EP4676876A1 - Process for producing hydrogen with electrically heated steam methane reforming - Google Patents

Process for producing hydrogen with electrically heated steam methane reforming

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Publication number
EP4676876A1
EP4676876A1 EP24707837.1A EP24707837A EP4676876A1 EP 4676876 A1 EP4676876 A1 EP 4676876A1 EP 24707837 A EP24707837 A EP 24707837A EP 4676876 A1 EP4676876 A1 EP 4676876A1
Authority
EP
European Patent Office
Prior art keywords
stream
heat
hydrogen
steam
carbon dioxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP24707837.1A
Other languages
German (de)
French (fr)
Inventor
Teja Schmid Mcguinness
Swatantra Kumar SHRIVASTAVA
Marion David
Elena Raulli
Frederic Judas
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Air Liquide SA, LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical Air Liquide SA
Publication of EP4676876A1 publication Critical patent/EP4676876A1/en
Pending legal-status Critical Current

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    • 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
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/384—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts with external heating of the catalyst
    • 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
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/48—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
    • 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
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • 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
    • C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
    • 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
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • 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
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0495—Composition of the impurity the impurity being water
    • 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
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0827—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel at least part of the fuel being a recycle stream
    • 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
    • C01B2203/085—Methods of heating the process for making hydrogen or synthesis gas by electric heating
    • 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
    • C01B2203/1258—Pre-treatment of the feed
    • C01B2203/1264—Catalytic pre-treatment of the feed
    • C01B2203/127—Catalytic desulfurisation
    • 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
    • C01B2203/14—Details of the flowsheet
    • C01B2203/146—At least two purification steps in series
    • C01B2203/147—Three or more purification 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
    • C01B2203/14—Details of the flowsheet
    • C01B2203/148—Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis gas

