WO2014170200A1 - Methods for production of liquid hydrocarbons from energy, co2 and h2o - Google Patents

Methods for production of liquid hydrocarbons from energy, co2 and h2o Download PDF

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Publication number
WO2014170200A1
WO2014170200A1 PCT/EP2014/057267 EP2014057267W WO2014170200A1 WO 2014170200 A1 WO2014170200 A1 WO 2014170200A1 EP 2014057267 W EP2014057267 W EP 2014057267W WO 2014170200 A1 WO2014170200 A1 WO 2014170200A1
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Prior art keywords
energy
carbon dioxide
liquid hydrocarbon
heat
hydrogen
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French (fr)
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Gunnar Sanner
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • 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
    • C01B13/0222—Preparation of oxygen from organic compounds
    • 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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/06—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen with inorganic reducing agents
    • C01B3/12—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0485—Set-up of reactors or accessories; Multi-step processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1516—Multisteps
    • C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • 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
    • C01B2203/0211—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step
    • C01B2203/0216—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step containing a non-catalytic steam reforming 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
    • C01B2203/02—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
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process

Definitions

  • the present invention relates to methods for production of liquid hydrocarbons from energy, C0 2 and H 2 0. Especially the present invention relates to integrated and energy efficient methods for transforming energy, C0 2 and H 2 0 to liquid
  • hydrocarbons applicable for use as fuel or for other purposes.
  • renewable energy energy-to-Liquid
  • RTL Renewable (energy )-to-Liquid
  • the main purpose of these reactions is as the name indicates to transform energy, as power and/or heat, to hydrocarbons that are liquid at room temperature and near atmospheric pressure.
  • energy source to renewable energy
  • hydrocarbons that are liquid at room temperature and near atmospheric pressure.
  • Energy upload not to limit the energy source to renewable energy, but include any form of power or heat input, and not to limit the end products to liquid, but include all types of hydrocarbons, we further use the term "Energy upload”.
  • the produced liquid hydrocarbons are compact energy carriers, easy to handle and applicable as raw materials for other processes such as production of polymers.
  • the solutions also produce substantial amounts of 0 2 , a gas useful for industrial purposes, e.g.: GTL, metal industry, oxyfuel power plants.
  • US2012/0228150 discloses the processing of syngas into synthetic liquid fuel in the form of alkanes. Hydrogen for the syngas is produced by electrolysis of water. Also disclosed is the production of methanol from hydrogen and carbon monoxide, where the hydrogen is obtained from thermal pyrolysis of methane.
  • US2012/0259025 discloses the formation of gaseous methane from hydrogen and carbon dioxide in a Sabatier reactor.
  • the hydrogen is obtained through water electrolyses.
  • the objective of the present invention is to provide an integrated method for transforming energy as power and/or heat, C0 2 and H 2 0 to liquid hydrocarbons.
  • a further objective is to provide a method with increased cost efficiency and increased energy efficiency of the process.
  • Yet another objective of the present invention is to provide a method which can be performed with thermal energy as the additional energy input, more preferably with sustainable energy as the additional energy input.
  • the goal is to produce alkanes and alcohols in liquid form at standard conditions (e.g.: 20 or 25 °C and 1 atmosphere pressure).
  • Hydrocarbons in liquid form are more valuable and transportable than hydrocarbons in gaseous form. Hydrocarbons in liquid form can be transported in ships and stored without use o pressure- and/or cooled tanks. In the consumer markets liquid hydrocarbons are used to a large extend in transportation sectors like cars, trucks, ships and planes. Liquid hydrocarbons are presently the highest priced energy products per energy unit.
  • the present invention provides an energy uploading method transferring energy into liquid hydrocarbon comprising steps a) preparing a mixture of hydrogen and carbon monoxide from carbon dioxide, H 2 0 and energy, b) reacting said mixture to form liquid hydrocarbon. c) transferring heat energy from the formed liquid hydrocarbon to the carbon dioxide and or the H 2 0.
