WO2011028133A1 - Method for producing synthesis gas from natural gas using a promoter and ceria in the form ce203 - Google Patents

Method for producing synthesis gas from natural gas using a promoter and ceria in the form ce203 Download PDF

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WO2011028133A1
WO2011028133A1 PCT/NO2010/000328 NO2010000328W WO2011028133A1 WO 2011028133 A1 WO2011028133 A1 WO 2011028133A1 NO 2010000328 W NO2010000328 W NO 2010000328W WO 2011028133 A1 WO2011028133 A1 WO 2011028133A1
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ceria
promoter
production
hydrogen
synthesis gas
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PCT/NO2010/000328
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French (fr)
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Erik Fareid
Tommy Schierning
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    • 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
    • C01B3/061—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 metal oxides with water
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    • 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
    • C01B3/38—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
    • C01B3/386—Catalytic partial combustion
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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
    • C01B2203/025—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]
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    • C01B2203/061—Methanol production
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    • C01B2203/06—Integration with other chemical processes
    • C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
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    • C01B2203/06—Integration with other chemical processes
    • C01B2203/068—Ammonia synthesis
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
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    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
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    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
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    • C01B2203/1052—Nickel or cobalt catalysts
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
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    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1064—Platinum group metal catalysts
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    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1064—Platinum group metal catalysts
    • C01B2203/107—Platinum catalysts
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1076—Copper or zinc-based catalysts
    • C—CHEMISTRY; METALLURGY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • 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
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • 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 concerns a process for producing hydrogen using a
  • promoter/catalyst/activator system and ceria in the form of Ce 2 0 3 by reacting the 5 ceria with the promoter in the presence of water for oxidizing the ceria into Ce0 2 and processing the produced Ce0 2 and promoter for reducing Ce0 2 into Ce 2 0 3 through the production of synthesis gas
  • Hydrogen is sought of as a clean source of energy. However, for the produced0 hydrogen to be part of a sustainable technology, such hydrogen must then be
  • JP patent 7069603 A Japan Petroleum Exploration Co, Otsuka Kiyoshi,
  • the process according to the present invention uses, however, a new type of promoter/catalyst/activator (see infra).
  • the prior art using ceria is based on the cerium oxide cycle.
  • Ce 2 0 3 is oxidized at 400 to 600 °C by splitting water according to the reaction:
  • synthesis gas is meant to include a mixture of gaseous carbon monoxide, CO, and hydrogen, H 2 .
  • natural gas may be one of the above mentioned gases in pure form or any mixture or composition of such gases.
  • Natural gas may also contain alkenes and/or alkynes of the same chain length as the alkanes.
  • Natural gas may also comprise a gas containing the above mentioned elements arriving to the system according to the present invention through any number of previous purification or synthesis steps.
  • low temperature is meant to include above -25 °C and below 200 °C.
  • intermediate temperature is meant to include temperatures in the interval 200-500°C.
  • high temperature is meant to include temperatures above 500°C.
  • the term "higher chain organic compounds” is meant to include carbon-containing compounds with a chain length of 2 carbon atoms or more, and also including atoms selected from the species oxygen, hydrogen and nitrogen optionally along with other hetero atoms.
  • promoter activator
  • catalyst are used interchangeably and are meant to include a substance promoting the relevant reaction at a reduced activation energy/reduced temperature as compared to the same reaction without the promoter/catalyst/activator.
  • the indicated parameters e.g. temperature, pressure, time intervals etc.
  • the indicated parameters are to be taken as guiding, including a deviation interval of ⁇ 10% of the given parameter.
  • Ceria cycle can be used at much lower temperatures using the present invention.
  • Ceria together with a promoter/catalyst/activator is used in the present invention at much lower temperatures and at a different reaction route than the prior art.
  • the low temperature water splitting with Ce 2 0 3 according to the present invention is taking place at 0 to 350 °C according to the following equation: promoter
  • the most preferable temperatures for reaction 1 are 50-150 °C.
  • a combination of reactions 1 and 2 will lead to the formation of synthesis gas that can be used for many purposes. Examples of such purposes are:
  • reaction 1 produces energy and adds a large amount of hydrogen into the equation.
  • the reaction is the water-gas shift reaction and is in practice carried out using two adiabatic fixed-bed reactors with cooling between the reactors.
  • the first reactor high temperature shift, operates at high temperature (590 - 620 K) and contains a classical catalyst, usually iron oxide promoted with chromium oxide.