Definitions

  • the invention relates to a process for producing hydrogen, comprising a steam methane reforming (SMR) step, wherein heat for the endothermic reforming reaction is partially provided by converting electrical energy into heat, and partially provided by combustion.
  • SMR steam methane reforming
  • the global hydrogen output is estimated at 70 Mt per year, most of which is produced by the steam methane reforming (SMR) process, in which natural gas reacts with steam to yield hydrogen (H2) and carbon monoxide (CO).
  • SMR steam methane reforming
  • This mixture referred to as synthesis gas or syngas, is further converted by means of a water-gas shift unit to yield a shifted synthesis gas mixture consisting mainly of hydrogen and carbon dioxide (CO2).
  • the location of the carbon dioxide capture is for instance the shifted synthesis gas, tail gas from a pressure swing adsorption unit, and flue gas.
  • the process for capturing the carbon dioxide may involve chemical absorption, in particular an amine wash, adsorption (e.g. a CO2 VPSA), cryogenic separation, or a membrane separation of the carbon dioxide to be captured.
  • the carbon dioxide in the shifted synthesis gas makes about 60 % of the total direct carbon dioxide emissions of the SMR process. This share can be captured with relative ease owing to the high concentration I partial pressure of carbon dioxide in the shifted synthesis gas.
  • the current industry standard is to capture the carbon dioxide on the shifted synthesis gas with a chemical wash, typically an amine wash, or with a cryogenic and membrane separation on the tail gas of a pressure swing adsorption (PSA) unit, after the hydrogen has been separated from the shifted synthesis gas by means of said PSA unit.
  • PSA pressure swing adsorption
  • the remaining about 40 % of the carbon dioxide emissions are linked to the combustion of residual carbon monoxide (CO) and methane (CH4) in the PSA tail gas and/or hydrocarbon-based fuel, to generate the heat required for the endothermic SMR reaction.
  • the flue gas With the recycle of PSA tail gas to the burners, the flue gas will contain all the direct carbon dioxide emissions of the SMR process. A capture rate of approximately 90 % can thus be achieved in the flue gas, albeit at a higher capture cost, owing to the low pressure of the flue gas, and the low partial pressure of carbon dioxide in the flue gas.
  • An alternative to a traditional SMR setup is to replace the firebox by an electrically heated reactor, and thus provide the required amount of heat for the reaction with electricity as the energy vector.
  • a SMR process such a solution would obviate the combustion of additional hydrocarbon fuel, and the consequent formation of a low pressure flue gas in which carbon dioxide capture is difficult. Under the assumption that electricity from a renewable energy source is used, it should reduce the carbon footprint of the process, and facilitate carbon capture.
  • An electrically heated SMR thus raises the prospect of a reduced carbon footprint, more cost efficient carbon capture, as well as a more compact reformer design, since the reformer design is no longer limited by the constraint of transferring heat from the furnace to the reformer tubes, which imposes a large surface area for the heat exchange in a conventional reformer.
  • an external power generator induces an electric current to pass through the reactor following a conductive path.
  • Heat is supplied to the SMR catalyst by dissipating power (Joule effect) through resistive media.
  • the resistive medium can consist of the catalyst structure directly, or of other conductive heating elements (wire, pipe wall, conductive pellets).
  • washcoated monoliths and other different structured catalysts have been studied for electrically heated steam or dry reforming, exploiting the conductivity of the structured material with respect to both heat and electricity when it is connected to a power source.
  • Another option is to fill the reactor with a mixture of catalyst pellets and electrically conductive particles able to drive an electric current through the packed bed.
  • the most straightforward application of the electric heating method is employing a distribution of heating elements not shaped as the catalyst but still allowing the passage of electric current dissipating the required heat to the reactive zone.
  • the main advantage of such a system is the improved heat transfer efficiency and the prospect of a better control of the temperature along the catalyst bed.
  • the issue related to the wall thermal resistance is then overcome, so that in principle a cold outer reactor surface can be obtained when a refractory layer is used to prevent dissipation of heat. Thanks to the internal heat supply a large external heat exchange surface area is no longer required to facilitate the heat transfer, so that much more compact solutions can be developed for the reactor configuration.
  • US 9,908,091 B1 discloses a furnace device for steam reforming of hydrocarbons (preferably methane) consisting of a combustion chamber hosting reactor tubes, burners, a voltage source and electrical conductors, so that the tubes can be heated both by the combustion of fuel in the burners, as well as by supplying electric current.
  • hydrocarbons preferably methane
  • the electric field essentially acts as a catalyst by lowering the activation energy of the reforming reaction, with the consequence that the reforming can be carried out at lower temperatures.
  • the underlying principle is that the electric field induces proton hopping amongst the water particles adsorbed on the catalyst surface (according to the so- called Grotthuss mechanism), and enables the migration of the 0 2 - (oxide) anions between the catalyst surface and the gas phase. Both of these phenomena reduce the surface potential of the catalyst and the activation barrier, boosting the reaction rate.
  • the reactor configuration includes coils internally or externally installed, and incorporates a magnetic material, such as magnetic nanoparticles or thin films.
  • a magnetic material such as magnetic nanoparticles or thin films.
  • a magnetic field is formed around it, which in turn generates a Foucault current.
  • Heat is generated as the power of this induced current is dissipated by Joule heating.
  • the heating mechanism occurs by magnetic hysteresis loss, while in the presence of macroscopic conducting material eddy currents are responsible for resistive heating.
  • the reforming step is followed by a water-gas shift step, in which water and carbon monoxide react to form hydrogen and carbon dioxide.
  • a (final) purification step most often in the form of a pressure swing adsorption (PSA) unit, the carbon dioxide, the unconverted methane and carbon monoxide, and any other components are separated from the hydrogen product.
  • PSA offgas also known as PSA tail gas, which is desorbed from the PSA unit at low pressure.
  • the PSA tail gas may account for up to 80 % of the total fuel required to generate the heat for the reforming reaction, with the remaining heat supplied in the form of a make-up fuel, generally a light hydrocarbon material such as natural gas.
  • a make-up fuel generally a light hydrocarbon material such as natural gas.
  • An electrically heated SMR process with carbon capture in which the carbon dioxide is captured by means of a cryogenic process on the PSA tail gas, and where the remaining PSA off-gas (which is rich in carbon monoxide and methane) is combusted to generate electricity for the electrical heated reformer, does not yield a significant improvement over a conventional SMR process in which the carbon dioxide is captured by means of a cryogenic process on the PSA tail gas, and in which the remaining PSA off-gas (which is rich in carbon monoxide and methane) is combusted to generate part of the heat required for the reforming reaction.
  • the electrically heated SMR is referred to as “e-SMR”.
  • a process for producing hydrogen comprising a) a steam methane reforming (SMR) step, to obtain a synthesis gas stream comprising hydrogen, carbon monoxide and carbon dioxide, by means of an endothermic reaction of a hydrocarbon containing feedstock stream and steam, wherein the heat for the endothermic reaction is provided by means of a first and a second heat portion, wherein the first heat portion is provided by converting electrical energy into heat, and the second heat portion is provided by combustion of a fuel; b) a water-gas shift step, comprising the conversion of carbon monoxide of the synthesis gas stream and steam to hydrogen and carbon dioxide, to obtain a shifted synthesis gas stream; c) a hydrogen production step, comprising separating hydrogen from the shifted synthesis gas stream, to obtain a hydrogen product stream and a tail gas stream; d) a tail gas separation step, comprising separating the tail gas stream into at least one fuel containing stream and a carbon dioxide product
  • the heat for the endothermic reaction is partially provided by converting electrical energy into heat and partially provided by combustion of a fuel.
  • the conversion of electrical energy into heat provides a first heat portion.
  • the combustion of a fuel provides a second heat portion.
  • the steam methane reforming according to step a) may also be referred to as a hybrid of electrically heated steam methane reforming (abbreviated e-SMR) and conventionally heated steam methane reforming.
  • the electrical energy is produced from an electrical energy source, preferably a source of renewable electrical energy.
  • the electrical energy is an electrical current.
  • the first heat portion is provided in the form of a first heat stream
  • the second heat portion is provided in the form of a second heat stream.
  • the hydrocarbon containing feedstock stream is a natural gas stream.
  • a pre-reforming step precedes the steam methane reforming (SMR) step.
  • SMR steam methane reforming
  • C2 and higher hydrocarbons
  • CH4 methane
  • a hydrodesulfurization step precedes the steam methane reforming (SMR) step, preferably precedes the pre-reforming step.
  • SMR steam methane reforming
  • sulphur compounds which may act as SMR catalyst poison are removed from the hydrocarbon containing feedstock stream.
  • water-gas shift step b the carbon monoxide (CO) in the synthesis gas stream obtained in step a) is converted with water (steam) in the well-known water-gas shift reaction to hydrogen and carbon dioxide.
  • the water-gas shift step is followed by a cooling step and a separation step, to separate process water as process condensate from the shifted synthesis gas stream.
  • step c) hydrogen is produced from the shifted synthesis gas stream by means of a hydrogen production step by separating hydrogen from the shifted synthesis gas stream.
  • the hydrogen production step comprises a pressure swing adsorption (PSA) step. That is, the hydrogen is separated from the shifted synthesis gas stream by means of a pressure swing adsorption (PSA) unit.
  • the hydrogen is separated from the shifted synthesis gas stream by means of a membrane unit.
  • a tail gas stream is produced.
  • the tail gas stream contains hydrogen, carbon dioxide, carbon monoxide and methane.
  • the tail gas stream may also be referred to as off-gas stream of the hydrogen production step.
  • the hydrogen product stream contains at least 90 % hydrogen per volume, preferably at least 95 % per volume, more preferred at least 99 % per volume.
  • the tail gas stream is separated into at least one fuel containing stream and a carbon dioxide product stream. That is, in the tail gas separation step d), the tail gas stream may be separated into one fuel containing stream and a carbon dioxide product stream. According to one alternative embodiment, in the tail gas separation step d), the tail gas stream may be separated into a plurality of fuel containing streams and a carbon dioxide product stream. For example, in the tail gas separation step d), the tail gas stream may be separated into a first fuel containing stream, a second fuel containing stream, optionally one or more further fuel containing stream(s), and a carbon dioxide product stream.
  • a carbon dioxide product stream is produced in the tail gas separation step d). That is, carbon is captured in the process by means of the tail gas separation step.
  • the carbon dioxide product stream may be compressed and sequestrated (carbon capture and storage, CCS) or further used (carbon capture and utilisation, CCU).
  • the carbon dioxide product stream contains at least 90 % carbon dioxide per volume, preferably at least 95 % per volume, more preferred at least 99 % per volume.
  • step e) at least a portion of the at least one fuel containing stream is combusted for providing the second heat portion. That is, according to one embodiment, when the tail gas stream is separated into one fuel containing stream and a carbon dioxide product stream according to step d), at least a portion of the one fuel containing stream is combusted for providing the second heat portion. According to one further embodiment, when the tail gas stream is separated into a first and a second fuel containing stream and a carbon dioxide product stream according to step d), at least a portion of the first fuel containing stream and optionally a portion of the second fuel containing stream is combusted for providing the second heat portion. Or vice versa, at least a portion of the second fuel containing stream and optionally a portion of the first fuel containing stream is combusted for providing the second heat portion.
  • the tail gas stream is separated into a first fuel containing stream, a second fuel containing stream, and the carbon dioxide product stream.
  • the process comprises
  • At least a portion of the first fuel containing stream is combusted for providing the second heat portion, or at least a portion of the second fuel containing stream is combusted for providing the second heat portion, or at least a portion of the first fuel containing stream and at least a portion of the second fuel containing stream is combusted for providing the second heat portion.
  • the first fuel containing stream is a hydrogen rich stream and the second fuel containing stream is an off-gas stream rich in carbon monoxide and methane.
  • the tail gas stream is separated into a hydrogen rich stream, an off-gas stream rich in carbon monoxide and methane, and the carbon dioxide product stream.
  • the off-gas stream produced in step d) according to this embodiment may also be referred to as off-gas stream of the tail gas separation step.
  • the off-gas stream contains carbon monoxide and methane, in particular the off-gas stream is rich in carbon monoxide and methane. According to one embodiment, the off-gas stream contains at least 50 % carbon monoxide and methane per volume, preferably at least 70 % per volume, more preferred at least 80 % per volume.
  • the hydrogen rich stream contains at least 50 % hydrogen per volume, preferably at least 55 % per volume, more preferred at least 60 % per volume.
  • the process comprises combusting at least a portion of the hydrogen rich stream for providing the second heat portion.
  • the hydrogen rich stream is completely combusted for providing the second heat portion.
  • the second heat portion accounts for at least 20 % of the sum of the first and second heat portions. That is, when the process comprises combusting at least a portion of the hydrogen rich stream for providing the second heat portion, the second heat portion accounts for at least 20 % of the sum of the first and second heat portion. According to one further embodiment in this regard, the second heat portion accounts for 20 % to 40 % of the sum of the first and second heat portions, preferably 25 % to 35 % of the sum of the first and second heat portions.
  • the process comprises recycling at least a portion of the off-gas stream to the hydrocarbon containing feedstock stream, so that a combined stream of hydrocarbon containing feedstock, off-gas and steam is supplied to the steam methane reforming (SMR) step.
  • said combined stream will contain at least the hydrocarbons contained in the feedstock stream, carbon monoxide and methane contained in the off-gas stream, and steam.
  • the off-gas stream is recycled to an unconverted hydrocarbon containing feedstock stream.
  • the off-gas stream is recycled to a desulfurized hydrocarbon containing feedstock stream.
  • the off-gas stream is recycled to a desulfurized and pre-reformed hydrocarbon containing feedstock stream.
  • the off-gas stream obtained in the tail gas separation step is recycled completely to the hydrocarbon containing feedstock stream.
  • the process comprises the combination of
  • the process comprises combusting at least a portion of the off-gas stream rich in carbon monoxide and methane for providing the second heat portion.
  • the off-gas stream rich in carbon monoxide and methane is completely combusted for providing the second heat portion.
  • the second heat portion accounts for at least 50 % of the sum of the first and second heat portions. That is, when the process comprises combusting at least a portion of the off-gas stream rich in carbon monoxide and methane for providing the second heat portion, the second heat portion accounts for at least 50 % of the sum of the first and second heat portion. According to one further embodiment in this regard, the second heat portion accounts for 50 % to 80 % of the sum of the first and second heat portions, preferably 60 % to 70 % of the sum of the first and second heat portions. According to one embodiment, the process comprises recycling at least a portion of the hydrogen rich stream to the shifted synthesis gas stream, so that a hydrogen enriched shifted synthesis gas stream is supplied to the hydrogen production step. Thereby, a hydrogen enriched shifted synthesis gas stream is obtained, which is supplied to the hydrogen production step c). Thereby, the hydrogen yield of the process is improved. According to one embodiment, the hydrogen rich stream is recycled completely to the shifted synthesis gas stream.
  • the process comprises the combination of
  • the at least one fuel containing stream is routed to a combustion device, wherein the combustion device is configured to generate a heat stream for providing the second heat portion.
  • the heat stream generated for providing the second heat portion may also be referred to as the second heat stream.
  • the heat stream comprises one hot flue gas stream or a plurality of hot flue gas streams.
  • the second heat portion is provided by combustion of hydrogen of the hydrogen rich stream, for example by means of a hydrogen burner.
  • the second heat portion is provided by combustion of carbon monoxide and methane of the off-gas stream rich in carbon monoxide and methane, for example by means of a conventional burner.
  • the combustion device is a fired heater or at least one burner.
  • the (second) heat stream may comprise a stream of hot flue gases from a fired heater to provide the second heat portion.
  • the at least one fuel containing stream may be utilised to operate a burner or a plurality of burners. Thereby, the burner or the plurality of burners provide(s) a stream of hot flue gases for providing the second heat portion.
  • the at least one fuel containing stream may be utilised to operate a plurality of burners which are arranged in multiple rows, as it is known to the skilled person for a typical firebox of a steam methane reformer.
  • the heat stream generated by the combustion device is utilised to provide the second heat portion and to close the heat balance of the process, wherein closing the heat balance of the process comprises at least one element from
  • the heat stream generated by the combustion device is utilised to provide the second heat portion and, in addition, to close the heat balance of the process.
