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Carbon-neutral process for generating electricity — Claire Technologies Corp. (US11848467B2)

Claire Technologies Corp. · Google Patents

Google Patents · Patents · License: Open Access

patent, google patents, intellectual property, US11848467B2, Claire Technologies Corp., Paul A. Allinson, en, 2023

ABSTRACT

Abstract

A method is described for generating carbon-neutral electricity using purified hydrogen as an energy source. A recyclable LOHC is provided to the process for reversible dehydrogenation. Hydrogen generated by dehydrogenation is purified and electrochemically converted to electricity. Heat for maintaining the dehydrogenation reaction temperature is derived from combustion of a portion of the liquid products from dehydrogenation, the portion combusted being less than or equal to the portion of carbon-neutral component included in the recyclable LOHC.

Description

PRIORITY

This application claims the benefit of the priority of U.S. provisional patent application Ser. No. 63/091,425, entitled âCarbon-Neutral Process for Generating Electricityâ, filed on Oct. 14, 2020, which is hereby incorporated in its entirety by reference herein.

FIELD OF THE INVENTION

This disclosure relates generally to a carbon-neutral process for generating electricity and to a liquid organic hydrogen carrier (LOHC) for supplying hydrogen for generating the carbon-neutral electricity. More specifically, this disclosure relates to methods of use of regenerable carbon-neutral compositions consisting of liquid organic hydrogen carriers used in processes to supply hydrogen to generate electricity under carbon-neutral conditions using processes and apparatus operating with a net zero atmospheric emission of carbon oxides.

BACKGROUND OF THE INVENTION

The invention relates to the field of electricity generation. Systems employing battery storage to supply electricity are known and readily available. But systems that depend exclusively on battery electrical storage are limited in battery capacity, limited by battery weight, and limited in operating time by the extended battery recharging time required.

A great deal of effort has been expended in developing systems that convert chemical energy into electricity. Having the capability of loading a gaseous, liquid, or solid material in the system for hydrogen conversion into electricity greatly increases the flexibility for the developing electrified economy. Hydrogen has been acknowledged for many years as a potential source of electrical energy by electrochemical hydrogen conversion that generates electrical energy. Hydrogen may be stored as a compressed gas or as liquid hydrogen at cryogenic temperatures. However, increasing the operating flexibility of an electric powered vehicle by providing high pressure hydrogen for electrochemical conversion and generation of additional electrical energy requires the storage of high-pressure hydrogen, along with its not insignificant associated risks. Furthermore, the lack of a hydrogen delivery infrastructure in virtually all locations limits applicability of a high-pressure hydrogen solution. Hydrogen may be stored as the captured or contained gas in various carrier media such as metal hydrides, high surface area carbon materials, and metal-organic framework materials. Generally, the contained hydrogen in such carrier media can be released by raising the temperature and/or lowering the hydrogen pressure.

Hydrogen can also be stored by means of reversible catalytic hydrogenation of unsaturated, usually aromatic, organic compounds. An organic hydrogen carrier, referred to herein as a âliquid organic hydrogen carrierâ (LOHC), is generally liquid at ambient conditions, and contains a significant amount of chemically bound hydrogen that may be liberated by an elevated temperature catalytic process. The release of hydrogen by dehydrogenation is an endothermic process, i.e., one which requires an input of heat, at a temperature where the dehydrogenation of the carrier can proceed with adequate reaction rates. A number of methods have been suggested for generating the heat required to maintain the dehydrogenation reaction step, including combustion of hydrogen that is generated in the process, or combustion of a supplied fuel to provide the necessary heat. Using generated hydrogen as combustion fuel has a significant impact on hydrogen availability for generating electricity. Burning a combustion fuel in the conventional method for heat generation creates greenhouse emissions, which serves to neutralize the benefit of using hydrogen as a source of system energy.

Conventional use of LOHC feedstocks as hydrogen carriers has had limited success on account of the relatively low efficiency of energy conversion, the challenges of operating a dehydrogenation reaction zone within size constraints while maintaining acceptable catalyst activity, and the requirement for generating thermal energy without using a portion of the generated hydrogen for thermal energy production and while maintaining carbon-neutral operation with hydrocarbon combustion.

Fossil fuels (e.g., coal, oil, and natural gas) have been powering economies for over 302 years, and currently supply over 80 percent of the world's energy. It is well established combustion of fossil fuels produces undesirable emissions such as greenhouse gases.

Atmospheric greenhouse gases are harmful to the environment because they absorb infrared radiation (IR) which is subsequently released and reflected into the atmosphere, thereby increasing the mean planetary temperature over time.

Rising global warming challenges due to greenhouse gas emissions necessitates a shift in the world's energy economies to alternative energy sources such as battery, solar and wind. Unfortunately, these alternative energy sources only makeup only about twenty percent of the world's current total energy economy.

Further, governmental regulating authorities continue to reduce the allowable greenhouse gas emissions for various fossil fuel emissions sources, including new vehicles.

Society is turning towards carbon-neutral (CN) electricity as it moves away from fossil fuels in an effort to significantly reduce Green House Gas (GHG) emissions. Electric Vehicles (EVs) are beginning to make an impact in the passenger car and pickup truck market, and they are anticipated to penetrate the short and medium-haul truck market. Limitations in energy density currently limit battery use in Class 7/8 long-haul tractor-trailers, trains, shipping, and aircraft. Battery banks are used to load-balance certain utility grids for short durations, typically 4 hours or less, but cannot support large back-up energy needs.

Hydrogen has been acknowledged for many years as a potential large-scale source of energy (âhydrogen economyâ). Hydrogen is a powerful fuel and produces on a mass basis three times the energy content of gasoline (120 MJ/kg vs. 44 MJ/kg). Further, combustion of hydrogen does not produce environmentally harmful IR-absorbing gas emissions.

However, numerous technical challenges are inhibiting the shift to a large-scale hydrogen economy. These challenges include, among other things, the difficulty of developing large scale long-term, safe delivery and storage infrastructures for compressed hydrogen.

Carbon-neutral systems utilizing hydrogen are known and readily available but currently available systems generally require high pressure compression in the 10,000-psig region for storage and use in fuel cells. A national high pressure hydrogen distribution infrastructure does not exist and is estimated to cost hundreds of billions of dollars to install.

