⁇ methanol) at - 49,5 °C.
  • Methanol can be regarded as a substance that has undergone a partial oxidation of methane. Accordingly, less heat is required (compared to methane or naphtha) in the reforming process, and the reformation process may be performed at a lower temperature. This means that there also is less production of by-product like NOx and CO. The last point is particularly important if the hydrogen is going to be used as a fuel for PEM fuel cells as these normally are poisoned by CO. Further, methanol is a liquid and therefore is readily transported to the hydrogen generation site.
  • this reactor produces hydrogen, at least in principle, in pure form, it also has the disadvantages that the heat generated in the burner tubes is not fully utilized for the methanol reforming reaction, and that the combustion gases contain a large amount of nitrogen along with the combustion products (essentially CO 2 and H 2 O and any excess air). Besides low energy efficiency, it becomes very inconvenient and costly to separate out the greenhouse gas CO for further use or deposition.
  • the hourly reactor effluent is reported to be 2.2 kg H 2 , 13.1 kg CO 2 , 3.3 kg H 2 O and 0.2 kg CO.
  • Catalysts for methanation of CO are described, but not the shift conversion of CO to CO 2 .
  • means for generating the necessary heat, or removal of CO 2 have not been included.
  • a method for production of hydrogen from an oxygenated hydrocarbon fuel comprising the steps of: a) introducing the fuel, steam and an oxygen containing gas into a reformer comprising a catalytic bed, wherein the oxygen containing gas is introduced through one or more tubes made of porous material, inserted into the catalytic bed to form a reformed gas comprising hydrogen, CO, CO 2 , any inerts and un-reacted reactants, b) removing said reformed gas from the reformer, and c) separating the reformed gas into a hydrogen rich fraction and a hydrogen poor fraction in a separate unit.
  • the oxygenated hydrocarbon fuel and water is optionally mixed in a storage tank.
  • a separate water tank is avoided.
  • cold climate water supply may be a problem due to freezing.
  • This problem is also avoided by mixing water and fuel, as the fuel acts as a anti-freeze solution.
  • the mixture of fuel and water may e.g. be adjusted to give the mixture a freezing point as low as -20 or -30 °C.
  • the water shift reaction will result in a higher yield of hydrogen from the process, and at the same time reduce the amount of CO in the exhaust gas to an acceptable level.
  • the gas leaving the shift reactor is optionally introduced into a selective oxygenator to remove remaining CO by oxidation to form CO 2 .
  • essential pure hydrogen is separated from the reformed gas by means of a selective hydrogen permeable membrane.
  • essential pure hydrogen is separated from the reformed gas by means of pressure swing adsorbtion.
  • the oxygenated hydrocarbon feed is according to a preferred embodiment, methanol.
  • the oxygen containing gas is preferably air, oxygen enriched air or oxygen.
  • the use of substantially pure oxygen as the oxygen containing gas will reduce the total gas volume as the inert nitrogen is not introduced into the catalytic bed.
  • the reduced gas volume makes it possible to build a less voluminous plant.
  • the reduced gas volume will also make the separation of gases easier.
  • the invention relates to a plant for production of essentially pure hydrogen from an oxygenated hydrocarbon fuel, comprising an autothermal reformer including a catalytic bed, means for feeding the fuel, steam and an oxygen containing gas into the reformer and a separator for separation of substantially pure hydrogen from the remaining gas, wherein the reformer includes tube(s) made of a porous material inserted into the catalytic bed for introduction of the oxygen containing gas.
  • a water gas shift reactor between the reformer and the separator.
  • a selective oxygenator may optionally be placed between the water gas shift reactor and the separator.
  • Fig. 1 is a diagram illustrating the ratio of hydrogen to carbon (H 2 /C) as a function of the ratio of oxygen to carbon (mol O 2 /mol C) in partial oxidation + steam reforming of methanol for different levels of oxygen;
  • Fig. 2 is a diagram illustrating the heat of reaction, ⁇ H (kJ/mol), as a function of the ratio of oxygen to carbon (mol O 2 /mol C) in partial oxidation + steam reforming of methanol for different levels of oxygen;
  • Fig. 3 is a flow diagram illustrating a possible process for distributed hydrogen production
  • Fig. 4 illustrates a preferred reactor for distributed hydrogen production from methanol
  • Fig. 5 is a diagram illustrating the fuel cell conversion efficiency as a function of hydrogen pressure.
  • Such an autothermal system simplifies the whole hydrogen generation considerably as all large heat exchange surfaces can be minimized or eliminated, as the heat is generated internally in the reactor.
  • the oxygen or air can be fed to reactor tlirough a variety of systems, including premixing the gases, through special feeding tubes or nozzles, or by a membrane, inside or prior to the reactor.
  • One advantage of feeding oxygen instead of air is that the volumes of the process equipment become smaller as the voluminous nitrogen (ca. 80 % in air) is avoided.
  • a further aspect that sometimes have to be considered, is handling of CO .
  • CO can be separated as efficiently as possible from the product.