  • “Closing the heat balance of the process” means in particular, that the heat generated by the combustion device is used to improve the heat integration of the process. That is, preferably no external heat source or a minimum of external heat is utilized to fulfil the internal heat requirements of the process.
  • the heat generated by the combustion device may be used for pre-heating the hydrocarbon containing feedstock stream before it enters the steam methane reforming (SMR) step, providing heat for the endothermic reaction in the steam methane reforming (SMR) step, pre-heating boiler feed water for the generation of steam, generating process steam for the steam methane reforming (SMR) step or the water-gas shift step, super-heating steam generated in the process, or a combination of the aforementioned.
  • SMR steam methane reforming
  • the carbon dioxide product stream is obtained by means of - at least one tail gas drying step
  • the carbon dioxide product stream is preferably produced by condensation of carbon dioxide from the dry and compressed tail gas stream, by which a stream of carbon dioxide in liquid form is obtained. In a subsequent distillation step of the liquid carbon dioxide, a pure carbon dioxide stream is obtained.
  • Condensation of the carbon dioxide leaves behind a stream of non-condensable gas components.
  • This stream mainly contains hydrogen, carbon monoxide, methane and small amounts of non-condensed carbon dioxide.
  • the hydrogen rich stream is obtained by means of a first membrane separation step, wherein the hydrogen rich stream is produced as the permeate stream, and a stream rich in carbon dioxide, carbon monoxide and methane is produced as the retentate stream.
  • the hydrogen rich stream is preferably produced by a first membrane separation step, wherein preferably the stream of non-condensable gas components is supplied to a first membrane separation unit.
  • the hydrogen rich stream is obtained from said first membrane separation unit as the permeate stream, whilst the retentate mainly contains carbon monoxide, methane and carbon dioxide.
  • the off-gas stream is obtained by means of a second membrane separation step, wherein the off-gas stream rich in carbon monoxide and methane is produced as the retentate stream, and a stream rich in carbon dioxide is produced as the permeate stream.
  • the off-gas stream is preferably produced by a second membrane separation step, wherein preferably the retentate stream obtained from the first membrane separation step is supplied to a second membrane separation unit.
  • the off-gas stream is obtained from said second membrane separation unit as the retentate stream, whilst the permeate mainly contains carbon dioxide, which may be recycled to the condensation step mentioned before.
  • the converting of electrical energy into heat for providing the first heat portion comprises at least one element from
  • the conversion of electrical energy or electrical power into heat, for providing the first heat portion may be realized by one or a combination of the aforementioned methods.
  • the hydrocarbon of the hydrocarbon containing feedstock stream is natural gas, and a molar ratio of natural gas consumed to hydrogen produced is 0.33 or less, preferably 0.32 or less.
  • One technical effect of the process according to the invention is reducing the amount of natural gas consumed throughout the process relative to a reference amount of hydrogen produced (for example, 1 Nm 3 of hydrogen produced).
  • the molar ratio of natural gas consumed to hydrogen produced is lower than 0.335, as shown in examples 1 and 2 in the following.
  • the consumed amount of natural gas does not necessarily refer to the hydrocarbon- containing feedstock exclusively, but may include further natural gas required as fuel, for example for the production of steam.
  • Figure 1 depicts a block flow diagram of a process according to comparative example 4,
  • Figure 2 depicts a block flow diagram of a first embodiment of the process according to the invention
  • Figure 3 depicts a block flow diagram of a second embodiment of the process according to the invention
  • Figure 4 depicts a block flow diagram of an embodiment of the tail gas separation step of the process according to the invention.
  • Figure 1 depicts a block flow diagram of a process 100 according to comparative example 4, wherein off-gas produced in the tail gas separation step is routed to a combustion device.
  • the heat produced by the combustion device is utilized to produce steam, and the steam is further utilized to generate electrical energy by means of a steam turbine and a generator.
  • the electrical energy is converted into heat for the endothermic reaction of the steam methane reforming (SMR) step.
  • SMR steam methane reforming
  • a hydrocarbon containing feedstock stream here a natural gas stream 1a
  • a hydrodesulfurization unit 25 is desulfurized in a hydrodesulfurization unit 25 to afford a desulfurized natural gas stream.
  • Said desulfurized natural gas stream is combined with steam stream 13a, which is a partial stream of steam stream 13.
  • the resulting combined stream of desulfurized natural gas and steam 2a is converted in a pre-reformer 26 to afford a stream of desulfurized and pre-reformed natural gas, containing mainly methane as the hydrocarbon component.
  • Said desulfurized and pre-reformed natural gas stream is combined with steam stream 13b, which is a partial stream of steam stream 13.
  • the resulting combined stream of pre-reformed desulfurized natural gas and steam 3a is introduced into an electrically heated SMR unit 27, in the following referred to as e- SMR unit 27.
  • the desulfurized and pre-reformed natural gas stream is reformed with steam to afford a stream of synthesis gas 4.
  • the reformer tubes (not shown) of the e-SMR unit 27 are heated by means of electrical energy, which is converted into heat.
  • the synthesis gas stream 4 is introduced into a water-gas shift unit 28, in which carbon monoxide of the synthesis gas stream 4 is converted with steam into hydrogen and carbon dioxide, to afford a shifted synthesis gas stream 5.
  • the shifted synthesis gas stream 5 contains mainly hydrogen and carbon dioxide, but also unconverted carbon monoxide and methane.
  • the shifted synthesis gas stream 5 is introduced into a cooling and separation unit 29, in which water contained in the shifted synthesis gas is condensed and withdrawn from the unit 29 as a water condensate stream 11.
  • Said water condensate stream 11 is supplied to a boiler 35, which is also supplied with demineralized water via demineralized water stream 12.
  • a steam stream 13 is produced, which is divided up into the steam partial streams 13a and 13b, to supply the pre-reformer unit 26 and the e-SMR unit 27 with steam.
  • An essentially water-free (dried) shifted synthesis gas stream 5a is withdrawn from the cooling and separation unit 29, and a hydrogen rich stream 9 is combined with said stream to afford a hydrogen enriched dried shifted synthesis gas stream 6.
  • This stream 6 is introduced into a hydrogen production unit, here a pressure swing adsorption (PSA) unit 30, in which a hydrogen product stream 7 and a tail gas stream 8 is produced.
  • PSA pressure swing adsorption
  • the hydrogen product stream 7 is optionally further purified and discharged from the process for further use.
  • the tail gas stream 8 is introduced into the tail gas separation unit 31 , in which the tail gas stream is separated into the hydrogen rich stream 9, a carbon dioxide product stream 54, and an off-gas stream 10. How the hydrogen rich stream 9, the carbon dioxide product stream 54, and the off-gas stream 10 can be specifically obtained will be discussed further below in connection with Figure 4.
  • the hydrogen rich stream 9 produced in the tail gas separation unit 31 is completely recycled to the dry shifted synthesis gas stream 5a discharged from the cooling and separation unit 29, to afford the hydrogen enriched shifted synthesis gas stream 6.
  • the off-gas stream 10 is fed in its entirety to a combustion device, here a fired heater 32, and burned with combustion air to generate heat.
  • the heat generated in the fired heater 32 is utilized in the form of two heat streams 17a and 17b. That is, a part of the generated heat is utilized to close the heat balance of the process (stream 17b), and the remaining part is utilized to generate steam by means of a steam system 33.
  • a flue gas stream 16 is produced, which mainly comprises carbon dioxide and which is discharged from the fired heater.
  • the steam system 33 is also supplied with demineralized water by means of a demineralized water stream 14.
  • a steam stream 15 thereby produced in the steam system 33 is fed to a steam turbine and generator unit 34, in which electrical energy is produced in the form of an electrical current 18, which is used for generating heat in the e-SMR unit 27.
  • the electrical current 18 produced by the steam turbine and generator unit 34 reduces the amount of electrical power input required for the e-SMR unit. So the main benefit of this approach is the reduction of electricity demand from an external source. However, carbon dioxide emissions are not as much reduced as in the following examples of processes according to the invention.
  • FIG. 2 depicts a block flow diagram of a process 200 according to one example of the invention, in the following referred to as example 1.
  • an off-gas stream 10 produced in the tail gas separation unit 31 is fed to the natural gas stream 1a, to afford a combined stream of natural gas and off-gas 1 b.
  • the steam methane reforming (SMR) unit 27a of the process 200 is a hybrid SMR unit, in which the heat for the endothermic SMR reaction is provided by converting electrical energy into heat, and is provided by combustion of a fuel. Electrical energy is provided by means of an electrical current 19, from which a first heat portion is generated by converting the electrical energy of the electrical current 19 into heat.
  • a heat stream 20a is generated by combustion of a fuel, which provides the second heat portion for the endothermic SMR reaction in hybrid SMR unit 27a.
  • the fuel required for the combustion is hydrogen, which is contained in hydrogen rich stream 9.
  • Said hydrogen rich stream 9 is produced in the tail gas separation unit 31 and fed to a combustion device 32 to generate heat, in order to provide the second heat portion required for the endothermic SMR reaction.
  • the combustion device 32 is a fired heater, which produces two heat streams 20a and 20b.
  • the two heat streams are for instance derived from hot flue gas streams.
  • the heat stream 20a is utilised to provide heat for the hybrid SMR unit 27a.
  • the heat stream 20b is utilised to provide heat to close the heat balance of the overall process.
  • a hydrocarbon containing feedstock stream here a natural gas stream 1a
  • the off-gas partial stream 10 contains mainly carbon monoxide and methane.
  • the combination of said streams afford a combined stream of natural gas and off-gas 1 b, which is desulfurized in a hydrodesulfurization unit 25 to afford a desulfurized combined stream of natural gas and off-gas.
  • Said stream is combined with steam stream 13a, which is a partial stream of steam stream 13.
  • the resulting combined stream 2b of desulfurized natural gas, off-gas and steam is converted in a pre-reformer unit 26 to afford a combined stream of desulfurized and pre-reformed natural gas and off-gas, containing mainly methane as the hydrocarbon component.
  • Said stream is combined with steam stream 13b, which is a partial stream of steam stream 13.
  • the resulting combined stream 3b of pre-reformed desulfurized natural gas, off-gas and steam is introduced into the hybrid SMR unit 27a.
  • the desulfurized and pre-reformed natural gas and off-gas is reformed with steam to afford a stream of synthesis gas 4.
  • the reformer tubes (not shown) of the hybrid SMR unit 27a are heated by means of electrical energy, which is converted into heat. This heat represents the first heat portion required for the endothermic steam methane reforming reaction. Electrical energy is provided by means of an electric current 19, which comprises electricity from a renewable energy source. Furthermore, the reformer tubes of the hybrid SMR unit 27a are heated by heat which is provided by heat stream 20a. This heat represents the second heat portion required for the endothermic steam methane reforming reaction. Heat stream 20a is derived from a hot flue gas stream generated in the fired heater 32.
  • the heat stream 20a is derived from burning hydrogen of the hydrogen rich stream 9 in a plurality of hydrogen burners.
  • the synthesis gas stream 4 produced in the hybrid SMR unit 27a is introduced into a water-gas shift unit 28, in which carbon monoxide of the synthesis gas stream 4 is converted with steam into hydrogen and carbon dioxide, to afford a shifted synthesis gas stream 5.
  • the shifted synthesis gas stream 5 contains mainly hydrogen and carbon dioxide, but also unconverted carbon monoxide and methane.
  • the shifted synthesis gas stream 5 is introduced into a cooling and separation unit 29, in which water contained in the shifted synthesis gas is condensed and withdrawn from the unit 29 as a water condensate stream 11.
  • Said water condensate stream 11 is supplied to a boiler 35, which is also supplied with demineralized water via demineralized water stream 12.
  • a steam stream 13 is produced, which is divided up into the steam partial streams 13a and 13b, to supply the pre-reformer unit 26 and the hybrid SMR unit 27a with steam.
  • An essentially water-free shifted synthesis gas stream 5a is withdrawn from the cooling and separation unit 29. Said stream 5a is introduced into a hydrogen production unit, here a pressure swing adsorption (PSA) unit 30, in which a hydrogen product stream 7 and a tail gas stream 8 are produced.
  • PSA pressure swing adsorption
  • the hydrogen product stream 7 is optionally further purified and discharged from the process for further use.
  • the tail gas stream 8 is introduced into the tail gas separation unit 31 , in which the tail gas stream is separated into the hydrogen rich stream 9, a carbon dioxide product stream 54, and the off-gas stream 10. How the hydrogen rich stream 9, the carbon dioxide product stream 54, and the off-gas stream 10 can be specifically obtained will be discussed further below in connection with Figure 4.
  • the off-gas stream 10 produced in the tail gas separation unit 31 is completely recycled to the natural gas stream 1a to afford the combined stream of natural gas and off-gas 1b.
  • the hydrogen rich stream 9 is routed to the combustion device, here a fired heater 32, and burned with combustion air to generate a flue gas stream 16, and heat streams 20a and 20b derived from the flue gas stream.
  • the heat generated in the fired heater 32 is utilized in the form of two heat streams 20a and 20b, which fulfil two different functions.
  • the heat stream 20a is utilised to provide the second heat portion required for the endothermic reaction in the hybrid SMR unit 27a.
  • the heat stream 20b is utilised to provide heat to close the heat balance of the overall process 200. This may involve pre-heating of process streams such as 1 b, 2b, 3b or 4, or production of steam for the endothermic steam methane reforming reaction in the hybrid SMR unit 27a.
  • the first heat portion i.e. conversion of electrical energy into heat
  • the second heat portion i.e. the combustion of a fuel (hydrogen)
  • the material and heat integration according to example 1 represented by Figure 2 provides a significant reduction of the natural gas feed flow 1a compared to comparative example 4 represented by Figure 1 . Furthermore, it leads to lower carbon dioxide emissions.
  • heat integration is improved by exploiting the heat value of the hydrogen rich stream 9, which is preferably totally burnt as a fuel in order to supply part of the heat needed for the endothermic reaction and close the heat balance of the process. Given that the total hydrogen rich stream 9 is burnt and no recycle to the hydrogen production unit 30 is envisaged, high pressure in the tail gas separation unit 31 is no longer required, enabling savings in the compression costs.
  • FIG. 3 depicts a block flow diagram of a process 300 according to one example of the invention, in the following referred to as example 2.
  • the off-gas stream 10 is utilised for combustion in the fired heater 32 for generating the heat streams 20a and 20b.
  • the hydrogen rich stream is not combusted, but recycled to the dried shifted synthesis gas stream 51 , to afford a hydrogen enriched dried shifted synthesis gas stream.
  • the hydrogen yield in terms of the hydrogen product stream 7 is improved.
  • the combustion involves the whole off-gas stream 10.
  • the first heat portion i.e. conversion of electrical energy into heat
  • the second heat portion i.e. the combustion of a fuel (off-gas)
  • Burning the off-gas stream in the combustion device 32 entails a much lower electricity consumption compared to all of the comparative examples 1 to 4 and example 1 , without compromising the overall carbon capture efficiency, which is reflected in the still lower direct carbon dioxide emissions compared to comparative example 3 and slightly higher direct carbon dioxide emissions compared to comparative example 4.
  • the natural gas request is reduced in comparison to all of the comparative examples 1 to 4.
  • FIG. 4 depicts a block flow diagram of a process 400, which represents a partial process of the process according to the invention, and which represents an example of the tail gas separation step of the process of the invention.
  • the tail gas stream 8 is fed to a first compressor stage 36, where it is compressed to medium pressure, for instance a pressure of 5 to 20 bar.
  • the resulting compressed tail gas stream 50 is fed to a dryer unit 37, in which any trace of water is removed completely, in order to prevent water from solidifying in downstream steps of the process.
  • the dried tail stream thereby obtained is fed to a second compressor stage 38, in which the dried tail gas stream is further compressed to a higher pressure.
  • the resulting dried and compressed tail gas stream 52 is fed to a cooling and separation unit 39, in which the tail gas is cooled down to enable condensation of carbon dioxide and separation of the same from the non-condensable gas constituents.
  • a liquid carbon dioxide stream 53 thereby obtained is fed to a cryogenic distillation unit 40, in which pure carbon dioxide is obtained as a bottom product.
  • Said bottom product, which contains carbon dioxide at the desired purity, is discharged from the cryogenic distillation unit 40 as the carbon dioxide product stream 54.
  • the top distillate from the unit 40, the distillation column overhead product stream 58, is recycled to the second compressor stage 38.
  • the retentate stream 56 of the first membrane unit 41 is fed to a second membrane unit 42, where most of the remaining carbon dioxide is released as a permeate stream 57, which is recycled back to the second com pressor stage 38.
  • the retentate of the second membrane unit 42 consists of mostly carbon monoxide and methane, which is discharged from the second membrane unit 42 as the off-gas stream 10.
  • hydrodesulfurization (HDS) unit pre-reformer e-SMR unit a hybrid SMR unit water-gas shift unit cooling and separation unit pressure swing adsorption (PSA) unit (hydrogen production unit) tail gas separation unit fired heater (combustion device) steam system steam turbine and generator boiler first compressor stage (medium pressure) dryer unit second compressor stage (high pressure) cooling and separation unit cryogenic distillation unit first membrane unit second membrane unit compressed tail gas stream (medium pressure) dried tail gas stream compressed dried tail gas stream (high pressure) liquid carbon dioxide stream carbon dioxide product stream stream stream of non condensables retentate stream of first membrane unit permeate stream of second membrane unit distillation column overhead product stream
  • PSA pressure swing adsorption