  • the step a) comprises decomposition of carbon dioxide into carbon monoxide and oxygen.
  • step a) further comprises reacting a part of the carbon monoxide with H 2 0 to form carbon dioxide and hydrogen and transferring the formed carbon dioxide to the decomposition of carbon dioxide.
  • step a) comprises decomposition of water into oxygen and hydrogen.
  • step a) comprises combined steam reforming and carbon dioxide reforming.
  • the present invention also provides an energy uploading method transferring energy into liquid hydrocarbon comprising steps d) preparing hydrogen from H 2 0 and energy, e) preparing a mixture of hydrogen and carbon dioxide, f) reacting said mixture to form liquid hydrocarbon, g) transferring heat energy from the formed liquid hydrocarbon to the carbon dioxide and or the H 2 0.
  • oxygen is produced as a by-product.
  • the method comprises transferring heat from the oxygen to the carbon dioxide and or the H 2 0.
  • the energy supplied is heat energy, and in an aspect thereof the energy supplied is sustainable energy.
  • step c) or g) comprises converting heat from exothermic reactions to power to be used in endothermic processes
  • liquid in connection with hydrocarbons, alkanes and alcohols as used herein refers to phase condition of the hydrocarbon at near atmospheric conditions.
  • the method could also be used to produce gas alkanes
  • the source of the carbon dioxide for the method can be any known C0 2 source such as C0 2 from reservoirs, C0 2 captured from industry or C0 2 captured from air, or combinations thereof.
  • Thermal energy can be utilized as energy input.
  • sustainable energy is employed as the sole or main energy input, e.g.: solar thermal, geothermal.
  • Other thermal energy sources could also be used like nuclear;
  • Applicable energy sources also include other type of energy (bio or fossil fuel)
  • the main principals of the present invention may be employed in the production o alkanes, alcohols and other liquid hydro carbons.
  • the total reaction schemes for alkancs is
  • the present invention would be C0 2 -neutral since as much CO 2 is bound in the process as is released when the fuel is burned, if renewable power/heat is used as energy input and C0 2 used is captured from industry or from air.
  • the process could utilize C0 2 from reservoirs, C0 2 captured from industry or CO 2 captured from air.
  • the present solution may utilize heat as energy input, and thereby lower the cost of the energy needed to run the process.
  • the present invention could be used as a renewable energy or nuclear energy storage and/or energy export route. Periodically over-supply of renewable energy or nuclear energy can by this method be utilized to convert 11 2 0 and CO 2 to liquid fuels; hence the renewable energy would be exported as "Renewable hydrocarbons *" , CO 2 -ncutral liquid hydrocarbon fuels.
  • the processes of the alkane production and the alcohol production may be combined so that a combination of liquid alkanes and alcohols are obtained from energy. H20 and carbon dioxide.
  • Figure 1 i llustrates a first embodiment for alkane production.
  • Figure 2 illustrates a second embodiment for alcohol production.
  • Figure 3 illustrates an alternative third embodiment for alkane production.
  • Figure 4 illustrates a fourth embodiment for alcohol production.
  • Figure 5 illustrates an alternative fifth embodiment for alkane production.
  • Figure 6 ill ustrates a sixth embodiment for alcohol production.
  • Figure 7 is a schematically illustration of the main principal of the present invention.
  • Figure 8 illustrates the transfer o heat between inlet streams and product streams. Principal description of the invention
  • the present invention provides an integrated solution to convert energy as power and/or heat to liquid fuels.
  • energy Upload endothermic reactions are being employed or considered employed for the storage of renewable energy sources such as geothermal heat, sun light or wind energy resources.
  • the renewable- or other types of energy provide the energy to react H 2 0 with C0 2 to form hydrocarbons.