  • the dominant product gases will be H , CO and excess H O and N 2 if air is used. After condensation of the steam, it therefore is a significant advantage that it is only H 2 /CO 2 separation that is left. This separation can be performed by standard techniques using ammine wash, PSA (pressure swing adsorption) or membranes.
  • Figure 3 illustrates a preferred embodiment of the present invention.
  • the preferred feed, methanol is introduced into the system through a feed line 1 to a storage tank 2.
  • Water is added into the system either as illustrated by water feed line 3 into a line 4 leading from the storage tank to the reforming plant, or by adding water into the storage tank 2 separately or together with the methanol.
  • Methanol and water in line 4 are heated in a heat exchanger 5 before they are introduced into autothermal reformer 6.
  • Air, oxygen enriched air or oxygen is introduced into the autothermal reformer 6 through line 7.
  • the autothermal reformer 6 is preferably a reformer 6 as illustrated in figure 4.
  • the reformer 6 comprises a catalytic bed 23 through which the reactants flow, and one or more tube(s) 24. These tubes are either porous for distribution of air, oxygen enriched air or oxygen or having a semi permeable membrane allowing transport through the membrane of oxygen but not nitrogen.
  • the existing semi permeable membranes for selective transport of oxygen are Oxygen ion Transport Membranes (OTM).
  • An OTM membrane is a dense membrane, e.g. in form of a tube, allowing transport of oxygen ions across the membrane.
  • the hot gas leaving the reformer 6 in a line 8 is cooled down in a heat exchanger 9 before it is introduced into an optional shift reactor 10, where CO generated in the reformer is removed according to reaction II above.
  • the gas leaving the shift reactor 10 through line 11 is introduced into an optional selective oxygenator 12 if it is found necessary to remove remaining CO down to the ppm level by oxidation of traces of CO to CO 2 .
  • the gas leaving the selective oxygenator in line 13 can be cooled further down in a heat exchanger 14 before it is introduced into a separator 15 which separates hydrogen from CO 2 .
  • the separator 15 may be based on any technology suitable for separation of hydrogen and CO 2 , such as amine wash, Pressure Swing Adsorption (PSA) or membranes.
  • PSA Pressure Swing Adsorption
  • the configuration of the heat exchangers, e.g. 9 and 14, depends on the actual requirements of the process, like the temperature needed for the catalytic processes in the optional reactors 10 and 12 and the separator 15.
  • Separated CO 2 leaves the separator 15 through a line 16 for compression or liquefaction and storage or depositing, whereas hydrogen leaves the separator in a line 17.
  • the hydrogen in line 17 may be compressed in a compressor 18.
  • the hydrogen leaving the compressor 18 in line 19 is led to a hydrogen storage 20.
  • Hydrogen in storage 20 is taken out of the storage in a line 21 for further use tlirough a line 21.
  • all or parts of the produced hydrogen may be taken out in a line 22 for direct use in a fuel cell or other uses.
  • Unconverted methanol and steam may be condensed, e.g. as indicated by the dotted line after the heat exchanger 14 and then recycled through the lines 1 or 3.
  • any unconverted gas may wholly or partially be recycled whereas rest gas may be burned.
  • Methanol and steam are effectively reformed to form a reformed gas in temperatures in the reformer in the 250 to 350 °C range.
  • This temperature is sufficiently low to allow simple integration with a PEM fuel cell operated at ca. 80 °C or above, and at the same time gives high methanol conversion.
  • Another option is to operate at a higher temperature, in the 350-600 °C range, if increased fluxes of oxygen transport are facilitated by a higher temperature, as is the case for dense oxygen ion transport membranes.
  • the inventive method makes it possible to make a compact plant for hydrogen production. As only oxygen (ions) is transported through the tube wall, there will be no nitrogen on the fuel side and in the reformed gas product. T s lowers the total gas flow in the system and makes it easier to separate CO 2 for deposition. This arrangement also facilitates a design of the reactor that will minimize temperature gradients, and thereby reduce by-products and maximize conversion.
  • the effect of hydrogen dilution through the fuel cell (FC) stack is illustrated in figure 5.
  • the upper curve just illustrates that for a typical total pressure of 3 bar in the FC stack, the pressure is unchanged when the hydrogen is consumed during the series of cells when the feed to the stack is undiluted hydrogen.
  • Such essentially undiluted hydrogen is obtained through the present invention by autothermal reforming of methanol with oxygen followed by condensing of steam to water and separating out CO 2 .
  • the two next curves demonstrate the large reduction in the hydrogen partial pressure when hydrogen is obtained by conventional steam reforming of methane or methanol, respectively. Similar partial pressures occur for autothermal reforming with oxygen, whereas the internal nitrogen present when the ATR is performed with air naturally lowers the hydrogen pressure further.
  • the present method and plant is therefore an attractive solution for distributed production of hydrogen. Even at the reaction temperature mentioned above, the temperature will be 200-300 °C lower than needed for reforming of naphtha.