  • the second reactor low temperature shift, contains a more active catalyst, usually copper on a mixed support composed of zinc oxide and aluminum oxide, and operates in the temperature range of 470 - 520 K.
  • the reaction can be carried out at all practical pressures, e.g. atmospheric.
  • the hydrogen produced may be used in a hydrogen fuel cell, it may be combusted or used in any other way to produce energy or other chemical substances.
  • the present invention uses ceria/Gd/Zirconia mixtures in combination with any of the substances listed below as promoter/activator/catalyst (described in the "catalyst system”) :
  • the above disclosed catalyst system may be supported by any known support system, e.g. Al 2 0 3 , Ti0 2 , etc.
  • a reactor including any known reactor types may be used, some may be fixed bed, fluidized bed, radial flow, axial flow, etc.
  • Ceria/Gd/Zirconia including trace amounts of promoter metal (trace amounts being more than 0, e.g. 0,1 to 10 weight %) and being present in the form of solid particles. This may support the above indicated ceria cycle, optionally with the recycling of methane for driving the reduction of ceria.
  • trace amounts of promoter metal trace amounts being more than 0, e.g. 0,1 to 10 weight % and being present in the form of solid particles.
  • That water is divided into hydrogen and oxygen at low temperatures.
  • the hydrogen and synthesis gas may be used as fuel or as a raw material for numerous processes.
  • the present invention produces energy in the form of hydrogen or in the form of synthesis gas far more effectively than similar processes operating at higher temperatures.
  • Synthesis gas is produced at low to medium temperatures.
  • the process according to the present invention may inter alia be used for: producing organic compounds, e.g. methanol, ethanol, urea or higher chain organic compounds;
  • inorganic compounds e.g. ammonia, cyanides, C0 2 , fertilizer; producing any form of energy, e.g. electrical energy and/or heat; and for producing energy without the emission of C0 2
  • the present invention may be considered as a two step process with one step reducing the catalytic matrix of ceria or similar and the second step being the water - splitting with production of hydrogen.
  • the present invention may be coupled with the methanation process shown in the reaction below:
  • the methanation reaction is exothermic and occurring at a temperature of 150 to 600 °C.
  • the heat developed during this reaction will be used to produce electricity or other forms of energy, while methane is recycled to the reduction of ceria as described in equation 1. This means that the energy obtained by low temperature water splitting may be used entirely for energy production.
  • the catalyst system may be any solid mixture combination comprising Gd plus Ceria a combination of Gd plus Ceria and Zirconia plus Ceria solid mixture. It is also possible to have a mix of all of these components.
  • the catalyst system must have a small loading of the metals listed above.
  • the promoter loading may optionally be as low as 0,1% and will be above 0 and may preferably lie within the interval 0,1 to 3 weight % , and will give very good water splitting (reaction 1) results at
  • the suggested temperature area is 0-400 °C, with 50-150 °C as the preferred area.
  • the amount of promoter is suggested to be in the area of 0,1 to 10 weight % with the preferred area of more than 0 % by weight and preferably 0,1 to 3 weight %.
  • the same catalyst disclosed supra may be used to produce the synthesis gas.
  • the suggested temperature interval for the production of synthesis gas (reaction 2) is 200-600°C, with the preferred interval 300-500°C.
  • the catalyst/ promoter system can be made based on all known methods of catalyst production based on salts of each component and mixed before the solid catalyst/promoter is formed. It can be based on insipient wetness principles, sol gel processes etc. Brief account of the figures.
  • Figure 1 Synthesis gas production from ceria cycle.
  • Figure 2 Synthesis gas for ammonia production.
  • FIG. 3 Synthesis gas as fuel for a synthesis gas engine. Detailed use of the invention.
  • Ceria (Ce0 2 , Ce 2 0 3 ) is always combined with a promoter chosen from the list supra (also optionally including Gd and Zirconia, see supra).
  • FIG. 1 The figure shows a feed of natural gas (assuming 100% methane) being mixed (1) with Ceria (Ce0 2 ) and fed by the aid of a controller (2) adjusting the correct amount of ceria to a reactor or reactor compartment (3) where the Ce0 2 is reduced to Ce 2 0 3 and hence methane is oxidized.
  • the product gas is CO and H 2 , synthesis gas with a H 2 :CO concentration ratio of 2: 1.