Systems utilizing LOHCs to transport labile hydrogen via existing fossil fuel delivery systems to remote sites where, after dehydrogenation, they provide hydrogen to power fuel cells are known, but they cannot currently operate in a carbon-neutral (CN) mode without a CN external power or heat supply.

There have been efforts to eliminate IR-absorbing gas emissions from LOHC-based hydrogen production processes. However, this method requires the generation and/or storage of a sufficient amount of electricity to ensure continued operations of the hydrogen production process.

Current methods also require additional electrical storage and battery management equipment. In addition, drawing electricity for the heating element from downstream equipment (e.g., a fuel cell) reduces the amount of electricity available for the target application (e.g., powering an electrical motor in a vehicle).

Others have suggested combusting produced hydrogen to generate the heat for dehydrogenation of the LOHC. However, this method lowers the amount of hydrogen available for use by downstream equipment (e.g., a hydrogen fuel cell), thereby reducing the efficiency of the overall system.

One approach known in the art employs a combustible/evaporable fossil fuel or biofuel additive to the LOHC feed. The additive is then separated during the hydrogen production process and combusted to form heat for dehydrogenation of the LOHC. However, combustion of the additive produces IR-absorbing gas emissions, thereby increasing the total atmospheric concentration of these harmful gases, and requires separation of the additive prior to combustion, adding an additional process step. Furthermore, the additive decreases the amount of LOHC in the total feed, thereby reducing the amount of hydrogen produced as compared to a feed containing 100% LOHC.

Accordingly, there is a need for a LOHC-based process for producing hydrogen which eliminates or reduces the net increase in atmospheric GHG emissions, and which is not completely reliant on chemical or energy products (e.g., hydrogen and electricity) needed by downstream equipment such as for example fuel cells, hydrogen internal combustion engines, and the like.

SUMMARY OF THE INVENTION

In one aspect, the compositions, methods and apparatus described herein provide for a scalable system for generating, storing, and delivering CN energy at ambient conditions integrated into a carbon-neutral energy facility (CNEF).

In another aspect, a scalable system is disclosed herein designed for use in green-fields, brown-fields and to complement existing oil refineries and chemical plants maximizing the use of their existing infrastructure.

In yet another aspect, a scalable system is disclosed herein that operates to complement and balance renewable electrical generating systems by utilizing excess electrical energy to electrolyze water into hydrogen and oxygen when excess power is available and to convert the stored hydrogen into electricity during periods of electrical deficit.

In a further aspect, a scalable system is disclosed herein that may be configured to function as a rehydrogenation facility that is transportable to location for reloading liquid organic hydrogen carriers (LOHCs) with CN hydrogen for local use.

In another aspect, a cyclic process is disclosed herein that is suitable for generating electricity from one or more renewable sources using low-pressure hydrogen either provided from external sources or generated internally within the process.

In yet another aspect, a cyclic process is disclosed herein that employs a regenerable LOHC produced after the use of a primary LOHC to generate electricity wherein spent LOHC is regenerated with hydrogen that is sourced from a carbon-neutral source of energy, including electricity from renewable sources including geothermal, hydroelectric, solar, wind, water and the like, and stored energy derived therefrom.

In yet another aspect, additional step-wise processes and devices capable of performing those processes are disclosed herein employing methods to store and release electrical energy in the form of chemical energy within interconvertible LOHC compositions having labile hydrogen content, using carbon-neutral sources of hydrogen and electrical energy so that no net release or addition to the level of atmospheric carbon occurs.

In yet a further aspect, processes and devices capable of performing those processes are disclosed herein employing methods to recharge labile hydrogen depleted LOHC compositions with hydrogen, using carbon-neutral sources of hydrogen and electrical energy so that no net release or addition to the level of atmospheric carbon occurs.

In yet a further aspect, processes and devices capable of performing those processes are disclosed herein employing methods to harvest labile hydrogen from regenerated and hydrogen enriched LOHC compositions to generate electrical energy under conditions that result in no net release or addition to the level of atmospheric carbon.

The present invention is directed to a process for generating carbon-neutral electricity using hydrogen as the energy source.

In one aspect, the invention provides a recyclable Liquid Organic Hydrogen Carrier (recyclable LOHC) and a process for operating a hybrid hydrogen-electric vehicle having the range of travel and ease of refueling generally available with internal combustion engine vehicles, while maintaining carbon-neutral emissions during vehicle operation. The vehicle has a hybrid power system, using a combination of battery storage for providing electrical energy for vehicle propulsion, and an recyclable LOHC supplied to the vehicle for generating hydrogen by catalytic dehydrogenation, the hydrogen then being electrochemically converted on-board the vehicle to produce electrical energy for operating and propelling the vehicle. The produced electrical energy may be used directly to operate the vehicle or stored in on-board battery storage for use as needed.

In one aspect, the invention provides a recyclable LOHC and a process for renewable electricity storage in stationary devices via hydrogen electrochemical conversion. The recyclable LOHC is available for conversion to hydrogen and an unloaded aromatic substrate as electrical energy demand changes, for generation of carbon-neutral electricity via the hydrogen and for recycling of at least a portion of the unloaded aromatic substrate for reuse as a component of the recyclable LOHC. In one aspect, the heat energy for dehydrogenation may be provided by combustion internal to a stationary device, or the heat energy may be supplied from an external source, such as external renewable electricity.

In one aspect, the invention provides a process using a recyclable LOHC that is chemically stable and normally liquid at ambient conditions. In one aspect, the invention provides a low-cost LOHC blend that balances the available supplies of carbon-neutral and conventionally sourced hydrogen-rich hydrocarbons for carbon-neutral electricity.

In one aspect, the process is a hydrogen-to-electricity process. As used herein, the phase âhydrogen-to-electricityâ refers to the electrochemical conversion of hydrogen to electricity. An electrochemical conversion device used in the hydrogen-to-electricity process may be a fuel cell, such as a PEMFC or a SOFC, for oxidizing hydrogen with oxygen from air supplied to the device, producing at least water and an external electrical current. An organic hydrogen carrier, such as the recyclable LOHC, may supply the hydrogen through catalytic dehydrogenation. At least a portion of the unloaded aromatic substrate recovered from the dehydrogenation step may be recycled as recycle liquid and catalytically hydrogenated to generate additional recyclable LOHC.