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  • Chemical & Material Sciences (AREA)
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  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Hydrogen, Water And Hydrids (AREA)

Abstract

L'invention concerne un procédé de production d'hydrogène à partir d'un combustible hydrocarboné oxygéné comprenant les étapes consistant: a) à introduire le combustible, la vapeur et un gaz renfermant de l'oxygène dans un reformeur comprenant un lit catalytique, le gaz renfermant de l'oxygène étant introduit dans un ou de plusieurs tubes conçus dans un matériau poreux, introduits dans le lit catalytique de manière à former un reformat renfermant de l'hydrogène, du CO, du CO2, des matières inertes quelconques et des réactifs qui n'ont pas réagis, b) à éliminer le reformat du reformeur et c) à séparer le reformat en une fraction riche en hydrogène et en une fraction pauvre en hydrogène dans une unité distincte. L'invention concerne également des installations permettant de mettre en oeuvre le procédé.
PCT/NO2004/000299 2003-10-06 2004-10-06 Production d'hydrogene a partir de methanol WO2005033003A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP04775080A EP1680354A1 (fr) 2003-10-06 2004-10-06 Production d'hydrogene a partir de methanol

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NO20034468A NO20034468D0 (no) 2003-10-06 2003-10-06 Hydrogenproduksjon fra metanol
NO20034468 2003-10-06

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NO (1) NO20034468D0 (fr)
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7419648B2 (en) 2004-07-16 2008-09-02 Shell Oil Company Process for the production of hydrogen and carbon dioxide
US9957161B2 (en) 2015-12-04 2018-05-01 Grannus, Llc Polygeneration production of hydrogen for use in various industrial processes
US10228131B2 (en) 2012-06-27 2019-03-12 Grannus Llc Polygeneration production of power and fertilizer through emissions capture
US10435343B2 (en) 2016-04-13 2019-10-08 Northwestern University Efficient catalytic greenhouse gas-free hydrogen and aldehyde formation from alcohols
CN110550604A (zh) * 2019-10-17 2019-12-10 华润智慧能源有限公司 一种火电耦合甲醇制氢的新型热力系统
CN110844883A (zh) * 2019-10-28 2020-02-28 中科院大连化学物理研究所张家港产业技术研究院有限公司 氢分离与水煤气重整一体式低压制氢系统及其方法
CN110937573A (zh) * 2019-10-28 2020-03-31 中科液态阳光(苏州)氢能科技发展有限公司 氢气混合余气重整方法
CN111377403A (zh) * 2020-04-23 2020-07-07 广东大昆科技有限公司 一种静默紧凑型可移动甲醇低温液相重整制氢系统