  • the solid Ce 2 0 3 is separated (4), mixed with water (5) and fed to a reactor (6) where the Ce 2 0 3 is oxidized to Ce0 2 .
  • the product gas is H 2 .
  • the solid is separated (7) and mixed with methane (1).
  • the solid is cycled between reactors (3) and (6).
  • the gas from the separators (4) and (7) is mixed (8) and the synthesis gas can be used as a raw material for other processes.
  • Synthesis gas produced from the method described in Figure 1 is heat exchanged to ambient temperature (25) and mixed with air (26).
  • the mixture is burned in a synthesis gas engine (27) producing power, the hot flue gas is heat exchanged (28) and may be treated elsewhere. Examples
  • Example 1 describes the flow sheet where synthesis gas is produced by the new invention. To replace some of the Ceria that may be lost during the circulation and reduction/oxidation cycle of Ceria there will be add up of Ceria.
  • Ceria particles broken down will also be a purged from the system (not indicated on the flow sheet).
  • Methane is fed to the syngas (synthesis gas) reactor and reacted to syngas at a temperature of 450 °C and a pressure of 1 bar.
  • the reaction of methane to syngas takes place by reducing the Ceria.
  • the exit synthesis gas and Ceria may be cooled by the incoming methane stream to around 100 °C and separated. Water vapor at 1 bar and 100 °C is added to the reduced Ceria and oxidized by producing hydrogen from the water.
  • the oxidized ceria is then separated from the hydrogen and recycled to the methane reactor where it again is reduced.
  • the produced syngas and the produced hydrogen may be used separately or mixed.
  • Example 2 describes the new invention used in the production of a gas mixture for the production of ammonia.
  • the production of the syngas is described in Example 1 with all the benefits being the same compared to the known processes of producing ammonia today.
  • the compression energy of the syngas before entering the LT and HT shift reactors and the methanation will be strongly reduced due to the reduced volume of syngas.
  • the reduced volume is only 60 % of a standard process, which will be the case for the rest of the production process.
  • Nitrogen will be produced separately by a membrane and added to the syngas to produce the ammonia feed gas.
  • the LT reactor is operated at 230 °C and 39 bar, while the HT shift is operated at 440 °C and 38 bar and the methanation reactor is operated at 340 °C and 37 bar.
  • the new invention as described in Example 1 supra strongly reduces the need for high temperature energy in the syngas production.
  • the LT and HT shift reactors and the methanator is run at the same conditions as a standard ammonia production plant and will produce the same amount of heat.
  • the energy reduction related to the compression will be reduced by 40 % and so will all the reactor volumes.
  • the investment for a plant built using the new technology may be as low as 1/3 compared to any known processes today.
  • the energy demand may be as low as 1/3 compared to any known process today.
  • Ir iridium or a combination of Ir and a co-metal taken among noble metals (for example Pt, Pd)
  • Ru ruthenium Co (copper) Rh (Rhodium) - Ag (silver)
  • the reduction of ceria and the production of synthesis gas 200-600°C, more preferred 300-500°C, are that the promoter/catalyst/activator system allows reaction temperatures below the temperatures used in the state of the art, as well as using H 2 0 for regenerating the ceria and not CO as in the prior art.
  • the reduction of ceria is conducted at 400-600°C by using CH 4
  • the oxidation with water is conducted at 100-200°C by using H 2 0 and coupling this to different chemical and electrical processes.
  • the processes according to the present invention are thus conducted at significantly lower temperatures than what is conventional and thus at a lower energy consumption than what is possible with the prior art.

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Abstract

The present invention concerns a process for producing hydrogen from a feed of natural gas using a promoter and ceria in the form of Ce2O3 by reacting the ceria with the promoter in the presence of water for oxidizing the ceria into CeO2 and processing the produced CeO2 and promoter for reducing CeO2 into Ce2O3 through the production of synthesis gas. It is also described promoters suitable for performing the process.

Description

METHOD FOR PRODUCING SYNTHESIS GAS FROM NATURAL GAS USING A PROMOTER AND CERIA
IN THE FORM CE203
The present invention concerns a process for producing hydrogen using a
promoter/catalyst/activator system and ceria in the form of Ce203 by reacting the 5 ceria with the promoter in the presence of water for oxidizing the ceria into Ce02 and processing the produced Ce02 and promoter for reducing Ce02 into Ce203 through the production of synthesis gas
Background for the invention:
Hydrogen is sought of as a clean source of energy. However, for the produced0 hydrogen to be part of a sustainable technology, such hydrogen must then be
based on green energy like solar, wind or other renewable energy sources.