In one aspect, the process uses hydrogen as an energy source for generating carbon-neutral electrical energy, and the process may comprise supplying a recyclable LOHC to a dehydrogenation reaction zone that is maintained at dehydrogenation reaction conditions, catalytically dehydrogenating the recyclable LOHC in the dehydrogenation reaction zone and recovering gaseous hydrogen and an unloaded aromatic substrate therefrom; combusting an amount of the unloaded aromatic substrate that is less than or equal to the predetermined target blend fraction to provide sufficient thermal energy to maintain the dehydrogenation reaction conditions; recovering the remaining amount of unloaded aromatic substrate for recycle as recycle liquid; and converting at least a portion of the gaseous hydrogen generated by dehydrogenation in an electrochemical conversion device to generate the carbon-neutral electrical energy. The recyclable LOHC supplied to the dehydrogenation reaction zone may contain a predetermined target blend fraction of the hydrogenated carbon neutral component, and at least about 5 weight % carbon-neutral labile hydrogen that is available for removal by catalytic dehydrogenation. The remaining amount of unloaded aromatic substrate may be recycled as a recycle component and catalytically hydrogenated in the preparation of the recyclable LOHC.

PRIORITY

FIELD OF THE INVENTION

BACKGROUND OF THE INVENTION

Further, governmental regulating authorities continue to reduce the allowable greenhouse gas emissions for various fossil fuel emissions sources, including new vehicles.

SUMMARY OF THE INVENTION

The present invention is directed to a process for generating carbon-neutral electricity using hydrogen as the energy source.

In one aspect, the process may be a cyclic process for providing hydrogen for electricity generation and to enable recycle and reuse of liquid components in the cyclic process. Accordingly, the process may further comprise forming an unloaded hydrogen carrier comprising a recycle component and the predetermined target blend fraction, based on the weight of the unloaded hydrogen carrier, of a carbon-neutral component; and adding carbon-neutral hydrogen to the unloaded hydrogen carrier by catalytic hydrogenation to form the recyclable LOHC comprising the hydrogenated recycle component and the hydrogenated carbon-neutral component. The LOHC is then supplied to a catalytic dehydrogenation process to liberate the labile hydrogen from the LOHC. Electrical energy is generated by electrochemical conversion of the liberated hydrogen.

In another aspect, the process may further comprise adding carbon-neutral hydrogen by catalytic hydrogenation to a recycle component to form the hydrogenated recycle component and adding carbon neutral hydrogen by catalytic hydrogenation to a carbon-neutral component to form the hydrogenated carbon-neutral component. The recyclable LOHC is formed by blending the hydrogenated recycle component with the predetermined target blend fraction, based on the weight of the recyclable LOHC, of the hydrogenated carbon neutral component.

In another aspect, the process may include adding hydrogen to the unloaded hydrogen carrier at one stage of the cycle, and reversibly recovering the hydrogen at another stage of the process, the loaded and unloaded recyclable LOHC cycling through the stages with little or no chemical modification of the underlying substrate structure, and with a net zero carbon footprint.

In another aspect, the process may be a cyclic process in which a recyclable LOHC circulates within an energy delivery system that has a net zero carbon footprint, i.e. is carbon neutral. Carbon neutral hydrocarbon components of the recyclable LOHC may be prepared from precursors, such as biomass, that recycle atmospheric CO2. Combustion of these carbon-neutral components balances carbon emissions with carbon removal and is therefore carbon-neutral with respect to the hydrocarbon components. Labile hydrogen that is provided to the process by the LOHC feedstock may be blue or green hydrogen, generated by a process that balances carbon emissions with carbon removal, or that eliminates carbon emissions altogether.

A majority of the recyclable LOHC circulates through the process as the hydrogen carrier. An energy input requirement of the process involves the endothermic nature of the dehydrogenation reaction, which requires input of thermal energy to maintain suitable dehydrogenation reaction conditions. Achieving carbon-neutral combustion for generating the thermal energy may be at least partially achieved by adding a minor amount, termed the target blend fraction, of a hydrogenated carbon-neutral component to the recyclable LOHC. After the recyclable LOHC has been converted to gaseous hydrogen and an unloaded aromatic substrate, a portion of the unloaded aromatic substrate less than or equal to the specified target blend fraction value is combusted to generate thermal energy for maintaining the overall system operation as a carbon-neutral process. At least a portion of the remaining unloaded aromatic substrate may be recycled for preparation of fresh recyclable LOHC.

Carbon-neutral hydrogen provided to the recyclable LOHC by catalytic hydrogenation for subsequent removal and electrochemical conversion is supplied in sufficient quantities to meet the electrical energy needs of the process. Carbon-neutral hydrogen may be classified as green or blue hydrogen. Carbon-neutral hydrogen that is produced by electrolysis of water using renewable energy may be characterized as green hydrogen. Carbon-neutral or carbon-negative hydrogen that is produced by hydrocarbon oxidation with carbon capture and storage (CCS), or by partial oxidation or thermal pyrolysis of biomass, or by hydrocarbon pyrolysis with solid carbon capture, may be characterized as blue hydrogen.

In one aspect, the process is provided to operate as a carbon neutral process using the particular recyclable LOHC. The dehydrogenation reaction zone is maintained at dehydrogenation reaction temperature using carbon-neutral thermal energy generated by combustion in a combustion zone of an amount of unloaded aromatic substrate less than or equal to a target blend fraction amount of the unloaded aromatic substrate. The generated hydrogen from dehydrogenation is purified for use in fuel cells, including PEMFC, SOFC and other technologies using procedures and equipment that are particularly designed to enable carbon-neutral system operation.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates a schematic of the process for generating carbon-neutral electricity from a recyclable LOHC feed, according to some embodiments.

FIG. 2 illustrates a schematic of an embodiment for supplying heat to a dehydrogenation reaction zone to generate hydrogen for conversion in a PEMFC.

FIG. 3 illustrates a schematic of an embodiment for supplying heat to a dehydrogenation reaction zone to generate hydrogen for conversion in a SOFC.

FIG. 4 illustrates an embodiment of a process for storing carbon-neutral (CN) electrical energy during periods when excess renewable electricity is available from the grid.