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19907796A1 (de) * 1999-02-24 2000-02-24 Daimler Chrysler Ag Reaktor zur Wasserstofferzeugung
EP1094030A2 (fr) * 1999-10-20 2001-04-25 Nippon Chemical Plant Consultant Co., Ltd. Méthode et dispositif de génération d'hydrogène par reformage
US6338833B1 (en) * 1999-03-05 2002-01-15 Haldor Topsoe A/S Process for autothermal catalytical stream reforming
US20020071975A1 (en) * 2000-12-11 2002-06-13 Toyota Jidosha Kabushiki Kaisha Hydrogen gas generating systems, fuel cell systems and methods for stopping operation of fuel cell system
WO2003062141A1 (fr) * 2002-01-23 2003-07-31 Statoil Asa Procede de preparation d'un gaz de synthese par reformage autothermique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19907796A1 (de) * 1999-02-24 2000-02-24 Daimler Chrysler Ag Reaktor zur Wasserstofferzeugung
US6338833B1 (en) * 1999-03-05 2002-01-15 Haldor Topsoe A/S Process for autothermal catalytical stream reforming
EP1094030A2 (fr) * 1999-10-20 2001-04-25 Nippon Chemical Plant Consultant Co., Ltd. Méthode et dispositif de génération d'hydrogène par reformage
US20020071975A1 (en) * 2000-12-11 2002-06-13 Toyota Jidosha Kabushiki Kaisha Hydrogen gas generating systems, fuel cell systems and methods for stopping operation of fuel cell system
WO2003062141A1 (fr) * 2002-01-23 2003-07-31 Statoil Asa Procede de preparation d'un gaz de synthese par reformage autothermique

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7419648B2 (en) 2004-07-16 2008-09-02 Shell Oil Company Process for the production of hydrogen and carbon dioxide
US10228131B2 (en) 2012-06-27 2019-03-12 Grannus Llc Polygeneration production of power and fertilizer through emissions capture
US9957161B2 (en) 2015-12-04 2018-05-01 Grannus, Llc Polygeneration production of hydrogen for use in various industrial processes
US10611634B2 (en) 2015-12-04 2020-04-07 Grannus, Llc Polygeneration production of hydrogen for use in various industrial processes
US10435343B2 (en) 2016-04-13 2019-10-08 Northwestern University Efficient catalytic greenhouse gas-free hydrogen and aldehyde formation from alcohols
CN110550604A (zh) * 2019-10-17 2019-12-10 华润智慧能源有限公司 一种火电耦合甲醇制氢的新型热力系统
CN110550604B (zh) * 2019-10-17 2024-06-07 华润智慧能源有限公司 一种火电耦合甲醇制氢的新型热力系统
CN110844883A (zh) * 2019-10-28 2020-02-28 中科院大连化学物理研究所张家港产业技术研究院有限公司 氢分离与水煤气重整一体式低压制氢系统及其方法
CN110937573A (zh) * 2019-10-28 2020-03-31 中科液态阳光(苏州)氢能科技发展有限公司 氢气混合余气重整方法
CN110937573B (zh) * 2019-10-28 2023-08-22 中科液态阳光(苏州)氢能科技发展有限公司 氢气混合余气重整方法
CN110844883B (zh) * 2019-10-28 2023-12-08 中科院大连化学物理研究所张家港产业技术研究院有限公司 氢分离与水煤气重整一体式低压制氢系统及其方法
CN111377403A (zh) * 2020-04-23 2020-07-07 广东大昆科技有限公司 一种静默紧凑型可移动甲醇低温液相重整制氢系统

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