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Abstract

The invention relates to a process for producing hydrogen, comprising a steam methane reforming (SMR) step for producing synthesis gas. In the process, heat for the endothermic reaction is partially provided by converting electrical energy into heat to afford a first heat portion, and partially provided by combustion of a fuel to afford a second heat portion. The synthesis gas is subject to a water-gas shift step and the shift product is separated into a hydrogen product and a the tail gas. The latter is subject to a tail gas separation step, producing at least one fuel containing stream and a carbon dioxide product stream. At least a portion of the at least one fuel containing stream is combusted for providing the second heat portion.

Description

04 March 2024 / StefSta
AIR LIQUIDE Reference: 2023P00059WO
Process for producing Hydrogen with electrically heated steam methane reforming
Technical field
The invention relates to a process for producing hydrogen, comprising a steam methane reforming (SMR) step, wherein heat for the endothermic reforming reaction is partially provided by converting electrical energy into heat, and partially provided by combustion.
AIR LIQUIDE ref. 2023P00059WQ 04 March 2024 Background art
The global hydrogen output is estimated at 70 Mt per year, most of which is produced by the steam methane reforming (SMR) process, in which natural gas reacts with steam to yield hydrogen (H2) and carbon monoxide (CO). This mixture, referred to as synthesis gas or syngas, is further converted by means of a water-gas shift unit to yield a shifted synthesis gas mixture consisting mainly of hydrogen and carbon dioxide (CO2).
Steam methane reforming is a strongly endothermic process, which requires a significant amount of heat to be provided for the reforming reaction. In standard SMR units, this heat is provided by combustion of a hydrocarbon containing fuel, leading to a high carbon footprint for this process, with approximately 10 tonnes of direct carbon dioxide (CO2) emissions for every tonne of hydrogen produced. It is estimated that the hydrogen production from SMR alone accounts for approximately 1.5 % of global carbon dioxide emissions.
Several setups have consequently been proposed to reduce the carbon footprint of hydrogen production through steam methane reforming, by capturing the carbon dioxide from various locations in the process. The location of the carbon dioxide capture is for instance the shifted synthesis gas, tail gas from a pressure swing adsorption unit, and flue gas. The process for capturing the carbon dioxide may involve chemical absorption, in particular an amine wash, adsorption (e.g. a CO2 VPSA), cryogenic separation, or a membrane separation of the carbon dioxide to be captured.
The carbon dioxide in the shifted synthesis gas makes about 60 % of the total direct carbon dioxide emissions of the SMR process. This share can be captured with relative ease owing to the high concentration I partial pressure of carbon dioxide in the shifted synthesis gas. The current industry standard is to capture the carbon dioxide on the shifted synthesis gas with a chemical wash, typically an amine wash, or with a cryogenic and membrane separation on the tail gas of a pressure swing adsorption (PSA) unit, after the hydrogen has been separated from the shifted synthesis gas by means of said PSA unit.
The remaining about 40 % of the carbon dioxide emissions are linked to the combustion of residual carbon monoxide (CO) and methane (CH4) in the PSA tail gas and/or hydrocarbon-based fuel, to generate the heat required for the endothermic SMR reaction. With the recycle of PSA tail gas to the burners, the flue gas will contain all the direct carbon dioxide emissions of the SMR process. A capture rate of approximately 90 % can thus be achieved in the flue gas, albeit at a higher capture cost, owing to the low pressure of the flue gas, and the low partial pressure of carbon dioxide in the flue gas.
An alternative to a traditional SMR setup is to replace the firebox by an electrically heated reactor, and thus provide the required amount of heat for the reaction with electricity as the energy vector. In a SMR process, such a solution would obviate the combustion of additional hydrocarbon fuel, and the consequent formation of a low pressure flue gas in which carbon dioxide capture is difficult. Under the assumption that electricity from a renewable energy source is used, it should reduce the carbon footprint of the process, and facilitate carbon capture.
An electrically heated SMR thus raises the prospect of a reduced carbon footprint, more cost efficient carbon capture, as well as a more compact reformer design, since the reformer design is no longer limited by the constraint of transferring heat from the furnace to the reformer tubes, which imposes a large surface area for the heat exchange in a conventional reformer.
Various technologies have been proposed for electric heated reactors, each with their own challenges. In particular, four main concepts are under investigation for electric heated reforming (resistive heating, induction heating, electric field reforming, microwave reforming), which are described in further detail in the following.
Resistive heating
According to this method, an external power generator induces an electric current to pass through the reactor following a conductive path. Heat is supplied to the SMR catalyst by dissipating power (Joule effect) through resistive media. The resistive medium can consist of the catalyst structure directly, or of other conductive heating elements (wire, pipe wall, conductive pellets). In literature, washcoated monoliths and other different structured catalysts have been studied for electrically heated steam or dry reforming, exploiting the conductivity of the structured material with respect to both heat and electricity when it is connected to a power source. Another option is to fill the reactor with a mixture of catalyst pellets and electrically conductive particles able to drive an electric current through the packed bed. Otherwise, the most straightforward application of the electric heating method is employing a distribution of heating elements not shaped as the catalyst but still allowing the passage of electric current dissipating the required heat to the reactive zone.
The main advantage of such a system is the improved heat transfer efficiency and the prospect of a better control of the temperature along the catalyst bed. The issue related to the wall thermal resistance is then overcome, so that in principle a cold outer reactor surface can be obtained when a refractory layer is used to prevent dissipation of heat. Thanks to the internal heat supply a large external heat exchange surface area is no longer required to facilitate the heat transfer, so that much more compact solutions can be developed for the reactor configuration.
US 9,908,091 B1 discloses a furnace device for steam reforming of hydrocarbons (preferably methane) consisting of a combustion chamber hosting reactor tubes, burners, a voltage source and electrical conductors, so that the tubes can be heated both by the combustion of fuel in the burners, as well as by supplying electric current.
Electro-reforming
Some scientific studies have demonstrated that when an electric field is applied to the catalyst bed of a reforming reactor, a conversion above thermal equilibrium is observed, thus raising the prospect of higher conversion rates at lower reforming temperatures.
The electric field essentially acts as a catalyst by lowering the activation energy of the reforming reaction, with the consequence that the reforming can be carried out at lower temperatures. The underlying principle is that the electric field induces proton hopping amongst the water particles adsorbed on the catalyst surface (according to the so- called Grotthuss mechanism), and enables the migration of the 02- (oxide) anions between the catalyst surface and the gas phase. Both of these phenomena reduce the surface potential of the catalyst and the activation barrier, boosting the reaction rate.
Inductive Some applications of this concept are described in the literature. The reactor configuration includes coils internally or externally installed, and incorporates a magnetic material, such as magnetic nanoparticles or thin films. When an alternating current runs through the coil, a magnetic field is formed around it, which in turn generates a Foucault current. Heat is generated as the power of this induced current is dissipated by Joule heating. In the presence of nanoparticle systems the heating mechanism occurs by magnetic hysteresis loss, while in the presence of macroscopic conducting material eddy currents are responsible for resistive heating.
There are claims that this technology could allow shortened start up periods and reduced energy losses due to a fast and more homogeneous heating response.
Microwave heating
Initial investigations suggested that the use of microwaves to heat a dielectric material in catalytic reactions leads to conversion above thermal equilibrium. Later studies claimed, however, that this was entirely due to an uneven distribution of the electromagnetic field and local hot spots.
Disclosure of the invention
In a steam methane reforming (SMR) process that aims to produce hydrogen, the reforming step is followed by a water-gas shift step, in which water and carbon monoxide react to form hydrogen and carbon dioxide. In a (final) purification step, most often in the form of a pressure swing adsorption (PSA) unit, the carbon dioxide, the unconverted methane and carbon monoxide, and any other components are separated from the hydrogen product. These other components form the PSA offgas, also known as PSA tail gas, which is desorbed from the PSA unit at low pressure.
In a conventional SMR unit, the PSA tail gas may account for up to 80 % of the total fuel required to generate the heat for the reforming reaction, with the remaining heat supplied in the form of a make-up fuel, generally a light hydrocarbon material such as natural gas. The combustion of this make-up fuel, which is avoided in an electrically heated SMR unit, thus only accounts for approximately 5 to 20 % of the direct carbon dioxide emissions on an SMR, and the question of the use of the PSA tail gas in an electrically heated SMR unit remains open.
The following table gives an example for the breakdown of carbon dioxide emissions (in kg emitted CO2 per kg produced H2) for conventional low steam export and high steam export SMR units. The data shown is based on simulation results.
Although the heat transfer efficiency in a conventional SMR unit (firebox) is low, with roughly 50% of the heat transferred to the reformer tubes and promoting the reforming reaction, most of the residual heat in the flue gas is recovered, either by heating various streams in the process or by generating steam. The conventional SMR process is thus highly integrated, typically reaching an overall heat efficiency of 90 % or more. In contrast, in an electrically heated SMR unit, only the heat available in the synthesis gas can be used for internal process heat integration, and it is thus challenging for an electrically heated SMR to close the heat balance of the overall process without considering additional heat sources or the combustion of at least a portion of an off- gas, which would have an adverse impact on the carbon dioxide emissions reduction.
It can be considered to burn the carbon monoxide and methane containing PSA offgas (tail gas) generated in an electrically heated SMR unit to close the heat balance, by generating steam required for the reforming process, and by producing steam which can be exported or fed to a turbine to generate part of the electricity requirement of the process. However, by this concept only very small improvements in natural gas consumption and direct carbon dioxide emissions compared to conventional SMR are obtained, which is shown based on simulation data in the following table. The electrically heated SMR is referred to as “e-SMR”.
1Carbon intensity of electricity: 262 gCO2eq/kWh in EU27 in 2021 2LHV (lower heating value) of Natural Gas: 46.5 M J/kg Hence, although emissions linked to the combustion of the make-up fuel have been avoided, the make-up fuel only accounted for a small portion of the direct carbon dioxide emissions, and the overall emissions of the SMR process are not reduced significantly. Considering indirect emissions linked to the generation of the electric power, taking the EU 27 average of 2021 , one finds that the total direct & indirect emissions have in fact increased. Similarly the total energy input into the system, whether in the form of the LHV of Natural Gas or as electric energy, has also increased relative to the reference conventional SMR.
Considering that the economics of hydrogen production are heavily driven by the operational expenditures (OPEX), it becomes clear from the above that even a relatively low cost of renewable electricity alone cannot justify an electrically heated SMR setup at current energy prices.
In the context of carbon pricing, in which governments implement a carbon tax for instance, an electrically heated SMR concept with carbon capture becomes more compelling. However, there is still the challenge for such a concept that a stream containing unconverted carbon monoxide and methane will be produced by the process, for which a use must be found, which will not penalize the economics of the solution while avoiding contributing to the carbon dioxide emissions of the process.
An electrically heated SMR process with carbon capture, in which the carbon dioxide is captured by means of a cryogenic process on the PSA tail gas, and where the remaining PSA off-gas (which is rich in carbon monoxide and methane) is combusted to generate electricity for the electrical heated reformer, does not yield a significant improvement over a conventional SMR process in which the carbon dioxide is captured by means of a cryogenic process on the PSA tail gas, and in which the remaining PSA off-gas (which is rich in carbon monoxide and methane) is combusted to generate part of the heat required for the reforming reaction. This is shown in the table below, where the data is based on simulation results. The electrically heated SMR is referred to as “e-SMR”.