  • This illustration is a simplification as the process is normal ly performed as at least a two step process, wherein power is supplied in electrolysis of water to form hydrogen and oxygen and then in a second step the hydrogen i s reacted with carbon dioxide to form hydrocarbons.
  • the combined process has the potential of utilizing heat as renewable energy input and thereby provides a more cost efficient process, since heat usually has lower cost per energy unit than power
  • the input energy is transmitted into the solutions as heat or power. This energy shall be used for the chemical reactions purposes. Rest heat in the in the produced outflowing chemicals (alkanes/alcohols. and 0 2 ) may advantageously be reclaimed by heat exchange systems. This heat is transferred into the inflowing chemicals ⁇ CO 2 and H 2 0). To secure limited energy leakage, insulation will be provided around all processes with high temperature. This construction will make the solutions very energy efficient. By this the input energy will efficiently be used to fill the gap between the high chemical energy potential in produced alkanes or alcohols and the low chemical energy potential in the inflowing CO 2 and H 2 0.
  • Figure 8 shows one set up of such combination of insulation and heat transfer from outflowing to inflowing chemicals.
  • Pipe-in-pipe solution with countercurrent flow ensures a heat gradient that allows heat to go from outflowing chemicals to inflowing. Theoretically i f all heat is regained the energy input needed or the heat energy produced is determined by the energy produced and released by the chemical reactions.
  • the energy efficiency of the conversion is enforced by insulation around the converter and heat transfer from outflowing products to inflowing material streams, by use of countercurrent pipe-in-pipe system as illustrated in figure 8, or any other methods of transferring heat.
  • Heat based power generation could be built as part of this heat transfer from warm to cold product streams. This power generation is marked as star in the exothermic processes in the figures 1 to 6. This power could be used as input to endothermic processes.
  • Figure 1 illustrates a first embodiment of the present invention for the production of alkanes.
  • the process is split into three reactions, decomposition of C0 2 , CO/H 2 O reaction and alkane synthesis.
  • Each of these steps are in them self known processes but the integrated combination as disclosed is new.
  • C0 2 is split into CO and 0 2 with energy as input. Some o the CO is led into CO/H 2 0 reaction where it is transformed to H 2 and C0 2 . The produced CO 2 is led back to the decomposition of C0 2 while II 2 is led into the alkane synthesis. The alkane synthesis also receives some CO from the decomposition of C0 2 process. Water produced in the alkane synthesis process is led back to the CO/H 2 0 reaction.
  • the named processes can be performed at different conditions and the present invention is not limited to any of these known methods.
  • the energy consumption and production is also illustrated in figure 2 by the fat arrows and the stars.
  • Energy is added to the C0 2 decomposition process to provide the heat for the process. This heat can at least partly be supplied by pre-heating the C0 2 with surplus of energy from the exothermic alkane synthesis or CO/H 2 0 reaction.
  • Figure 3 and 4 illustrate two further embodiments of the present invention comprising two reactions; steam/C02 reforming and alkane or alcohol synthesis to produce alkane or alcohol.
  • Figures 5 and 6 illustrate two further embodiments of the present invention comprising two reactions; water splitting and alkane or alcohol synthesis to produce alkane or alcohol.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Energy uploading method transferring energy into liquid hydrocarbon comprising the steps a) preparing a mixture of hydrogen and carbon monoxide from carbon dioxide, H2O and energy, b) reacting said mixture to form liquid hydrocarbon, c) transferring heat energy from the formed liquid hydrocarbon to the carbon dioxide and or the H2O.

Description

Methods for production of liquid hydrocarbons from energy, C02 and H20
The present invention relates to methods for production of liquid hydrocarbons from energy, C02 and H20. Especially the present invention relates to integrated and energy efficient methods for transforming energy, C02 and H20 to liquid
hydrocarbons applicable for use as fuel or for other purposes.