Dissociation of water (water-splitting) has been recognized as an essential source of Hydrogen production, but has up to date been correlated to high demand of energy and thereby low efficiencies. 5 Thus there is a demand for an environmentally sustainable method for producing cheap synthesis gas, and especially synthesis gas comprising hydrogen.
Prior art:
Below are some of the articles that deal with the production of hydrogen through different technologies: 0 Matsouka M, Kitano M, Takeuchi M, Tsujimaru K, Anpo K and Thomas JM (2007)
'Photocata lysis for new energy production. Recent advances in photocata lysis water splitting reactions for hydrogen production' Catalysis today, 6. March 2007.
Balachandran U, Lee TH and Dorris SE (2007) 'Hydrogen production by water dissociation using mixed conducting dense ceramic membranes' International5 Journal of Hydrogen Energy, Volume 32, no. 4, March 2007, page 451-456.
Ginosar DM, Petkovic LM, Glenn AW and Burch KC (2007) 'Stability of supported platinum sulfuric acid decomposition catalysis for use in thermo chemical water splitting cycles' International journal of hydrogen energy, Volume 32, no.4, March 2007, page 482-488. Otsuka, Hatano and Morikawa (1983) Ή2 from H20 by reduced Ce02' Tokyo Institute of technology.
Sano T, Kojima M, Hasegawa, Tsuji M and Tamaura Y (1996) Thermo chemical water-splitting by a carbon -bearing Ni(II) ferrite at 300°C International Journal of hydrogen energy, Volume 21, no. 9, September 1996, page 781-787.
Mohapatra SK, Misra M, Mahajan VK and Raja KS (2007) Ά novel method for the synthesis of titania nano tubes using sono electro chemical method and its application for photo electro chemical splitting of water' Journal of catalysis , Volume 246, no. 2, 10 March 2007, page 362-369. Ni M, Leung MKH, Leung DYC and Sumathy K (2007) 'A review and recent development in photo-catalysis water-splitting using Ti02 for hydrogen production' Renewable and sustainable energy reviews, Volume 11 no.3, April 2007, page 401- 425.
Shangguan W (2007) 'Hydrogen evolution from water splitting on nano composite photo-catalysts' Science and Technology of advanced materials, Volume 8, no. 1-2, January-March 2007, page 76-81, APNF International Symposium on
Nanotechnology in environmental Protection and Pollution (ISNEPP2006).
US patent 6.972.119 (Taguchi et al., December 6, 2005) 'Apparatus for forming hydrogen'. US Patent 6.838.071 (Olsvik et al., January 4, 2005) 'Process for preparing a H2- rich gas and C02-rich gas at high pressure'.
Kundakovic Lj., Mullins DR, Overbury SH (2000) 'Adsorption and reaction of H20 and CO on oxidized and reduced Rh/CeOx(III) surfaces' Surface Science, Volume 457, Issues 1-2, 1 June 2000, Pages 51-62. Below are some of the articles that deal with the production of synthesis gas through different technologies:
Rostrup-Nielsen JR (1984) 'Catalytic steam reforming' in Anderson JR and Boudart M (eds.) Catalysis. Science and Technology, Springer-Verlag, Berlin, pp- 1-117. Czuppon TA, Knez SA and Rovner JM (1992) 'Ammonia' in: Kroschwitz JI, Howe- Grant M (eds.) Kirk-Othmer Encyclopedia of Chemical Technology vol 2, 4th ed., Wiley, New York, pp. 638-691.
Rostrup-Nielsen JR (1993) 'Production of synthesis gas' Catal. Today 18 305-324. Pena MA, Gomez JP and Fierro JLG (1996) 'New catalytic routes for syngas and hydrogen production' Appl. Catal. 144 7-57.
Balachandran U, Dusek JT, Maiya PS, Ma B, Mieville RL, Kleefisch MS and Udovich CA (1997) 'Ceramic membrane reactor for converting methane to syngas' Catal. Today 36 265-272. K. Outsuka et al., "The production of Synthesis Gas by the Redox of Cerium Oxide", Studies in Surface Science and Catalysis (1997) 107 (Natural Gas Conversion IV), 531-536.