FIG. 5 illustrates an embodiment of a process for generating-CN electrical energy during periods when a reduced amount of electricity is available from the grid by converting hydrogen liberated from stored R-LOHC into CN electricity within a fuel cell.

FIG. 6 illustrates an embodiment of a process, including combustion means to supply heat for operating a dehydrogenation reactor.

GLOSSARY

As used herein, âliquid organic hydrogen carrierâ or âLOHCâ refers to an hydrogenated organic substrate selected from monocyclic, polycyclic, heterocyclic and homocyclic organic compounds that can be processed to release chemically bound hydrogen via dehydrogenation and are liquid at standard temperature and pressure (STP, 0Â° C., 1 bar).

As used herein, the term âR-LOHCâ refers to a regenerated or hydrogen-enriched hydrogenated form of the liquid organic hydrogen carrier.

As used herein, the term âS-LOHCâ refers to a spent or hydrogen-deficient dehydrogenated form of the liquid organic hydrogen carrier.

As used herein, the term âlabile hydrogenâ refers to the portion of chemically bound hydrogen in a hydrogenated LOHC that may be reversibly removed by dehydrogenation, and subsequently reversibly replaced by a following hydrogenation reaction.

As used herein, the term ârecyclable LOHCâ refers to a liquid organic hydrogen carrier that may be, in sequential process steps, dehydrogenated to remove at least a portion of the hydrogen atoms contained in the carrier, and rehydrogenated to replace at least a portion of the removed hydrogen atoms.

As used herein, the term âsecondary componentâ containing carbon-neutral carbon to the LOHC feed in sufficient amount to at least equal the carbon atoms being exhausted during the generation process. The exhausted carbon atoms may include vented hydrocarbons and/or vented carbon oxides. The carbon in the secondary component is termed as âcarbon-neutral carbonâ by reason of its origin from carbon compounds that are captured from the atmosphere or from flue gas that is being vented to the atmosphere, including CO2.

Unless otherwise indicated, the acronym âCNEFâ is intended to refer to carbon-neutral energy facility.

Unless otherwise indicated, the acronym âMCHâ is intended to refer to methylcyclohexane.

Unless otherwise indicated, the acronym âBTXâ is intended to refer to a mixture of benzene, toluene, and xylene, in any ratio.

Unless otherwise indicated, the acronym âGHGâ is intended to refer to a greenhouse gas found in the earth's atmosphere that may absorb and emit radiant energy within the thermal infrared range. Unless otherwise indicated, the term âCNâ is intended to refer to âcarbon-neutralâ compositions, processes and apparatus employing these compositions. The process of generating hydrogen from a blended LOHC feed and of generating electricity from the generated hydrogen is termed as âcarbon-neutralâ by reason of the purposeful addition of the secondary component containing carbon-neutral carbon to the LOHC feed in sufficient amount to at least equal the number of carbon atoms being exhausted during the electrical generation process, including vented hydrocarbons and vented carbon oxides.

Unless otherwise indicated, the term âcarbon-neutral carbonâ or âCNCâ further includes carbon compounds that are captured from the atmosphere, including carbon oxides, and from combustion processes and from flue gas emissions that would otherwise persist or be released into the atmosphere.

As used herein, the term âwt %â as used here is equivalent to âpercent by weightâ.

As used herein, the term âbi-modalâ refers to the ability of the blended LOHC to carry labile hydrogen for release in a dehydrogenation device and the ability for the CN component contained in the LOHC to be combusted without attracting carbon penalties.

The term âunloaded hydrogen carrierâ refers to a C6-C8 hydrocarbon having the capacity to capture chemically bound hydrogen in a catalytic hydrogenation process. An unloaded hydrogen carrier may be a single or double ring aromatic, such as benzene, toluene or decalin. In some circumstances, the unloaded hydrogen carrier may further comprise one or more partially hydrogenated carriers such as cyclohexene and cyclohexadiene, or the corresponding partially hydrogenated analogs of toluene and decalin.

DETAILED DESCRIPTION OF EMBODIMENTS

However, embodiments described herein may be practiced without these specific details. In other instances, well-known methods, procedures, components, and mechanical apparatuses have not been described in detail so as not to unnecessarily obscure aspects of the embodiments.

Where permitted, all publications, patents and patent applications cited in this application are herein incorporated by reference in their entirety; to the extent such disclosure is not inconsistent with the modified fuels described herein.

Unless otherwise specified, the recitation of a genus of elements, materials, or other components, from which an individual component or mixture of components can be selected, is intended to include all possible sub-generic combinations of the listed components and mixtures thereof. Also, âincludeâ and its variants are intended to be non-limiting, such that recitation of items in a list is not to the exclusion of other like items that may also be useful in the materials, compositions, and methods of this process.

Reference will be made in detail to various embodiments, examples of which are illustrated in the accompanying drawings. In the following detailed description, numerous specific details are set forth to provide a thorough understanding of the present disclosure and the embodiments described herein. However, embodiments described herein may be practiced without these specific details. In other instances, well-known methods, procedures, components, and mechanical apparatuses have not been described in detail so as not to unnecessarily obscure aspects of the embodiments.

Conventional fossil fuel generated electricity, as well as electricity demand, varies overtime, sometimes daily, or seasonally, or annually. Variations in supply become even more pronounced when the utility produces electricity from renewable sources. Conventional methods of renewable electricity generation are at the mercy of changing solar radiation, wind, and wave patterns.

Accordingly, one embodiment of the present disclosure includes a CN generation system is provided for compensating for the variations in electricity generation and demand by means of generating a highly energetic LOHC material based on chemically bound hydrogen using excess electricity as supplied for electrolysis of water to generate hydrogen which is then chemically bound to the LOHC by catalytic hydrogenation, forming an R-LOHC product which may be exported for external use or stockpiled for use when conditions change and electricity demand outpaces available supply. When the electricity used for electrolysis, whether supplied from a utility grid or supplied by local and/or internal generation, is generated from renewable energy sources, the R-LOHC produced in the system is considered to be carbon-neutral with respect to the labile hydrogen content of the R-LOHC product.