Background
The transformation of renewable energy, ¾0 and C02 to liquid hydrocarbons could be named Renewable (energy )-to-Liquid (RTL). The main purpose of these reactions is as the name indicates to transform energy, as power and/or heat, to hydrocarbons that are liquid at room temperature and near atmospheric pressure. Not to limit the energy source to renewable energy, but include any form of power or heat input, and not to limit the end products to liquid, but include all types of hydrocarbons, we further use the term "Energy upload". The produced liquid hydrocarbons are compact energy carriers, easy to handle and applicable as raw materials for other processes such as production of polymers. In addition to hydrocarbons, the solutions also produce substantial amounts of 02, a gas useful for industrial purposes, e.g.: GTL, metal industry, oxyfuel power plants.
Different processes are known for performing Energy upload today. The main principle of the existing Energy upload plants is decomposition of water to form hydrogen and oxygen gas, and thereafter combine hydrogen with C02 to form hydrocarbons.
Prior art An energy system for connecting Energy Upload plants with corresponding energy Offload plants and form a closed energy system are disclosed in WO2012/069635 and WO2012/069636.
US2012/0228150 discloses the processing of syngas into synthetic liquid fuel in the form of alkanes. Hydrogen for the syngas is produced by electrolysis of water. Also disclosed is the production of methanol from hydrogen and carbon monoxide, where the hydrogen is obtained from thermal pyrolysis of methane.
US2012/0259025 discloses the formation of gaseous methane from hydrogen and carbon dioxide in a Sabatier reactor. The hydrogen is obtained through water electrolyses. Objectives of the invention
The objective of the present invention is to provide an integrated method for transforming energy as power and/or heat, C02 and H20 to liquid hydrocarbons.
A further objective is to provide a method with increased cost efficiency and increased energy efficiency of the process.
Yet another objective of the present invention is to provide a method which can be performed with thermal energy as the additional energy input, more preferably with sustainable energy as the additional energy input.
The goal is to produce alkanes and alcohols in liquid form at standard conditions (e.g.: 20 or 25 °C and 1 atmosphere pressure). Hydrocarbons in liquid form are more valuable and transportable than hydrocarbons in gaseous form. Hydrocarbons in liquid form can be transported in ships and stored without use o pressure- and/or cooled tanks. In the consumer markets liquid hydrocarbons are used to a large extend in transportation sectors like cars, trucks, ships and planes. Liquid hydrocarbons are presently the highest priced energy products per energy unit.
It is an aim to provide an energy efficient process. The present invention provides an energy uploading method transferring energy into liquid hydrocarbon comprising steps a) preparing a mixture of hydrogen and carbon monoxide from carbon dioxide, H20 and energy, b) reacting said mixture to form liquid hydrocarbon. c) transferring heat energy from the formed liquid hydrocarbon to the carbon dioxide and or the H20.
In one aspect of the present in vention the step a) comprises decomposition of carbon dioxide into carbon monoxide and oxygen.
In a further aspect step a) further comprises reacting a part of the carbon monoxide with H20 to form carbon dioxide and hydrogen and transferring the formed carbon dioxide to the decomposition of carbon dioxide.
In yet a further aspect the step a) comprises decomposition of water into oxygen and hydrogen.
In another aspect of the present invention the step a) comprises combined steam reforming and carbon dioxide reforming.
The present invention also provides an energy uploading method transferring energy into liquid hydrocarbon comprising steps d) preparing hydrogen from H20 and energy, e) preparing a mixture of hydrogen and carbon dioxide, f) reacting said mixture to form liquid hydrocarbon, g) transferring heat energy from the formed liquid hydrocarbon to the carbon dioxide and or the H20.
According to a further aspect of any of the methods according to the present invention oxygen is produced as a by-product. In a further aspect the method comprises transferring heat from the oxygen to the carbon dioxide and or the H20.
In one aspect of the present invention the energy supplied is heat energy, and in an aspect thereof the energy supplied is sustainable energy.