JP patent 7069603 A, Japan Petroleum Exploration Co, Otsuka Kiyoshi,
(1995.03.14). It is also known to produce synthesis gas over ceria at 600-800°C according to the reaction
CH4 + H20 = CO + 3H2
The process according to the present invention uses, however, a new type of promoter/catalyst/activator (see infra). The prior art using ceria is based on the cerium oxide cycle. In the ceria cycle Ce203 is oxidized at 400 to 600 °C by splitting water according to the reaction:
Ce203 + H20 = 2Ce02 + H2
The reduction of ceria (Ce02) is then carried out at high temperature of 2000 °C using e.g. solar reflectors according to the equation shown below:
2Ce02 = Ce203 + V2 02 As can be seen from the above indicated ceria cycle the Cerium is reduced and subsequently oxidized through the splitting of water into hydrogen and oxygen. However, the indicated high temperature of 2000°C is detrimental for using this cycle for splitting water in practice. Definition of terms
In the present disclosure the term "synthesis gas" is meant to include a mixture of gaseous carbon monoxide, CO, and hydrogen, H2.
In the present disclosure the term "natural gas" is meant to encompass all types of gas comprising gaseous alkanes (CnH2n+2 wherein n = 1-20, more preferred wherein n = 1-10, e.g. methane, ethane, propane, butane, hexane, heptane, octane, nonane, decane, etc.) and wherein such a gas additionally may include other gases as well, e.g. C02, CO, H20, gaseous compounds including nitrogen (e.g. NH3, NO, NOx), sulphur (e.g. S02), oxygen, phosphor and also trace amounts of other gases (e.g. noble gases). The term "natural gas" may be one of the above mentioned gases in pure form or any mixture or composition of such gases. "Natural gas" may also contain alkenes and/or alkynes of the same chain length as the alkanes.
"Natural gas" may also comprise a gas containing the above mentioned elements arriving to the system according to the present invention through any number of previous purification or synthesis steps. In the present disclosure the term "low temperature" is meant to include above -25 °C and below 200 °C.
In the present disclosure the term "medium temperature" is meant to include temperatures in the interval 200-500°C.
In the present disclosure the term "high temperature" is meant to include temperatures above 500°C.
In the present disclosure the term "higher chain organic compounds" is meant to include carbon-containing compounds with a chain length of 2 carbon atoms or more, and also including atoms selected from the species oxygen, hydrogen and nitrogen optionally along with other hetero atoms. In the present disclosure the terms "promoter", activator" and "catalyst" are used interchangeably and are meant to include a substance promoting the relevant reaction at a reduced activation energy/reduced temperature as compared to the same reaction without the promoter/catalyst/activator.
In the present context the indicated parameters (e.g. temperature, pressure, time intervals etc.) are to be taken as guiding, including a deviation interval of ±10% of the given parameter.
Disclosure of the present invention
It has now been found that the ceria cycle can be used at much lower temperatures using the present invention. Ceria together with a promoter/catalyst/activator (see infra) is used in the present invention at much lower temperatures and at a different reaction route than the prior art.
The low temperature water splitting with Ce203 according to the present invention is taking place at 0 to 350 °C according to the following equation: promoter
Ce203 + H20 = 2Ce02 + H2 1. (Ceria oxidation)
The reduction of ceria is done at 200 to 500 °C according to the following reaction scheme: promoter
2Ce02 + CH4 = Ce203 + CO + 2H2 2. (Ceria reduction)
The most preferable temperatures for reaction 1 are 50-150 °C.
A combination of reactions 1 and 2 will lead to the formation of synthesis gas that can be used for many purposes. Examples of such purposes are:
Ammonia synthesis
Methanol synthesis Fischer-Tropsch process
Gas turbine fuel
Carbon Capture and Storage CCS
The main advantages with the present invention are that reaction 1. produces energy and adds a large amount of hydrogen into the equation.
From the synthesis gas even more hydrogen can be produced by the equation:
CO + H20 = C02 + H2 3.
The reaction is the water-gas shift reaction and is in practice carried out using two adiabatic fixed-bed reactors with cooling between the reactors. The first reactor, high temperature shift, operates at high temperature (590 - 620 K) and contains a classical catalyst, usually iron oxide promoted with chromium oxide. The second reactor, low temperature shift, contains a more active catalyst, usually copper on a mixed support composed of zinc oxide and aluminum oxide, and operates in the temperature range of 470 - 520 K. The reaction can be carried out at all practical pressures, e.g. atmospheric.