Another embodiment of the present disclosure includes a CN electricity generation system and a corresponding process which provides stockpiled R-LOHC feedstock for a catalytic dehydrogenation process to produce hydrogen as an electrochemical feedstock for generating electricity, thereby balancing electricity shortfalls when present in a conventional generating grid.

A further embodiment of the present disclosure includes a process for balancing electricity production using renewable sources of electricity without the variation of electricity generation when using a natural energy source, such as but not limited to solar, wind, geothermal, hydroelectric, and the like.

A yet further embodiment of the present disclosure includes a process that provides a source of a portable LOHC product that may be used in fuel cell containing machines, vehicles and stationary power modules.

A further embodiment of the present disclosure includes a process that provides for the on-demand generation of carbon-neutral electricity.

Described below are processes and systems that provide carbon-neutral electricity. Reference will be made in detail to various embodiments, examples of which are illustrated in the accompanying drawings. In the following detailed description, numerous specific details are set forth in order to provide a thorough understanding of the present disclosure and the embodiments described herein. However, embodiments described herein may be practiced without these specific details. In other instances, well known methods, procedures, components, and mechanical apparatuses have not been described in detail so as not to unnecessarily obscure aspects of the embodiments.

A recyclable LOHC is provided for delivering carbon-neutral electricity via labile hydrogen that is chemically stored in the recyclable LOHC. The recyclable LOHC is a hydrogen rich carbonaceous material that is chemically stable and normally liquid at ambient conditions, having a large hydrogen capacity, but without the associated risks that are inherent with high pressure hydrogen gas storage. The labile hydrogen may be reversibly removed from the recyclable LOHC during dehydrogenation without decomposing the underlying aromatic substrate structure of the carrier. Furthermore, the recyclable LOHC provides a reliable and stable source of hydrogen without the net positive CO2 emissions that are generally associated with hydrocarbon combustion to provide the thermal energy for dehydrogenation.

The recyclable LOHC may be a cycloparaffin with a hydrogen storage capacity of at least about 5 weight % labile hydrogen, and in some cases at least about 6 weight % labile hydrogen. The recyclable LOHC may comprise a cyclic saturated hydrocarbon such as cyclohexane, methylcyclohexane and/or decalin; reversible dehydrogenation conversion of the recyclable LOHC produces the corresponding aromatic substrate: benzene, toluene, or naphthalene. The recyclable LOHC may comprise at least about 80 weight % methylcyclohexane (MCH), or at least about 90 weight % MCH, or in a range from 95 to 99.9 weight % MCH. The recyclable LOHC may comprise a blend of a hydrogenated carrier component, such as a hydrogenated recycle component recovered from a hydrogen-to-electricity generation process, from 0.1-25 weight % of a hydrogenated carbon-neutral component that is prepared from carbon-neutral precursors, and at least about 5 weight % added carbon-neutral hydrogen that is available for removal in a reversible dehydrogenation reaction.

The recyclable LOHC may be produced for use in the process by blending a recycle component and a predetermined target blend fraction, based on the weight of the blend, of a carbon-neutral component; and adding at least about 5 weight % carbon-neutral hydrogen to the unloaded hydrogen carrier by catalytic hydrogenation to form the recyclable LOHC.

Alternatively, the recyclable LOHC may be produced by combining a hydrogenated recycle component and a predetermined target blend fraction, based on the weight of the recyclable LOHC, of a hydrogenated carbon-neutral component, the recyclable LOHC also containing at least about 5 weight % carbon-neutral hydrogen.

The recycle component may be an aromatic substrate material comprising one or a combination of aromatic substrates, such as benzene, toluene, and/or naphthalene, that may be combined with the carbon-neutral component and the combination catalytically hydrogenated to form the recyclable LOHC. Alternatively, the recycle component may be hydrogenated prior to blending with a hydrogenated carbon-neutral component to form the recyclable LOHC.

At least a portion of the recycle component may be recovered from a hydrogen to electricity generation process, in which hydrogen is delivered as chemically bound hydrogen, liberated by dehydrogenation, and an unloaded aromatic substrate byproduct from dehydrogenation recovered as at least a portion of the recycle component. The recycle component may also contain relatively minor amounts of dehydrogenation reaction byproducts, including incompletely dehydrogenated hydrogen carrier and single and multi-ring aromatics. The recycle component may include toluene as the unloaded aromatic substrate, and non-toluene dehydrogenation byproducts, such as MCH, partially dehydrogenated MCH, xylene, and multi-ring aromatics. The recycle component may contain at least 50 weight % toluene; in some instances, at least 75 weight % toluene; in some instances, at least 93 weight % toluene. At least 10 weight % of the recycle component may be recovered from a hydrogen-to-electricity generation process.

As the recycle component is included in the recyclable LOHC as a source of hydrogen only, a make-up component from a conventional source may be included in the recycle component to make up for shortfall in available supply. The recycle component may comprise up to 100 weight % make-up component, though as use of the present process progresses, progressively more of the recycle component will be recovered from a hydrogen-to-electricity process, such that at least 20 weight %, or at least 50 weight %, or at least 70 weight %, or at least 90 weight % of the recycle component will be recovered from a hydrogen-to-electricity process. The make-up component may comprise at least 50 weight % toluene, or at least 70 weight %, or at least 90 weight % toluene, or at least 95 weight % toluene, up to and including 100 weight % toluene.

A carbon neutral component is included as an additive in the unloaded hydrogen carrier for maintaining carbon neutral operation of the process. The carbon-neutral component is produced from molecular precursors either that are produced with no CO2 generation, that are produced with recycled atmospheric CO2, or that are produced with CO2 capture and ultimate storage generated during their production, any of which do not result in a net increase in atmospheric CO2

In one embodiment, the carbon-neutral carrier contained in the recyclable LOHC is produced from biomass. Biomass from plant or animal sources can be purposely grown energy crops, wood or forest residues, waste from food crops, horticultural waste, or food processing residues. Production of carbon-neutral carrier from biomass generally involves one or more biomass conversion steps, such as pyrolysis, gasification, anaerobic digestion, or fermentation. Typical reaction products from these processing methods include one or more of methanol, ethanol, methane, acetic acid, lactic acid, and syngas. One or more of these biomass conversion products may be used to generate an aromatic precursor of the carbon neutral carrier.