In one aspect of the methods the liquid hydrocarbon is alcohol CnH2n+iOH, where n= l -20, preferably n=l -6.
In another aspect of the methods the liquid hydrocarbon is alkane C„H2n+2, where n=5-17, preferably n=5-10.
In yet another aspect of the methods according to the present invention, wherein the step c) or g) comprises converting heat from exothermic reactions to power to be used in endothermic processes
The term "liquid" in connection with hydrocarbons, alkanes and alcohols as used herein refers to phase condition of the hydrocarbon at near atmospheric conditions. For alkanes the number of carbon atoms within the compound being between 5 and 17 which is equivalent to the number of carbon atoms being higher than or equal to five for the alkane to be described as liquid, whereas for alcohols also compounds with only one carbon atom such as methanol falls within the term liquid, typically alcohols are n= 1-5. The method could also be used to produce gas alkanes
(n=l ,2,3,4) or solid alkanes where n>=18.
The source of the carbon dioxide for the method can be any known C02 source such as C02 from reservoirs, C02 captured from industry or C02 captured from air, or combinations thereof.
Thermal energy can be utilized as energy input. In an attractive embodiment sustainable energy is employed as the sole or main energy input, e.g.: solar thermal, geothermal. Other thermal energy sources could also be used like nuclear;
electricity input is also an option. Applicable energy sources also include other type of energy (bio or fossil fuel) The main principals of the present invention may be employed in the production o alkanes, alcohols and other liquid hydro carbons. The total reaction schemes for alkancs is
(n) C02 + (n+1) H20 => C„H2n+2 + (3n+l)/2 02,
wherein n=alkane number The total reaction schemes for alcohols is
(n) C02 + (n+1) H20 => CnH2n+1OH + (3/2)n 02, wherein n=alcohol number.
Examples of specific total reactions are:
• I6 CO2 + 18 H20 => 2 C8Hi8 + 25 02 (Octane)
• 2 C02 + 3 H20 => C2H5OH + 3 02 (Ethanol)
• 2 C02 + 4 I I2O => 2 CH3OH + 3 O2 (Methanol)
One or more of the following advantages can be obtained by the present invention:
• The present invention would be C02-neutral since as much CO2 is bound in the process as is released when the fuel is burned, if renewable power/heat is used as energy input and C02 used is captured from industry or from air.
• Combustion of the obtained liquid hydrocarbon as fuel will have less C02- footprint than crude oil based fuels due to no CO2 footprint in the production process, if renewable power/heat is used as energy input and C02 used is captured from industry or from air.
• The process could utilize C02 from reservoirs, C02 captured from industry or CO2 captured from air.
• The present solution may utilize heat as energy input, and thereby lower the cost of the energy needed to run the process.
• The present invention could be used as a renewable energy or nuclear energy storage and/or energy export route. Periodically over-supply of renewable energy or nuclear energy can by this method be utilized to convert 1120 and CO2 to liquid fuels; hence the renewable energy would be exported as "Renewable hydrocarbons*", CO2-ncutral liquid hydrocarbon fuels. In an aspect of the present invention the processes of the alkane production and the alcohol production may be combined so that a combination of liquid alkanes and alcohols are obtained from energy. H20 and carbon dioxide.
Brief description of the drawings The present invention wil l be exempli fied in further detail with reference to the enclosed figures.
Figure 1 i llustrates a first embodiment for alkane production.
Figure 2 illustrates a second embodiment for alcohol production.
Figure 3 illustrates an alternative third embodiment for alkane production. Figure 4 illustrates a fourth embodiment for alcohol production.
Figure 5 illustrates an alternative fifth embodiment for alkane production.
Figure 6 ill ustrates a sixth embodiment for alcohol production.