Based on the process according to the present invention it is obvious for a person skilled in the art that the C02 is easily separated from the hydrogen and can be stored or used in any desired way. This way of producing pure hydrogen and C02 is inexpensive and has almost no parasitic load (extra supplied energy) compared to any other separation process used today.
The hydrogen produced may be used in a hydrogen fuel cell, it may be combusted or used in any other way to produce energy or other chemical substances.
The present invention uses ceria/Gd/Zirconia mixtures in combination with any of the substances listed below as promoter/activator/catalyst (described in the "catalyst system") :
Pd (palladium )
Pt (platinum) Ir (iridium) or a combination of Ir and a co-metal taken among noble metals ( for example Pt, Pd)
- Ni (Nickel) u (ruthenium) - Co (copper)
- Rh (Rhodium) Ag (silver)
- Co (cobalt) W (tungsten) - All other catalyst alone or together with one or more of the metals
mentioned supra.
The above disclosed catalyst system may be supported by any known support system, e.g. Al203, Ti02, etc.
In the present invention a reactor including any known reactor types may be used, some may be fixed bed, fluidized bed, radial flow, axial flow, etc. The
Ceria/Gd/Zirconia including trace amounts of promoter metal (trace amounts being more than 0, e.g. 0,1 to 10 weight %) and being present in the form of solid particles. This may support the above indicated ceria cycle, optionally with the recycling of methane for driving the reduction of ceria. The advantages of the present invention are:
That water is divided into hydrogen and oxygen at low temperatures.
- The hydrogen and synthesis gas may be used as fuel or as a raw material for numerous processes. The present invention produces energy in the form of hydrogen or in the form of synthesis gas far more effectively than similar processes operating at higher temperatures.
Synthesis gas is produced at low to medium temperatures. - The process according to the present invention may inter alia be used for: producing organic compounds, e.g. methanol, ethanol, urea or higher chain organic compounds;
producing inorganic compounds, e.g. ammonia, cyanides, C02, fertilizer; producing any form of energy, e.g. electrical energy and/or heat; and for producing energy without the emission of C02
The present invention may be considered as a two step process with one step reducing the catalytic matrix of ceria or similar and the second step being the water - splitting with production of hydrogen.
The present invention may be coupled with the methanation process shown in the reaction below:
CO + 3H2 = CH4 + H20 4.
The methanation reaction is exothermic and occurring at a temperature of 150 to 600 °C. The heat developed during this reaction will be used to produce electricity or other forms of energy, while methane is recycled to the reduction of ceria as described in equation 1. This means that the energy obtained by low temperature water splitting may be used entirely for energy production.
There are many other processes that may be a part of the new invention. Some of these are:
Ammonia production - Methanol production
Electricity production using a combination of syngas SOFC and hydrogen fuels cell Electricity production using hydrogen fuel cell with the production of pure C02 for storage
Electricity production using hydrogen with C02 sequestering
Ethanol Production - Urea production
All other processes that produces electricity, power, heat or chemicals that use syngas or hydrogen as raw materials
The catalyst system may be any solid mixture combination comprising Gd plus Ceria a combination of Gd plus Ceria and Zirconia plus Ceria solid mixture. It is also possible to have a mix of all of these components. The catalyst system must have a small loading of the metals listed above. The promoter loading may optionally be as low as 0,1% and will be above 0 and may preferably lie within the interval 0,1 to 3 weight % , and will give very good water splitting (reaction 1) results at
temperatures lower than 100 °C. The suggested temperature area is 0-400 °C, with 50-150 °C as the preferred area.
The amount of promoter is suggested to be in the area of 0,1 to 10 weight % with the preferred area of more than 0 % by weight and preferably 0,1 to 3 weight %.
The same catalyst disclosed supra may be used to produce the synthesis gas. The suggested temperature interval for the production of synthesis gas (reaction 2) is 200-600°C, with the preferred interval 300-500°C.
The catalyst/ promoter system can be made based on all known methods of catalyst production based on salts of each component and mixed before the solid catalyst/promoter is formed. It can be based on insipient wetness principles, sol gel processes etc. Brief account of the figures.
Figure 1: Synthesis gas production from ceria cycle. Figure 2: Synthesis gas for ammonia production.
Figure 3: Synthesis gas as fuel for a synthesis gas engine. Detailed use of the invention.