As carbon contained in the carbon-neutral component is itself carbon neutral, it is classified as a renewable energy source, and therefore available as a combustion source for the process. Therefore, for purposes of this disclosure, CO2 generated from combustion of the carbon-neutral component or its hydrogenated carbon-neutral carrier analog is termed âgreen CO2â to indicate that the generated CO2 has been recycled from the atmosphere, and does not contribute to a net increase in atmospheric CO2. Likewise, the process of using the recyclable LOHC for generating electricity is carbon neutral.

The unloaded hydrogen carrier may comprise the recycle component, the predetermined target blend fraction, based on the weight of the unloaded hydrogen carrier, of the carbon-neutral component, and at least about 5 weight % chemically bound carbon-neutral hydrogen as labile hydrogen.

The unloaded hydrogen carrier may comprise at least 20 weight % of the recycle component.

Generally, the unloaded hydrogen carrier comprises at least 0.1 weight % carbon neutral component; in some instances, in a range from 0.1-25 weight % carbon-neutral component; in some instances, in a range from 0.5-15 weight % carbon-neutral component; in some instances, in a range from 0.5-6 weight % carb neutral component. As used herein, the proportion of the carbon-neutral component in the unloaded hydrogen carrier, based on the total unloaded hydrogen carrier, is termed the âtarget blend fractionâ.

The recycle component of the unloaded hydrogen carrier may include contaminants, such as byproducts from the dehydrogenation reaction, that are usefully reduced in concentration or removed from the unloaded hydrogen carrier prior to or during hydrogenation. Purification of the unloaded hydrogen carrier by removal or conversion of the contaminants, may include process steps such as hydrogenation, distillation, liquid-liquid separation, crystallization, absorption onto a solid absorbent, and the like.

The recyclable LOHC that is to be delivered for generating electricity may be prepared by catalytic hydrogenation of one or more toluene-based precursors. A carbon-neutral toluene prepared from carbon-neutral precursors may be included. A recycle liquid from a hydrogen-to-electricity process, comprising toluene, may be included. One or more of the toluene-based precursors may be catalytically hydrogenated individually to contain at least about 5 weight % labile hydrogen, and the hydrogenated MCH products blended to form the recyclable LOHC. One or more of the toluene-based precursors may be blended to form an unloaded hydrogen carrier, that then may be catalytically hydrogenated to form the recyclable LOHC. In effect, the recyclable LOHC may be prepared by any combination of blending steps and catalytic hydrogenation steps to prepare the recyclable LOHC.

The catalytic hydrogenation step includes passing the hydrogenation zone feedstocks in liquid or vapor phase over a suitable hydrogenation catalyst that is maintained at a temperature in a range of 200Â° to 300Â° C. and at a positive pressure of up to 20 bar. The hydrogenation catalyst may be powdered or in extrudate form. In one aspect, the catalyst may comprise a metal, such as nickel, cobalt, or a mixture thereof. The metal mixture may further be compounded with molybdenum. In another aspect, the hydrogenation catalyst may comprise palladium, platinum, or a mixture thereof. The metal composition may be supported on an oxide material comprising, for example, alumina, silica, titania, or a mixture thereof in any ratio. An additional component or alternative support may include an acidic zeolite with 10 or 12 angstrom ring openings such as faujasite, Beta zeolite or ZSM-5. The hydrogenation catalyst composition may be sulfided prior to use. The hydrogenation reaction may be conducted in an existing refinery having suitable catalyst reaction and support facilities to produce the recyclable LOHC with a purity suitable for use in the present process.

The recyclable LOHC and the process for using the recyclable LOHC as a hydrogen source for carbon-neutral electricity generation is carbon-neutral with respect to the carbon and CO2 emissions, by reason of the carbon-neutral portion of the recyclable LOHC formulation. The recyclable LOHC is also carbon-neutral with respect to the hydrogen gas generated by the carrier by reason of the source of the stored hydrogen. The carbon-neutral hydrogen source for the hydrogenation step is produced by methods that either produce no CO2 or that recycle atmospheric CO2. Green hydrogen is carbon-neutral hydrogen that may be produced by electrolysis of water using renewable energy such as wind, solar, hydroelectric, or geothermal energy sources. Blue hydrogen is carbon-neutral or carbon-negative hydrogen that may be produced by hydrocarbon oxidation with carbon capture and storage (CCS), or by partial oxidation or thermal pyrolysis of biomass, or by hydrocarbon pyrolysis with solid carbon capture. Carbon dioxide sequestration is an exemplary CCS process.

Recyclable LOHC is converted in an endothermic dehydrogenation process to liberate labile hydrogen from the carrier and to produce an unloaded aromatic substrate. A portion of unloaded aromatic substrate may be employed as combustion fuel for preheating the dehydrogenation reaction zone feed, for maintaining the dehydrogenation reaction zone temperature, and for supplying other thermal needs. Additional thermal energy may be required for other aspects of operation. In the case of terrestrial vehicles such as trucks, this additional thermal energy may be needed for traveling in mountainous regions or against a significant headwind. In the case of water vehicles, this additional thermal energy may be needed during storms at sea. In the case of aircraft, this additional thermal energy may be needed for ascending to cruising altitude or when encountering significant headwind conditions.

For maintaining carbon neutral operation, the relative amount of unloaded aromatic substrate that is available for combustion is less than or equal to the relative amount of hydrogenated carbon-neutral component in the recyclable LOHC feed. Accordingly, a target blend fraction is defined as the weight % of hydrogenated carbon neutral component that is present in the recyclable LOHC. The target blend fraction may be in a range from 0.1-25 weight %; in another aspect, from 0.5-15 weight %, in another aspect, from 1-6 weight %. The target blend fraction is also the fractional amount of carbon-neutral component blended in the unloaded hydrogen carrier prior to hydrogenation to form the recyclable LOHC. The target blend fraction may be established in one of several ways. For example, the target blend fraction may be an industry-wide standard for all LOHC blends. Alternatively, the target blend fraction may be a characteristic property of fuels designated by vehicle type, with fuels specifically tailored for one or more of cars, trucks, boats, ships, buses, trains, and aircraft. Alternatively, the recyclable LOHC may be formulated with a target blend fraction of carbon neutral LOHC for a specific vehicle or even a specific journey, using a blending or service facility that supplies fuel to the vehicle.