1Carbon intensity of electricity: 262 gCO2eq/kWh in EU27 in 2021
2LHV (lower heating value) of Natural Gas: 46.5 MJ/kg
It can be assumed that the same is true for comparable processes with an amine wash as the carbon capture method. Although the emissions linked to the combustion of make-up fuel have been avoided in comparative example 4, the combustion of the carbon monoxide and methane containing off-gas once again yields a flue gas in which carbon capture is difficult and costly, with the consequence that the direct carbon dioxide emissions are not reduced significantly. Here again, the emissions linked to the generation of electric power may lead to an increase in total direct & indirect emissions relative to a conventional SMR, and the total energy input exceeds that of the conventional SMR.
It is one general object of the present invention to propose a process which overcomes the aforementioned drawbacks.
It is one further object of the present invention to propose a process with a lower amount of direct and/or indirect carbon dioxide emissions. It is one further object of the present invention to propose a process with a lower consumption of hydrocarbon containing feedstock and/or fuel.
It is one further object of the present invention to propose a process which finds, for an at least in part electrically heated SMR unit, a utilisation for the remaining hydrogen, carbon monoxide and methane contained in the tail gas or off-gas of a PSA or carbon capture unit.
It is one further object of the present invention to propose a process with a suitable heat integration for an at least in part electrically heated SMR process, which does not involve burning additional fuel.
A contribution to the at least partial solution of at least one of the above mentioned objects is provided by the subject-matter of the independent claims. The dependent claims provide preferred embodiments which contribute to the at least partial solution of at least one of the objects. Preferred embodiments of elements of a category according to the invention shall, if applicable, also be preferred for components of same or corresponding elements of a respective other category according to the invention.
The terms "having", "comprising" or "containing" etc. do not exclude the possibility that further elements, ingredients etc. may be comprised. The indefinite article “a” or "an" does not exclude that a plurality may be present.
In general, at least one of the underlying problems is at least partially solved by a process for producing hydrogen, the process comprising a) a steam methane reforming (SMR) step, to obtain a synthesis gas stream comprising hydrogen, carbon monoxide and carbon dioxide, by means of an endothermic reaction of a hydrocarbon containing feedstock stream and steam, wherein the heat for the endothermic reaction is provided by means of a first and a second heat portion, wherein the first heat portion is provided by converting electrical energy into heat, and the second heat portion is provided by combustion of a fuel; b) a water-gas shift step, comprising the conversion of carbon monoxide of the synthesis gas stream and steam to hydrogen and carbon dioxide, to obtain a shifted synthesis gas stream; c) a hydrogen production step, comprising separating hydrogen from the shifted synthesis gas stream, to obtain a hydrogen product stream and a tail gas stream; d) a tail gas separation step, comprising separating the tail gas stream into at least one fuel containing stream and a carbon dioxide product stream; e) combusting at least a portion of the at least one fuel containing stream for providing the second heat portion.
In the steam methane reforming (SMR) step a), the heat for the endothermic reaction is partially provided by converting electrical energy into heat and partially provided by combustion of a fuel. The conversion of electrical energy into heat provides a first heat portion. The combustion of a fuel provides a second heat portion.
The steam methane reforming according to step a) may also be referred to as a hybrid of electrically heated steam methane reforming (abbreviated e-SMR) and conventionally heated steam methane reforming. According to one embodiment, the electrical energy is produced from an electrical energy source, preferably a source of renewable electrical energy. According to one embodiment, the electrical energy is an electrical current.
According to one embodiment, the first heat portion is provided in the form of a first heat stream, and the second heat portion is provided in the form of a second heat stream.
According to one embodiment, the hydrocarbon containing feedstock stream is a natural gas stream.
According to one embodiment, a pre-reforming step precedes the steam methane reforming (SMR) step. In the pre-reforming step, higher hydrocarbons (C2 and higher) are converted with steam to methane (CH4).
According to one embodiment, a hydrodesulfurization step precedes the steam methane reforming (SMR) step, preferably precedes the pre-reforming step. In the hydrodesulfurization step, sulphur compounds which may act as SMR catalyst poison are removed from the hydrocarbon containing feedstock stream. In the water-gas shift step b), the carbon monoxide (CO) in the synthesis gas stream obtained in step a) is converted with water (steam) in the well-known water-gas shift reaction to hydrogen and carbon dioxide.
According to one embodiment, the water-gas shift step is followed by a cooling step and a separation step, to separate process water as process condensate from the shifted synthesis gas stream.
According to step c), hydrogen is produced from the shifted synthesis gas stream by means of a hydrogen production step by separating hydrogen from the shifted synthesis gas stream. According to one preferred embodiment, the hydrogen production step comprises a pressure swing adsorption (PSA) step. That is, the hydrogen is separated from the shifted synthesis gas stream by means of a pressure swing adsorption (PSA) unit. According to an alternative embodiment, the hydrogen is separated from the shifted synthesis gas stream by means of a membrane unit. In the hydrogen production step, a tail gas stream is produced. In one embodiment, the tail gas stream contains hydrogen, carbon dioxide, carbon monoxide and methane. The tail gas stream may also be referred to as off-gas stream of the hydrogen production step.
According to one embodiment, the hydrogen product stream contains at least 90 % hydrogen per volume, preferably at least 95 % per volume, more preferred at least 99 % per volume.
In the tail gas separation step d), the tail gas stream is separated into at least one fuel containing stream and a carbon dioxide product stream. That is, in the tail gas separation step d), the tail gas stream may be separated into one fuel containing stream and a carbon dioxide product stream. According to one alternative embodiment, in the tail gas separation step d), the tail gas stream may be separated into a plurality of fuel containing streams and a carbon dioxide product stream. For example, in the tail gas separation step d), the tail gas stream may be separated into a first fuel containing stream, a second fuel containing stream, optionally one or more further fuel containing stream(s), and a carbon dioxide product stream.
A carbon dioxide product stream is produced in the tail gas separation step d). That is, carbon is captured in the process by means of the tail gas separation step. The carbon dioxide product stream may be compressed and sequestrated (carbon capture and storage, CCS) or further used (carbon capture and utilisation, CCU). According to one embodiment, the carbon dioxide product stream contains at least 90 % carbon dioxide per volume, preferably at least 95 % per volume, more preferred at least 99 % per volume.
According to step e), at least a portion of the at least one fuel containing stream is combusted for providing the second heat portion. That is, according to one embodiment, when the tail gas stream is separated into one fuel containing stream and a carbon dioxide product stream according to step d), at least a portion of the one fuel containing stream is combusted for providing the second heat portion. According to one further embodiment, when the tail gas stream is separated into a first and a second fuel containing stream and a carbon dioxide product stream according to step d), at least a portion of the first fuel containing stream and optionally a portion of the second fuel containing stream is combusted for providing the second heat portion. Or vice versa, at least a portion of the second fuel containing stream and optionally a portion of the first fuel containing stream is combusted for providing the second heat portion.
It was found that according to the process of the invention, consumption of hydrocarbon containing feedstock, in particular natural gas, will be significantly lower in comparison to the process according to comparative example 4. Furthermore, carbon dioxide emissions (direct and/or indirect carbon dioxide emissions) will be significantly lower.
According to one embodiment, in the tail gas separation step, the tail gas stream is separated into a first fuel containing stream, a second fuel containing stream, and the carbon dioxide product stream.
Thereby, according to one embodiment, the process comprises
- combusting at least a portion of the first fuel containing stream for providing the second heat portion and/or
- combusting at least a portion of the second fuel containing stream for providing the second heat portion.
That is, according to this embodiment, at least a portion of the first fuel containing stream is combusted for providing the second heat portion, or at least a portion of the second fuel containing stream is combusted for providing the second heat portion, or at least a portion of the first fuel containing stream and at least a portion of the second fuel containing stream is combusted for providing the second heat portion.
According to one embodiment, the first fuel containing stream is a hydrogen rich stream and the second fuel containing stream is an off-gas stream rich in carbon monoxide and methane.
According to this embodiment, in the tail gas separation step d), the tail gas stream is separated into a hydrogen rich stream, an off-gas stream rich in carbon monoxide and methane, and the carbon dioxide product stream. The off-gas stream produced in step d) according to this embodiment may also be referred to as off-gas stream of the tail gas separation step.
The off-gas stream contains carbon monoxide and methane, in particular the off-gas stream is rich in carbon monoxide and methane. According to one embodiment, the off-gas stream contains at least 50 % carbon monoxide and methane per volume, preferably at least 70 % per volume, more preferred at least 80 % per volume.
According to one embodiment, the hydrogen rich stream contains at least 50 % hydrogen per volume, preferably at least 55 % per volume, more preferred at least 60 % per volume.
According to one embodiment, the process comprises combusting at least a portion of the hydrogen rich stream for providing the second heat portion. According to one further embodiment, the hydrogen rich stream is completely combusted for providing the second heat portion.
According to one embodiment, the second heat portion accounts for at least 20 % of the sum of the first and second heat portions. That is, when the process comprises combusting at least a portion of the hydrogen rich stream for providing the second heat portion, the second heat portion accounts for at least 20 % of the sum of the first and second heat portion. According to one further embodiment in this regard, the second heat portion accounts for 20 % to 40 % of the sum of the first and second heat portions, preferably 25 % to 35 % of the sum of the first and second heat portions. According to one embodiment, the process comprises recycling at least a portion of the off-gas stream to the hydrocarbon containing feedstock stream, so that a combined stream of hydrocarbon containing feedstock, off-gas and steam is supplied to the steam methane reforming (SMR) step. According to one embodiment, said combined stream will contain at least the hydrocarbons contained in the feedstock stream, carbon monoxide and methane contained in the off-gas stream, and steam. According to one embodiment, the off-gas stream is recycled to an unconverted hydrocarbon containing feedstock stream. According to one embodiment, the off-gas stream is recycled to a desulfurized hydrocarbon containing feedstock stream. According to one further embodiment, the off-gas stream is recycled to a desulfurized and pre-reformed hydrocarbon containing feedstock stream. According to one further embodiment, the off-gas stream obtained in the tail gas separation step is recycled completely to the hydrocarbon containing feedstock stream.
According to one preferred embodiment, the process comprises the combination of
- combusting at least a portion of the hydrogen rich stream for providing the second heat portion, and
- recycling at least a portion of the off-gas stream to the hydrocarbon containing feedstock stream, so that a combined stream of hydrocarbon containing feedstock, off-gas and steam is supplied to the steam methane reforming (SMR) step.
According to one embodiment, the process comprises combusting at least a portion of the off-gas stream rich in carbon monoxide and methane for providing the second heat portion. According to one further embodiment, the off-gas stream rich in carbon monoxide and methane is completely combusted for providing the second heat portion.