Ceria (Ce02, Ce203) is always combined with a promoter chosen from the list supra (also optionally including Gd and Zirconia, see supra).
Figure 1. The figure shows a feed of natural gas (assuming 100% methane) being mixed (1) with Ceria (Ce02) and fed by the aid of a controller (2) adjusting the correct amount of ceria to a reactor or reactor compartment (3) where the Ce02 is reduced to Ce203 and hence methane is oxidized. The product gas is CO and H2, synthesis gas with a H2:CO concentration ratio of 2: 1. The solid Ce203 is separated (4), mixed with water (5) and fed to a reactor (6) where the Ce203 is oxidized to Ce02. The product gas is H2. The solid is separated (7) and mixed with methane (1). The solid is cycled between reactors (3) and (6). The gas from the separators (4) and (7) is mixed (8) and the synthesis gas can be used as a raw material for other processes.
Figure 2. Synthesis gas produced from the method described in Figure 1 (ref. nos. 1-8) is compressed (9) and mixed with process water (10). The excess heat is removed (11, 13 and 14) before the gas enters the high and low temperature shift reactors (12 and 15) where the water-gas shift reaction (equation 3) is carried out. C02 is separated (17) and the C02 lean gas is methanated (18) to remove all CO and C02 in the gas. The excess heat in the CO and C02 free gas is removed (19, 20 and 21) and water is flashed off (22). Nitrogen is separated from air (24) and mixed with the H2 rich gas (23) giving synthesis gas for ammonia production. The separated C02 may be used for urea production utilizing the produced ammonia. The total C02 emission from this combination is much lower than any known processes.
Figure 3. Synthesis gas produced from the method described in Figure 1 is heat exchanged to ambient temperature (25) and mixed with air (26). The mixture is burned in a synthesis gas engine (27) producing power, the hot flue gas is heat exchanged (28) and may be treated elsewhere. Examples
The examples infra refer to the figures mentioned supra.
Example 1. Figure 1 describes the flow sheet where synthesis gas is produced by the new invention. To replace some of the Ceria that may be lost during the circulation and reduction/oxidation cycle of Ceria there will be add up of Ceria.
Ceria particles broken down will also be a purged from the system (not indicated on the flow sheet). Methane is fed to the syngas (synthesis gas) reactor and reacted to syngas at a temperature of 450 °C and a pressure of 1 bar. The reaction of methane to syngas takes place by reducing the Ceria. The exit synthesis gas and Ceria may be cooled by the incoming methane stream to around 100 °C and separated. Water vapor at 1 bar and 100 °C is added to the reduced Ceria and oxidized by producing hydrogen from the water. The oxidized ceria is then separated from the hydrogen and recycled to the methane reactor where it again is reduced. The produced syngas and the produced hydrogen may be used separately or mixed. There is no addition of air or water to produce the syngas and only water vapors are added the hydrogen production reactor. Due to the fact that no air or water is added to the syngas production the size of the equipment will be strongly reduced compared to any previously known way of producing syngas. The reactor volume will be reduced by a factor of 5 meaning that the size with the new technology is only 20 % compared to previously known technology. Another advantage is that the syngas using the present invention may be produced at medium temperatures (450 °C), while the syngas production using any known technology needs to use temperatures in the range of 600 to 1000 °C. The new invention thus reduces the need for high temperature energy. As a side product of the new invention, hydrogen is produced at low temperatures (100 °C) and will be almost 100 % pure. Any known technology today can only produce hydrogen from water above 400 °C.
Example 2. Figure 2 describes the new invention used in the production of a gas mixture for the production of ammonia. The production of the syngas is described in Example 1 with all the benefits being the same compared to the known processes of producing ammonia today. In addition the compression energy of the syngas before entering the LT and HT shift reactors and the methanation will be strongly reduced due to the reduced volume of syngas. The reduced volume is only 60 % of a standard process, which will be the case for the rest of the production process. Nitrogen will be produced separately by a membrane and added to the syngas to produce the ammonia feed gas. The LT reactor is operated at 230 °C and 39 bar, while the HT shift is operated at 440 °C and 38 bar and the methanation reactor is operated at 340 °C and 37 bar. The new invention as described in Example 1 supra strongly reduces the need for high temperature energy in the syngas production. The LT and HT shift reactors and the methanator is run at the same conditions as a standard ammonia production plant and will produce the same amount of heat. However, as the volume of gas is only 60 % compared to a standard process the energy reduction related to the compression will be reduced by 40 % and so will all the reactor volumes. As a result of these benefits the investment for a plant built using the new technology may be as low as 1/3 compared to any known processes today. The energy demand may be as low as 1/3 compared to any known process today.