Figure 7 is a schematically illustration of the main principal of the present invention. Figure 8 illustrates the transfer o heat between inlet streams and product streams. Principal description of the invention
The main concept of the present invention is illustrated on figure 9. The present invention provides an integrated solution to convert energy as power and/or heat to liquid fuels. In the known process of Energy Upload endothermic reactions are being employed or considered employed for the storage of renewable energy sources such as geothermal heat, sun light or wind energy resources. The renewable- or other types of energy provide the energy to react H20 with C02 to form hydrocarbons. This illustration is a simplification as the process is normal ly performed as at least a two step process, wherein power is supplied in electrolysis of water to form hydrogen and oxygen and then in a second step the hydrogen i s reacted with carbon dioxide to form hydrocarbons. The combined process has the potential of utilizing heat as renewable energy input and thereby provides a more cost efficient process, since heat usually has lower cost per energy unit than power The input energy is transmitted into the solutions as heat or power. This energy shall be used for the chemical reactions purposes. Rest heat in the in the produced outflowing chemicals (alkanes/alcohols. and 02) may advantageously be reclaimed by heat exchange systems. This heat is transferred into the inflowing chemicals {CO 2 and H20). To secure limited energy leakage, insulation will be provided around all processes with high temperature. This construction will make the solutions very energy efficient. By this the input energy will efficiently be used to fill the gap between the high chemical energy potential in produced alkanes or alcohols and the low chemical energy potential in the inflowing CO 2 and H20.
Figure 8 shows one set up of such combination of insulation and heat transfer from outflowing to inflowing chemicals. Pipe-in-pipe solution with countercurrent flow ensures a heat gradient that allows heat to go from outflowing chemicals to inflowing. Theoretically i f all heat is regained the energy input needed or the heat energy produced is determined by the energy produced and released by the chemical reactions.
The following table shows the overall difference in enthalpy for three examples of Energy Upload reactions according to the present invention.
Figure imgf000007_0001
The energy efficiency of the conversion is enforced by insulation around the converter and heat transfer from outflowing products to inflowing material streams, by use of countercurrent pipe-in-pipe system as illustrated in figure 8, or any other methods of transferring heat. Heat based power generation could be built as part of this heat transfer from warm to cold product streams. This power generation is marked as star in the exothermic processes in the figures 1 to 6. This power could be used as input to endothermic processes.
Figure 1 illustrates a first embodiment of the present invention for the production of alkanes. Here the process is split into three reactions, decomposition of C02, CO/H2O reaction and alkane synthesis. Each of these steps are in them self known processes but the integrated combination as disclosed is new.
In the decomposition of C02 process C02 is split into CO and 02 with energy as input. Some o the CO is led into CO/H20 reaction where it is transformed to H2 and C02. The produced CO 2 is led back to the decomposition of C02 while II 2 is led into the alkane synthesis. The alkane synthesis also receives some CO from the decomposition of C02 process. Water produced in the alkane synthesis process is led back to the CO/H20 reaction. The named processes can be performed at different conditions and the present invention is not limited to any of these known methods. Taken as a whole the inlet streams are H20 and C02 and the outlet streams are liquid alkanes CnH2n+2 where n=5- l 7 and CK The energy consumption and production is also illustrated in figure 2 by the fat arrows and the stars. Energy is added to the C02 decomposition process to provide the heat for the process. This heat can at least partly be supplied by pre-heating the C02 with surplus of energy from the exothermic alkane synthesis or CO/H20 reaction.
Figure 2 illustrate a second embodiment of the present invention which differs from the embodiment of figure 2 only in that the alkane synthesis is replaced with an alcohol synthesis, so liquid hydrocarbon formed by the overall process is an alcohol C„I l2n i i H, where n>=l , preferably n=l-20, more pre erably n= l -l 0.