It will be apparent that the target blend fraction specification may vary from vehicle to vehicle, and from journey to journey. Accordingly, the composition of an MCH enriched recyclable LOHC may be selected for a particular journey or for a particular vehicle. In another embodiment, the target blend fraction of the MCH enriched recyclable LOHC may be determined as a regional or a corporate-wide average. An objective for establishing a target blend fraction of carbon-neutral fuel components in the MCH enriched recyclable LOHC is to significantly reduce or eliminate the CO2 emissions from hybrid hydrogen-electric vehicles. Establishing the target blend fraction allows the industry to specify an amount of carbon-neutral fuel components for carbon-neutral vehicle operation while meeting supply and price limitations.

The recyclable LOHC is suitable for use as a source of hydrogen for a vehicle having transmission capability to communicate the particular power module characteristics with service facilities. At least in part, the communication includes information to establish the target blend fraction requirement of the LOHC feed for the particular module, based on specific characteristics of the dehydrogenation reaction zone and other thermal needs of the module. The service facility providing the recyclable LOHC then blends an amount of hydrogenated carbon-neutral component into the majority hydrogenated recycle component to form a tailored fuel specific for the needs of the particular module, to ensure carbon-neutral operation of the module.

A power module of the invention supplies the electrical energy used by mobile or stationary devices. The power module comprises a first storage vessel for containing the recyclable LOHC prior to dehydrogenation, a second storage vessel for containing the unloaded aromatic substrate product from dehydrogenation, a dehydrogenation reaction zone for generating hydrogen from recyclable LOHC, a hydrogen purification capability for preparing the hydrogen for electrochemical conversion and electricity generation, a separation unit for separating unloaded aromatic substrate from dehydrogenation into a recycle liquid and a combustion liquid, and a combustion zone for combusting the combustion liquid to produce thermal energy for maintaining the dehydrogenation reaction zone at reaction conditions.

The power module includes two on-board liquid storage vessels, a first storage vessel for containing the recyclable LOHC as delivered to the vehicle and a second storage vessel for containing the recycle liquid recovered from dehydrogenation. The recyclable LOHC and the spent recycle liquid are low vapor pressure liquids that may be stored in vessels that would be suitable for gasoline, diesel fuel, aviation fuel and jet fuel storage. In one embodiment, the first and the second storage vessels are located separately in the vehicle. In another embodiment, the two storage vessels are combined into a single vessel, separated into two volumes within the storage vessel by a flexible bladder. As recyclable LOHC is supplied to the vehicle and the recycle liquid is removed, the relative size of the first volume containing the recyclable LOHC increases and that of the second volume containing the recycle liquid decreases. Likewise, as recyclable LOHC is consumed and the recycle liquid produced during vehicle operation, the capacity of the second volume containing the recycle liquid increases relative to that of the first volume containing the recyclable LOHC. A dual nozzle dispenses recyclable LOHC to the vehicle and at the same time extracts spent liquid fuel from the vehicle.

Producing purified hydrogen for electrochemical conversion generally involves condensing the normally liquid components of the dehydrogenated product, separating a gaseous hydrogen phase from the unloaded aromatic substrate phase, using one or a combination of liquid condensation, membrane separation, or filtration. One or more stages of separation may be used. In at least one of the stages, a refrigeration cycle may be included to facilitate separation of the remaining normally liquid components from the gaseous hydrogen product. The hydrogen may be cooled to a sub-ambient temperature of 0Â° C. or lower, or 10Â° C. or lower, or 20Â° C. or lower or 25Â° C. or lower. In addition to cooling, membrane separation or carbon filtration may be used in either the first cooling stage, the second cooling stage, or in both. The stages of purification are configured to produce a purified hydrogen stream with a purity of at least 99%, in some cases at least 99.96%.

A combustion chamber may be provided for burning the combustion liquid in the presence of preheated air to produce thermal energy as needed. The combustion chamber may be included in a forced air furnace, or in a gas turbine. Heated combustion exhaust gases from the combustion chamber may be used for maintaining the dehydrogenation reaction zone at dehydrogenation conditions and/or for preheating the recyclable LOHC prior to reaction. Preheating the recyclable LOHC may include vaporizing at least a portion of the dehydrogenation reaction zone feed. Preheating the recyclable LOHC may involve heat exchanging the heated exhaust gases with the LOHC prior to the reaction zone, using, for example, one or more of a shell and tube or a plate heat exchanger. Supplying heat to maintain the reaction zone temperature may involve passing heated exhaust gases through the reaction zone and around the catalyst-containing reactor tubes. Supplying heat for reaction may include using the exhaust gases to heat a circulating heat transfer fluid for conveying heat for reaction zone feed preheat or for reaction zone temperature control.

A fuel cell electrochemical device is provided on the vehicle for converting on-board generated carbon-neutral hydrogen to electrical power. The fuel cell device generates electricity by conversion of chemical energy of the hydrogen fuel and air into electricity through a pair of redox reactions. A suitable fuel cell for use in the vehicle is selected from an alkaline fuel cell (AFC), a Proton-Exchange Membrane Fuel Cell (PEMFC), a phosphoric acid fuel cell (PAFC), a molten carbonate fuel cell (MCFC) and an oxide ceramic or solid oxide fuel cell (SOFC). All may be operated with atmospheric oxygen from the environment as an oxidizer gas, with the result that no storage of the oxidizer gas is required. The fuel cell system may comprise one or more fuel cell units. In one embodiment, the fuel cell system comprises one or more Proton-Exchange Membrane Fuel Cells.

The electrochemical conversion device for converting carbon-neutral hydrogen to electrical power may include a solid oxide fuel cell (SOFC) device operating in a temperature range 500Â°â650Â° C. Approximately 30-35% of the energy generated in the SOFC is thermal energy that is suitable for at least partially maintaining the dehydrogenation reaction zone temperature. Gases exhausted from the anode side of the SOFC system include unreacted hydrogen and a small amount of unloaded aromatic substrate, such as toluene, that was carried with hydrogen feed to the SOFC from dehydrogenation. Gases exhausted from the cathode side of the SOFC system, including oxygen depleted air and water vapor, are combined with the anode exhaust stream in a catalytic conversion unit, which produces water, oxygen depleted air and CO2 from aromatic liquid oxidation. A recyclable LOHC feed for use with the SOFC device may be preselected to contain a target blend fraction in a range of 0.1-6 weight % of hydrogenated carbon-neutral component in order to maintain the overall carbon-neutral process.