According to one embodiment, the second heat portion accounts for at least 50 % of the sum of the first and second heat portions. That is, when the process comprises combusting at least a portion of the off-gas stream rich in carbon monoxide and methane for providing the second heat portion, the second heat portion accounts for at least 50 % of the sum of the first and second heat portion. According to one further embodiment in this regard, the second heat portion accounts for 50 % to 80 % of the sum of the first and second heat portions, preferably 60 % to 70 % of the sum of the first and second heat portions. According to one embodiment, the process comprises recycling at least a portion of the hydrogen rich stream to the shifted synthesis gas stream, so that a hydrogen enriched shifted synthesis gas stream is supplied to the hydrogen production step. Thereby, a hydrogen enriched shifted synthesis gas stream is obtained, which is supplied to the hydrogen production step c). Thereby, the hydrogen yield of the process is improved. According to one embodiment, the hydrogen rich stream is recycled completely to the shifted synthesis gas stream.
According to one preferred embodiment, the process comprises the combination of
- combusting at least a portion of the off-gas stream rich in carbon monoxide and methane for providing the second heat portion, and
- recycling at least a portion of the hydrogen rich stream to the shifted synthesis gas stream, so that a hydrogen enriched shifted synthesis gas stream is supplied to the hydrogen production step.
According to one embodiment, the at least one fuel containing stream is routed to a combustion device, wherein the combustion device is configured to generate a heat stream for providing the second heat portion. The heat stream generated for providing the second heat portion may also be referred to as the second heat stream.
In particular, the heat stream comprises one hot flue gas stream or a plurality of hot flue gas streams.
According to one embodiment, the second heat portion is provided by combustion of hydrogen of the hydrogen rich stream, for example by means of a hydrogen burner.
According to one embodiment, the second heat portion is provided by combustion of carbon monoxide and methane of the off-gas stream rich in carbon monoxide and methane, for example by means of a conventional burner.
According to one embodiment, the combustion device is a fired heater or at least one burner.
For example, the (second) heat stream may comprise a stream of hot flue gases from a fired heater to provide the second heat portion. According to one further example, the at least one fuel containing stream may be utilised to operate a burner or a plurality of burners. Thereby, the burner or the plurality of burners provide(s) a stream of hot flue gases for providing the second heat portion. In particular, the at least one fuel containing stream may be utilised to operate a plurality of burners which are arranged in multiple rows, as it is known to the skilled person for a typical firebox of a steam methane reformer.
According to one embodiment, the heat stream generated by the combustion device is utilised to provide the second heat portion and to close the heat balance of the process, wherein closing the heat balance of the process comprises at least one element from
- pre-heating the hydrocarbon containing feedstock stream before it enters the steam methane reforming (SMR) step,
- providing heat for the endothermic reaction in the steam methane reforming (SMR) step,
- pre-heating boiler feed water for the generation of steam ,
- generating process steam for the steam methane reforming (SMR) step or the water-gas shift step, and
- super-heating steam generated in the process.
According to this embodiment, the heat stream generated by the combustion device is utilised to provide the second heat portion and, in addition, to close the heat balance of the process.
“Closing the heat balance of the process” means in particular, that the heat generated by the combustion device is used to improve the heat integration of the process. That is, preferably no external heat source or a minimum of external heat is utilized to fulfil the internal heat requirements of the process. Hence, the heat generated by the combustion device may be used for pre-heating the hydrocarbon containing feedstock stream before it enters the steam methane reforming (SMR) step, providing heat for the endothermic reaction in the steam methane reforming (SMR) step, pre-heating boiler feed water for the generation of steam, generating process steam for the steam methane reforming (SMR) step or the water-gas shift step, super-heating steam generated in the process, or a combination of the aforementioned. Thereby, the aforementioned list is not intended to be exhaustive.
According to one embodiment, in the tail gas separation step, the carbon dioxide product stream is obtained by means of - at least one tail gas drying step,
- at least one tail gas compression step,
- a cooling and condensation step of the dried tail gas to obtain carbon dioxide in liquid form, and a distillation step of the liquid carbon dioxide to obtain the carbon dioxide product stream.
That is, the carbon dioxide product stream is preferably produced by condensation of carbon dioxide from the dry and compressed tail gas stream, by which a stream of carbon dioxide in liquid form is obtained. In a subsequent distillation step of the liquid carbon dioxide, a pure carbon dioxide stream is obtained.
Condensation of the carbon dioxide leaves behind a stream of non-condensable gas components. This stream mainly contains hydrogen, carbon monoxide, methane and small amounts of non-condensed carbon dioxide.
According to one embodiment, in the tail gas separation step, the hydrogen rich stream is obtained by means of a first membrane separation step, wherein the hydrogen rich stream is produced as the permeate stream, and a stream rich in carbon dioxide, carbon monoxide and methane is produced as the retentate stream.
That is, the hydrogen rich stream is preferably produced by a first membrane separation step, wherein preferably the stream of non-condensable gas components is supplied to a first membrane separation unit. The hydrogen rich stream is obtained from said first membrane separation unit as the permeate stream, whilst the retentate mainly contains carbon monoxide, methane and carbon dioxide.
According to one further embodiment, in the tail gas separation step, the off-gas stream is obtained by means of a second membrane separation step, wherein the off-gas stream rich in carbon monoxide and methane is produced as the retentate stream, and a stream rich in carbon dioxide is produced as the permeate stream.
That is, the off-gas stream is preferably produced by a second membrane separation step, wherein preferably the retentate stream obtained from the first membrane separation step is supplied to a second membrane separation unit. The off-gas stream is obtained from said second membrane separation unit as the retentate stream, whilst the permeate mainly contains carbon dioxide, which may be recycled to the condensation step mentioned before. According to one embodiment, the converting of electrical energy into heat for providing the first heat portion comprises at least one element from
- resistive heating,
- electro-reforming,
- inductive heating, and
- microwave heating.
Details of those methods were discussed before. The conversion of electrical energy or electrical power into heat, for providing the first heat portion, may be realized by one or a combination of the aforementioned methods.
According to one embodiment, the hydrocarbon of the hydrocarbon containing feedstock stream is natural gas, and a molar ratio of natural gas consumed to hydrogen produced is 0.33 or less, preferably 0.32 or less.
One technical effect of the process according to the invention is reducing the amount of natural gas consumed throughout the process relative to a reference amount of hydrogen produced (for example, 1 Nm3 of hydrogen produced). In particular, according to the invention, the molar ratio of natural gas consumed to hydrogen produced is lower than 0.335, as shown in examples 1 and 2 in the following. Thereby, the consumed amount of natural gas does not necessarily refer to the hydrocarbon- containing feedstock exclusively, but may include further natural gas required as fuel, for example for the production of steam.
Detailed description of exemplary embodiments
The invention will now be detailed by way of exemplary embodiments and examples with reference to the attached drawings. In the figures and the accompanying description, equivalent elements are each provided with the same reference marks.
In the drawings:
Figure 1 depicts a block flow diagram of a process according to comparative example 4,
Figure 2 depicts a block flow diagram of a first embodiment of the process according to the invention,
Figure 3 depicts a block flow diagram of a second embodiment of the process according to the invention,
Figure 4 depicts a block flow diagram of an embodiment of the tail gas separation step of the process according to the invention.
Figure 1 depicts a block flow diagram of a process 100 according to comparative example 4, wherein off-gas produced in the tail gas separation step is routed to a combustion device. The heat produced by the combustion device is utilized to produce steam, and the steam is further utilized to generate electrical energy by means of a steam turbine and a generator. The electrical energy is converted into heat for the endothermic reaction of the steam methane reforming (SMR) step.
A hydrocarbon containing feedstock stream, here a natural gas stream 1a, is desulfurized in a hydrodesulfurization unit 25 to afford a desulfurized natural gas stream. Said desulfurized natural gas stream is combined with steam stream 13a, which is a partial stream of steam stream 13. The resulting combined stream of desulfurized natural gas and steam 2a is converted in a pre-reformer 26 to afford a stream of desulfurized and pre-reformed natural gas, containing mainly methane as the hydrocarbon component. Said desulfurized and pre-reformed natural gas stream is combined with steam stream 13b, which is a partial stream of steam stream 13. The resulting combined stream of pre-reformed desulfurized natural gas and steam 3a is introduced into an electrically heated SMR unit 27, in the following referred to as e- SMR unit 27.
In the e-SMR unit 27, the desulfurized and pre-reformed natural gas stream is reformed with steam to afford a stream of synthesis gas 4. The reformer tubes (not shown) of the e-SMR unit 27 are heated by means of electrical energy, which is converted into heat. The synthesis gas stream 4 is introduced into a water-gas shift unit 28, in which carbon monoxide of the synthesis gas stream 4 is converted with steam into hydrogen and carbon dioxide, to afford a shifted synthesis gas stream 5. The shifted synthesis gas stream 5 contains mainly hydrogen and carbon dioxide, but also unconverted carbon monoxide and methane.
The shifted synthesis gas stream 5 is introduced into a cooling and separation unit 29, in which water contained in the shifted synthesis gas is condensed and withdrawn from the unit 29 as a water condensate stream 11. Said water condensate stream 11 is supplied to a boiler 35, which is also supplied with demineralized water via demineralized water stream 12. In the boiler 35, a steam stream 13 is produced, which is divided up into the steam partial streams 13a and 13b, to supply the pre-reformer unit 26 and the e-SMR unit 27 with steam.
An essentially water-free (dried) shifted synthesis gas stream 5a is withdrawn from the cooling and separation unit 29, and a hydrogen rich stream 9 is combined with said stream to afford a hydrogen enriched dried shifted synthesis gas stream 6. This stream 6 is introduced into a hydrogen production unit, here a pressure swing adsorption (PSA) unit 30, in which a hydrogen product stream 7 and a tail gas stream 8 is produced. The hydrogen product stream 7 is optionally further purified and discharged from the process for further use.
The tail gas stream 8 is introduced into the tail gas separation unit 31 , in which the tail gas stream is separated into the hydrogen rich stream 9, a carbon dioxide product stream 54, and an off-gas stream 10. How the hydrogen rich stream 9, the carbon dioxide product stream 54, and the off-gas stream 10 can be specifically obtained will be discussed further below in connection with Figure 4. The hydrogen rich stream 9 produced in the tail gas separation unit 31 is completely recycled to the dry shifted synthesis gas stream 5a discharged from the cooling and separation unit 29, to afford the hydrogen enriched shifted synthesis gas stream 6.
The off-gas stream 10 is fed in its entirety to a combustion device, here a fired heater 32, and burned with combustion air to generate heat. The heat generated in the fired heater 32 is utilized in the form of two heat streams 17a and 17b. That is, a part of the generated heat is utilized to close the heat balance of the process (stream 17b), and the remaining part is utilized to generate steam by means of a steam system 33. In the fired heater, a flue gas stream 16 is produced, which mainly comprises carbon dioxide and which is discharged from the fired heater. The steam system 33 is also supplied with demineralized water by means of a demineralized water stream 14. A steam stream 15 thereby produced in the steam system 33 is fed to a steam turbine and generator unit 34, in which electrical energy is produced in the form of an electrical current 18, which is used for generating heat in the e-SMR unit 27.
The electrical current 18 produced by the steam turbine and generator unit 34 reduces the amount of electrical power input required for the e-SMR unit. So the main benefit of this approach is the reduction of electricity demand from an external source. However, carbon dioxide emissions are not as much reduced as in the following examples of processes according to the invention.