Some, among others, of the differences/advantages that are associated with the process according to the present invention, facilitated by the use of a process for producing hydrogen from a feed of natural gas using a promoter/catalyst/activator system selected from the group consisting of
Pd (palladium )
Pt (platinum)
Ir (iridium) or a combination of Ir and a co-metal taken among noble metals ( for example Pt, Pd)
- Ni (Nickel)
Ru (ruthenium) Co (copper) Rh (Rhodium) - Ag (silver)
- Co (cobalt)
W (tungsten) all other catalyst alone or together with one or more of the metals mentioned supra and ceria in the form of Ce203 by reacting the ceria with the promoter in the presence of water for oxidizing the ceria into Ce02 and processing the produced Ce02 and promoter for reducing Ce02 into Ce203 through the production of synthesis gas, and wherein said processes are conducted at the following temperature intervals:
1) the oxidation of ceria and the production of hydrogen: -25 to 200°C, preferably 50 to 150°C,
2) the reduction of ceria and the production of synthesis gas: 200-600°C, more preferred 300-500°C, are that the promoter/catalyst/activator system allows reaction temperatures below the temperatures used in the state of the art, as well as using H20 for regenerating the ceria and not CO as in the prior art. In one embodiment of the process according to the present invention the reduction of ceria is conducted at 400-600°C by using CH4, and the oxidation with water is conducted at 100-200°C by using H20 and coupling this to different chemical and electrical processes. The processes according to the present invention are thus conducted at significantly lower temperatures than what is conventional and thus at a lower energy consumption than what is possible with the prior art.

Claims

Claims:
1. Process for producing hydrogen from a feed of natural gas using a
promoter/catalyst/activator system selected from the group consisting of
Pd (palladium ) - Pt (platinum)
Ir (iridium) or a combination of Ir and a co-metal taken among noble metals ( for example Pt, Pd)
- Ni (Nickel)
Ru (ruthenium) - Co (copper)
Rh (Rhodium) Ag (silver)
- Co (cobalt) W (tungsten) - all other catalyst alone or together with one or more of the metals
mentioned supra and ceria in the form of Ce203 by reacting the ceria with the promoter in the presence of water for oxidizing the ceria into Ce02 and processing the produced Ce02 and promoter for reducing Ce02 into Ce203 through the production of synthesis gas, and wherein said processes are conducted at the following temperature intervals:
1) the oxidation of ceria and the production of hydrogen: -25 to 200°C, preferably 50 to 150°C, 2) the reduction of ceria and the production of synthesis gas: 200-600°C, more preferred 300-500°C.
2. Process according to claim 1, wherein the catalyst system comprises components being a combination of a promoter and ceria and/or Gd plus Ceria and/or Zirconia plus Ceria or any solid mixture of said components.
3. Process according to any of the preceding claims, wherein the loading of the metal promoter in the catalyst is more than 0 %, preferably 0,1 - 10 %, more preferred 0,1 - 3 % by weight.
4. Use of the process according to any of the claims 1 - 3 for producing organic compounds, e.g. methanol, ethanol, urea or higher chain organic compounds.
5. Use of the process according to any of the claims 1 - 3 for producing inorganic compounds, e.g. ammonia, cyanides, C02, fertilizer.
6. Use of the process according to any of the claims 1 - 3 for producing any form of energy, e.g. electrical energy and/or heat.
7. Use of the process according to any of the claims 1 - 3 for producing energy without the emission of C02.
PCT/NO2010/000328 2009-09-04 2010-09-03 Method for producing synthesis gas from natural gas using a promoter and ceria in the form ce203 WO2011028133A1 (en)

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WO2016011473A1 (en) * 2014-07-25 2016-01-28 Rouge H2 Engineering Gmbh Method for producing hydrogen
CN106687408A (en) * 2014-07-25 2017-05-17 罗杰H2工程有限公司 Method for producing hydrogen
US10280079B2 (en) 2014-07-25 2019-05-07 Rouge H2 Engineering Gmbh Method for producing hydrogen
EP3172164B1 (en) 2014-07-25 2020-11-11 Rouge H2 Engineering GmbH Method for producing hydrogen
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