The total reactions of embodiment 1 and 2:
Alkane production (1):
(3n+l) C02 => (3n+l) CO + (3n+l)/2 02
(2n+l) CO + (2n+l) H20=> (2n+l) C02 + (2n+ l ) H2
(n) CO + (2n+l) ¾ => CnH2n+2 + n H20 Alcohol production (2):
(3n) C02 => (3n) CO + (3/2)n 02
(2n) CO + (2n) H20 => (2n) C02 + (2n) H2
(n) CO + (2n) H2 => CnH2n+1OH+ (n-1) H20 In a further embodiment of the present invention the processes of the first and the second embodiment may be combined so that a combination of liquid alkanes and alcohols are obtained from energy, 1120 and carbon dioxide.
Figure 3 and 4 illustrate two further embodiments of the present invention comprising two reactions; steam/C02 reforming and alkane or alcohol synthesis to produce alkane or alcohol.
The total reactions of embodiment 3 and 4:
Alkane production (3):
(2n+l) H20 + (n) C02 => (n) CO + (2n+l) H2 + (3n+l)/2 02
(n) CO + (2n+l) ¾ => CnH2n+2 + (n) H20 Alcohol production (4):
(2n) 1120 + (n) C02 => (n) CO + (2n) H2 + (3/2)n 02
(n) CO + (2n) H2 => C„H2n+1OH + (n-1) H20
Figures 5 and 6 illustrate two further embodiments of the present invention comprising two reactions; water splitting and alkane or alcohol synthesis to produce alkane or alcohol.
The total reactions of embodiment 5 and 6:
Alkane production (5):
(2n+l) H20 => (2n+ l ) ¾ + (2n+l )/2 02
(n) C02 + (2n+l) ¾ => CnH2n+2 + (n) H20 + (n/2) 02 Alcohol production (6):
(2n) H20 => (2n) H2 + (n) 02
(n) C02 + (2n) ¾ => CnH2n i ,OM + (n- 1 ) H20 +(n/2 ) 02

Claims

Energy uploading method transferring energy into liquid hydrocarbon comprising steps
a) preparing a mixture of hydrogen and carbon monoxide from carbon dioxide, H20 and energy,
b) reacting said mixture to form liquid hydrocarbon,
c) transferring heat energy from the formed liquid hydrocarbon to the carbon dioxide and or the H20.
Energy uploading method according to claim 1 , wherein step a) comprises decomposition of carbon dioxide into carbon monoxide and oxygen.
Energy uploading method according to claim 2, wherein step a) further comprises reacting a part of the carbon monoxide with H20 to form carbon dioxide and hydrogen and transferring the formed carbon dioxide to the decomposition of carbon dioxide.
Energy uploading method according to any one of the previous claims, wherein step a) comprises combined steam re orming and carbon dioxide reforming.
Energy uploading method transferring energy into liquid hydrocarbon comprising steps
d) preparing hydrogen from H20 and energy,
e) preparing a mixture of hydrogen and carbon dioxide,
f) reacting said mixture to form liquid hydrocarbon,
g) transferring heat energy from the formed liquid hydrocarbon to the carbon dioxide and or the H20.
Energy uploading method according to any one of the previous claims, wherein oxygen is produced as a by-product.
Energy uploading method according to claim 6. wherein the method comprises transferring heat from the oxygen to the carbon dioxide and or the H20.
Method according to any one of the previous claims, wherein the energy supplied is heat energy.
Method according to any one of the previous claims, wherein the energy supplied is sustainable energy.
10. Method according to any one of the previous claims, wherein the liquid
hydrocarbon is alcohol GYl Em lON, where n= l -20, preferably n= l -6.
1 1. Method according to any one of the claims 1 -9. wherein the liquid
hydrocarbon is alkane C„H2n+2, where n=5- 17, preferably n=5-10.
12. Method according to any one of the previous claims, wherein the step c) or g) comprises converting heat from exothermic reactions to power to be used in endothermic processes.
PCT/EP2014/057267 2013-04-19 2014-04-10 Methods for production of liquid hydrocarbons from energy, co2 and h2o Ceased WO2014170200A1 (en)

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