Figure 2 depicts a block flow diagram of a process 200 according to one example of the invention, in the following referred to as example 1. According to this example, an off-gas stream 10 produced in the tail gas separation unit 31 is fed to the natural gas stream 1a, to afford a combined stream of natural gas and off-gas 1 b. The steam methane reforming (SMR) unit 27a of the process 200 is a hybrid SMR unit, in which the heat for the endothermic SMR reaction is provided by converting electrical energy into heat, and is provided by combustion of a fuel. Electrical energy is provided by means of an electrical current 19, from which a first heat portion is generated by converting the electrical energy of the electrical current 19 into heat. A heat stream 20a is generated by combustion of a fuel, which provides the second heat portion for the endothermic SMR reaction in hybrid SMR unit 27a. The fuel required for the combustion is hydrogen, which is contained in hydrogen rich stream 9. Said hydrogen rich stream 9 is produced in the tail gas separation unit 31 and fed to a combustion device 32 to generate heat, in order to provide the second heat portion required for the endothermic SMR reaction. According to process 200, the combustion device 32 is a fired heater, which produces two heat streams 20a and 20b. The two heat streams are for instance derived from hot flue gas streams. The heat stream 20a is utilised to provide heat for the hybrid SMR unit 27a. The heat stream 20b is utilised to provide heat to close the heat balance of the overall process.
Details of the process according to example 1 are explained below.
A hydrocarbon containing feedstock stream, here a natural gas stream 1a, is combined with the off-gas stream 10, whereby the off-gas partial stream 10 contains mainly carbon monoxide and methane. The combination of said streams afford a combined stream of natural gas and off-gas 1 b, which is desulfurized in a hydrodesulfurization unit 25 to afford a desulfurized combined stream of natural gas and off-gas. Said stream is combined with steam stream 13a, which is a partial stream of steam stream 13. The resulting combined stream 2b of desulfurized natural gas, off-gas and steam is converted in a pre-reformer unit 26 to afford a combined stream of desulfurized and pre-reformed natural gas and off-gas, containing mainly methane as the hydrocarbon component. Said stream is combined with steam stream 13b, which is a partial stream of steam stream 13. The resulting combined stream 3b of pre-reformed desulfurized natural gas, off-gas and steam, is introduced into the hybrid SMR unit 27a.
In the hybrid SMR unit 27a, the desulfurized and pre-reformed natural gas and off-gas is reformed with steam to afford a stream of synthesis gas 4. The reformer tubes (not shown) of the hybrid SMR unit 27a are heated by means of electrical energy, which is converted into heat. This heat represents the first heat portion required for the endothermic steam methane reforming reaction. Electrical energy is provided by means of an electric current 19, which comprises electricity from a renewable energy source. Furthermore, the reformer tubes of the hybrid SMR unit 27a are heated by heat which is provided by heat stream 20a. This heat represents the second heat portion required for the endothermic steam methane reforming reaction. Heat stream 20a is derived from a hot flue gas stream generated in the fired heater 32. According to an alternative embodiment, the heat stream 20a is derived from burning hydrogen of the hydrogen rich stream 9 in a plurality of hydrogen burners. The synthesis gas stream 4 produced in the hybrid SMR unit 27a is introduced into a water-gas shift unit 28, in which carbon monoxide of the synthesis gas stream 4 is converted with steam into hydrogen and carbon dioxide, to afford a shifted synthesis gas stream 5. The shifted synthesis gas stream 5 contains mainly hydrogen and carbon dioxide, but also unconverted carbon monoxide and methane.
The shifted synthesis gas stream 5 is introduced into a cooling and separation unit 29, in which water contained in the shifted synthesis gas is condensed and withdrawn from the unit 29 as a water condensate stream 11. Said water condensate stream 11 is supplied to a boiler 35, which is also supplied with demineralized water via demineralized water stream 12. In the boiler 35, a steam stream 13 is produced, which is divided up into the steam partial streams 13a and 13b, to supply the pre-reformer unit 26 and the hybrid SMR unit 27a with steam.
An essentially water-free shifted synthesis gas stream 5a is withdrawn from the cooling and separation unit 29. Said stream 5a is introduced into a hydrogen production unit, here a pressure swing adsorption (PSA) unit 30, in which a hydrogen product stream 7 and a tail gas stream 8 are produced. The hydrogen product stream 7 is optionally further purified and discharged from the process for further use.
The tail gas stream 8 is introduced into the tail gas separation unit 31 , in which the tail gas stream is separated into the hydrogen rich stream 9, a carbon dioxide product stream 54, and the off-gas stream 10. How the hydrogen rich stream 9, the carbon dioxide product stream 54, and the off-gas stream 10 can be specifically obtained will be discussed further below in connection with Figure 4.
The off-gas stream 10 produced in the tail gas separation unit 31 is completely recycled to the natural gas stream 1a to afford the combined stream of natural gas and off-gas 1b.
The hydrogen rich stream 9 is routed to the combustion device, here a fired heater 32, and burned with combustion air to generate a flue gas stream 16, and heat streams 20a and 20b derived from the flue gas stream. Hence, the heat generated in the fired heater 32 is utilized in the form of two heat streams 20a and 20b, which fulfil two different functions. The heat stream 20a is utilised to provide the second heat portion required for the endothermic reaction in the hybrid SMR unit 27a. The heat stream 20b is utilised to provide heat to close the heat balance of the overall process 200. This may involve pre-heating of process streams such as 1 b, 2b, 3b or 4, or production of steam for the endothermic steam methane reforming reaction in the hybrid SMR unit 27a.
According to the example of Figure 2 (example 1), the first heat portion, i.e. conversion of electrical energy into heat, accounts for 70 % of the sum of heat provided for the endothermic reaction. The second heat portion, i.e. the combustion of a fuel (hydrogen), accounts for 30 % of the sum of heat provided for the endothermic reaction.
The material and heat integration according to example 1 represented by Figure 2 provides a significant reduction of the natural gas feed flow 1a compared to comparative example 4 represented by Figure 1 . Furthermore, it leads to lower carbon dioxide emissions. According to example 1 , represented by Figure 2, heat integration is improved by exploiting the heat value of the hydrogen rich stream 9, which is preferably totally burnt as a fuel in order to supply part of the heat needed for the endothermic reaction and close the heat balance of the process. Given that the total hydrogen rich stream 9 is burnt and no recycle to the hydrogen production unit 30 is envisaged, high pressure in the tail gas separation unit 31 is no longer required, enabling savings in the compression costs.
Furthermore, compared to comparative example 4 (and further comparative examples 1 to 3) represented by Figure 1 , the electrical power required for the endothermic reaction is substantially reduced, thanks to the contribution coming from the hydrogen combustion.
This is exemplified in the table below, which data is based on simulation results.
1Carbon intensity of electricity: 262 gCO2eq/kWh in EU27 in 2021
2LHV (lower heating value) of Natural Gas: 46.5 MJ/kg
With regard to the demand for electrical energy, it has to be taken into account that if electrical energy from a renewable energy source is used, no indirect carbon dioxide emissions are linked to such an electrical energy source.
Provided that indirect emissions are linked to the generation of electricity (assuming the carbon intensity of electricity due to the EU 27 basis), however, the total direct and indirect emissions have been decreased considerably, and are now lower than those of a conventional SMR with carbon capture (comparative example 3) and lower than those of a SMR setup according to comparative example 4. Similarly the total energy input has now decreased relative to comparative examples 3 and 4. Furthermore, the setup according to example 1 results in a lower overall energy input. Figure 3 depicts a block flow diagram of a process 300 according to one example of the invention, in the following referred to as example 2. In comparison to example 1 (represented by Figure 2), the off-gas stream 10 is utilised for combustion in the fired heater 32 for generating the heat streams 20a and 20b. The hydrogen rich stream is not combusted, but recycled to the dried shifted synthesis gas stream 51 , to afford a hydrogen enriched dried shifted synthesis gas stream. Thereby, the hydrogen yield in terms of the hydrogen product stream 7 is improved.
With regard to further details, the explanations according to process 200, represented by Figure 2, apply.
Preferably, the combustion involves the whole off-gas stream 10.
According to the example of Figure 3 (example 2), the first heat portion, i.e. conversion of electrical energy into heat, accounts for 36 % of the sum of heat provided for the endothermic reaction. The second heat portion, i.e. the combustion of a fuel (off-gas), accounts for 64 % of the sum of heat provided for the endothermic reaction.
Burning the off-gas stream in the combustion device 32 entails a much lower electricity consumption compared to all of the comparative examples 1 to 4 and example 1 , without compromising the overall carbon capture efficiency, which is reflected in the still lower direct carbon dioxide emissions compared to comparative example 3 and slightly higher direct carbon dioxide emissions compared to comparative example 4. The natural gas request is reduced in comparison to all of the comparative examples 1 to 4.
This is exemplified in the table below, which data is based on simulation results.
1Carbon intensity of electricity: 262 gCO2eq/kWh in EU27 in 2021
2LHV (lower heating value) of Natural Gas: 46.5 MJ/kg
Here also, it is preferable to apply this setup if electrical energy from a renewable energy source is used, such that there are no indirect emissions linked to the electrical energy source.
Considering the above example with indirect emissions (EU 27 basis), however, example 2 yields lower direct & indirect emissions than comparative examples 3 and 4, and results in a lower total energy input. Figure 4 depicts a block flow diagram of a process 400, which represents a partial process of the process according to the invention, and which represents an example of the tail gas separation step of the process of the invention.
The tail gas stream 8 is fed to a first compressor stage 36, where it is compressed to medium pressure, for instance a pressure of 5 to 20 bar. The resulting compressed tail gas stream 50 is fed to a dryer unit 37, in which any trace of water is removed completely, in order to prevent water from solidifying in downstream steps of the process. The dried tail stream thereby obtained is fed to a second compressor stage 38, in which the dried tail gas stream is further compressed to a higher pressure.
The resulting dried and compressed tail gas stream 52 is fed to a cooling and separation unit 39, in which the tail gas is cooled down to enable condensation of carbon dioxide and separation of the same from the non-condensable gas constituents. A liquid carbon dioxide stream 53 thereby obtained is fed to a cryogenic distillation unit 40, in which pure carbon dioxide is obtained as a bottom product. Said bottom product, which contains carbon dioxide at the desired purity, is discharged from the cryogenic distillation unit 40 as the carbon dioxide product stream 54. The top distillate from the unit 40, the distillation column overhead product stream 58, is recycled to the second compressor stage 38.
A stream of non-condensable gas constituents 55, discharged from the cooling and separation unit 39, is fed to a first membrane unit 41 , from which the hydrogen rich stream 9 is obtained as the permeate stream, and a retentate stream 56, which contains mostly carbon monoxide, methane and remaining carbon dioxide. The retentate stream 56 of the first membrane unit 41 is fed to a second membrane unit 42, where most of the remaining carbon dioxide is released as a permeate stream 57, which is recycled back to the second com pressor stage 38. The retentate of the second membrane unit 42 consists of mostly carbon monoxide and methane, which is discharged from the second membrane unit 42 as the off-gas stream 10. List of reference signs
100 process (comparative example 4)
200 process (example 1)
300 process (example 2)
400 sub-process (tail gas separation)
1a natural gas stream
1b combined stream of natural gas and off-gas
2a combined stream of desulfurized natural gas and steam
2b combined stream of desulfurized natural gas, steam, and off-gas
3a combined stream of pre-reformed desulfurized natural gas and steam
3b combined stream of pre-reformed desulfurized natural gas, steam and off-gas
4 synthesis gas stream
5 shifted synthesis gas stream
5a dried shifted synthesis gas stream
6 hydrogen enriched dried shifted synthesis gas stream
7 hydrogen product stream
8 tail gas stream
9 hydrogen rich stream
10 off-gas stream
11 water condensate stream
12 demineralized water stream
13 steam stream
13a, 13b steam partial stream
14 demineralized water stream
15 steam stream
16 flue gas stream
17a, 17b heat stream
18 electric current
19 electric current
20a, 20b heat stream
25 hydrodesulfurization (HDS) unit pre-reformer e-SMR unit a hybrid SMR unit water-gas shift unit cooling and separation unit pressure swing adsorption (PSA) unit (hydrogen production unit) tail gas separation unit fired heater (combustion device) steam system steam turbine and generator boiler first compressor stage (medium pressure) dryer unit second compressor stage (high pressure) cooling and separation unit cryogenic distillation unit first membrane unit second membrane unit compressed tail gas stream (medium pressure) dried tail gas stream compressed dried tail gas stream (high pressure) liquid carbon dioxide stream carbon dioxide product stream stream of non condensables retentate stream of first membrane unit permeate stream of second membrane unit distillation column overhead product stream

Claims

Claims
1. A process (200, 300) for producing hydrogen, the process comprising a) a steam methane reforming (SMR) step, to obtain a synthesis gas stream (4) comprising hydrogen, carbon monoxide and carbon dioxide, by means of an endothermic reaction of a hydrocarbon containing feedstock stream (1a, 1b) and steam, wherein the heat for the endothermic reaction is provided by means of a first and a second heat portion, wherein the first heat portion is provided by converting electrical energy into heat, and the second heat portion is provided by combustion of a fuel; b) a water-gas shift step, comprising the conversion of carbon monoxide of the synthesis gas stream and steam to hydrogen and carbon dioxide, to obtain a shifted synthesis gas stream (5); c) a hydrogen production step, comprising separating hydrogen from the shifted synthesis gas stream, to obtain a hydrogen product stream (7) and a tail gas stream (8); d) a tail gas separation step, comprising separating the tail gas stream into at least one fuel containing stream (9, 10) and a carbon dioxide product stream (54); e) combusting at least a portion of the at least one fuel containing stream for providing the second heat portion.
2. Process according to claim 1 , wherein in the tail gas separation step, the tail gas stream is separated into a first fuel containing stream, a second fuel containing stream, and the carbon dioxide product stream.
3. Process according to claim 2, wherein the process comprises
- combusting at least a portion of the first fuel containing stream for providing the second heat portion and/or
- combusting at least a portion of the second fuel containing stream for providing the second heat portion.
4. Process according to claim 2 or 3, wherein the first fuel containing stream is a hydrogen rich stream (9) and the second fuel containing stream is an off-gas stream (10) rich in carbon monoxide and methane.
5. Process according to claim 4, wherein the process comprises combusting at least a portion of the hydrogen rich stream for providing the second heat portion.
6. Process according to claim 5, wherein the second heat portion accounts for at least 20 % of the sum of the first and second heat portions.
7. Process according to claim 5 or 6, wherein the process comprises recycling at least a portion of the off-gas stream (10) to the hydrocarbon containing feedstock stream (1a), so that a combined stream of hydrocarbon containing feedstock, offgas and steam is supplied to the steam methane reforming (SMR) step.
8. Process according to claim 4, wherein the process comprises combusting at least a portion of the off-gas stream rich in carbon monoxide and methane for providing the second heat portion.
9. Process according to claim 8, wherein the second heat portion accounts for at least 50 % of the sum of the first and second heat portions.
10. Process according to claim 8 or 9, wherein the process comprises recycling at least a portion of the hydrogen rich stream to the shifted synthesis gas stream, so that a hydrogen enriched shifted synthesis gas stream (6) is supplied to the hydrogen production step.
11 . Process according to any one of the preceding claims, wherein the at least one fuel containing stream is routed to a combustion device (32), wherein the combustion device is configured to generate a heat stream (17b) for providing the second heat portion.
12. Process according to claim 11 , wherein the combustion device is a fired heater or at least one burner.
13. Process according claim 11 or 12, wherein the heat stream generated by the combustion device is utilised to provide the second heat portion and to close the heat balance of the process, wherein closing the heat balance of the process comprises at least one element from
- pre-heating the hydrocarbon containing feedstock stream before it enters the steam methane reforming (SMR) step,
- providing heat for the endothermic reaction in the steam methane reforming (SMR) step,
- pre-heating boiler feed water for the generation of steam,
- generating process steam for the steam methane reforming (SMR) step or the water-gas shift step, and
- super-heating steam generated in the process.
14. Process according to any one of the preceding claims, wherein in the tail gas separation step, the carbon dioxide product stream is obtained by means of
- at least one tail gas drying step,
- at least one tail gas compression step,
- a cooling and condensation step of the dried tail gas to obtain carbon dioxide in liquid form, and
- a distillation step of the liquid carbon dioxide to obtain the carbon dioxide product stream.
15. Process according to any one of claims 4 to 14, wherein in the tail gas separation step, the hydrogen rich stream is obtained by means of a first membrane separation step, wherein the hydrogen rich stream (9) is produced as the permeate stream, and a stream rich in carbon dioxide, carbon monoxide and methane is produced as the retentate stream (56).
16. Process according to any one of claims 4 to 15, wherein in the tail gas separation step, the off-gas stream is obtained by means of a second membrane separation step, wherein the off-gas stream (10) rich in carbon monoxide and methane is produced as the retentate stream, and a stream rich in carbon dioxide is produced as the permeate stream (57).
17. Process according to any one of the preceding claims, wherein the converting of electrical energy into heat for providing the first heat portion comprises at least one element from
- resistive heating, - electro-reforming,
- inductive heating, and
- microwave heating.
18. Process according to any one of the preceding claims, wherein the hydrocarbon of the hydrocarbon containing feedstock stream is natural gas, and wherein a molar ratio of natural gas consumed to hydrogen produced is 0.33 or less, preferably 0.32 or less.
EP24707837.1A 2023-03-09 2024-03-04 Process for producing hydrogen with electrically heated steam methane reforming Pending EP4676876A1 (en)

Applications Claiming Priority (2)

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EP23160893 2023-03-09
PCT/EP2024/055540 WO2024184290A1 (en) 2023-03-09 2024-03-04 Process for producing hydrogen with electrically heated steam methane reforming

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EP1858803B1 (en) * 2005-03-14 2016-07-06 Geoffrey Gerald Weedon A process for the production of hydrogen with co-production and capture of carbon dioxide
US20120291483A1 (en) * 2011-05-18 2012-11-22 Air Liquide Large Industries U.S. Lp Process For Recovering Hydrogen And Carbon Dioxide
DE102015004121A1 (en) 2015-03-31 2016-10-06 Linde Aktiengesellschaft Oven with electric and fuel-heated reactor tubes for steam reforming of a hydrocarbon-containing insert
JP2024530171A (en) * 2021-08-04 2024-08-16 ネクストケム テック エス．ピー．エー． Hydrogen production method linked with CO2 capture
US20250010259A1 (en) * 2021-11-15 2025-01-09 Topsoe A/S Blue hydrogen process and plant

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