The electrochemical conversion device for converting carbon-neutral hydrogen to electrical power may include a Proton-Exchange Membrane Fuel Cells (PEMFC) operating in a temperature range 50Â°â100Â° C. Only a small portion, is any, of the heat generated by a PEMFC may be available for use with the dehydrogenation reaction zone. The remaining heat for dehydrogenation with a PEMFC device is provided by combustion of a portion of the combustion liquid, the portion being specified by the target blend fraction. In this case, the target blend fraction may be in a range of 0.1-25 weight %; in another aspect, 0.5-15 weight %; and in another aspect, 1-10 weight %.

The dehydr

CLAIMS

Claims ( 30 )

What is claimed is:

1. A method for generating carbon-neutral electrical energy using hydrogen as the energy source, comprising:

a. supplying a recyclable LOHC to a dehydrogenation reaction zone that is maintained at dehydrogenation reaction conditions, the recyclable LOHC comprising a hydrogenated recycle component, a predetermined target blend fraction of a hydrogenated carbon neutral component, and at least about 5 weight % carbon-neutral labile hydrogen that is available for removal by catalytic dehydrogenation,

wherein the target blend fraction is defined as a proportion of a carbon-neutral component in an unloaded hydrogen carrier based on the total unloaded hydrogen carrier prior to hydrogenation to form the recyclable LOHC;

b. catalytically dehydrogenating the recyclable LOHC in the dehydrogenation reaction zone and recovering gaseous hydrogen and an unloaded aromatic substrate therefrom;

c. combusting an amount of the unloaded aromatic substrate that is less than or equal in weight % to the predetermined target blend fraction to provide sufficient thermal energy to maintain the dehydrogenation reaction conditions;

d. recovering the remaining amount of unloaded aromatic substrate; and

e. converting at least a portion of the gaseous hydrogen generated by dehydrogenation in an electrochemical conversion device to generate the carbon-neutral electrical energy.

2. The method of claim 1 , further comprising:

a. forming the unloaded hydrogen carrier comprising a recycle component and the carbon-neutral component; and

b. adding carbon-neutral hydrogen to the unloaded hydrogen carrier by catalytic hydrogenation to form the recyclable LOHC comprising the hydrogenated recycle component and the hydrogenated carbon-neutral component;

c. the unloaded hydrogen carrier being characterized by a labile hydrogen content of at least about 5 weight %.

3. The method of claim 1 , further comprising:

a. adding carbon-neutral hydrogen by catalytic hydrogenation to a recycle component to form the hydrogenated recycle component;

b. adding carbon-neutral hydrogen by catalytic hydrogenation to the carbon-neutral component to form the hydrogenated carbon-neutral component; and

c. blending the hydrogenated recycle component with the hydrogenated carbon-neutral component to form the recyclable LOHC.

4. The method of claim 1 , further comprising recycling at least a portion of the remaining amount of unloaded aromatic substrate as the recycle component to the recyclable LOHC.

5. The method of claim 1 , wherein at least a portion of the recycle component is recovered from a hydrogen-to-electricity generation process.

6. The method of claim 5 , wherein at least 10 weight % of the recycle component is recovered from a hydrogen-to-electricity generation process.

7. The method of claim 6 , wherein the recycle component recovered from a hydrogen-to-electricity generation process comprises at least 50 weight % toluene.

8. The method of claim 1 , wherein the hydrogenated carbon-neutral component is prepared from at least one carbon-neutral precursor.

9. The method of claim 8 , wherein the carbon-neutral precursor is ethanol produced by fermentation of biomass, the ethanol being catalytically cyclized to form the carbon-neutral component.

10. The method of claim 8 , wherein the carbon-neutral precursor is methanol produced from biomass, municipal solid waste, biogas, or recovered CO 2 from the atmosphere.

11. The method of claim 1 , wherein the carbon-neutral component comprises at least 90 weight % carbon-neutral toluene.

12. The method of claim 1 , wherein the carbon-neutral hydrogen is green hydrogen, generated by electrolysis of water using electrical energy that was generated from wind, solar, hydroelectric, or geothermal energy.

13. The method of claim 1 , wherein the carbon-neutral hydrogen is blue hydrogen produced by hydrocarbon oxidation with carbon capture and storage (CCS), or by partial oxidation or thermal pyrolysis of biomass, or by hydrocarbon pyrolysis with solid carbon capture.

14. The method of claim 1 , wherein the recyclable LOHC comprises at least 90 weight % MCH.

15. The method of claim 1 , wherein the target blend fraction is in a range of 0.1-25 weight %.

16. The method of claim 2 , wherein the unloaded hydrogen carrier comprises at least 20 weight % of the recycle component.

17. The method of claim 2 , wherein the unloaded hydrogen carrier comprises at least 90 weight % toluene.

18. The method of claim 1 , wherein the unloaded aromatic substrate recovered from the dehydrogenation reaction zone for recycle as the recycle component comprises toluene and dehydrogenation byproduct contaminants.

19. The method of claim 18 , wherein the recycle component comprises at least about 70 weight % toluene and less than about 30 weight % dehydrogenation byproduct contaminants selected from one or more of MCH, partially dehydrogenated MCH, xylene, and multi-ring aromatics.

20. The method of claim 18 , further comprising removing at least a portion of the dehydrogenation byproduct contaminants from the recycle component prior to or during the catalytic hydrogenation step.

21. The method of claim 1 , wherein the recyclable LOHC contains sufficient hydrogenated carbon-neutral component to convert at least 80 weight % of the labile hydrogen contained in the recyclable LOHC to gaseous hydrogen during catalytic dehydrogenation of the recyclable LOHC.

22. The method of claim 1 , wherein dehydrogenation reaction conditions include a dehydrogenation temperature in a range of 350Â° C. and 600Â° C.

23. The method of claim 1 , wherein gaseous hydrogen and the unloaded liquid substrate are generated in the dehydrogenation process, and wherein from 0.1-25 weight % of the unloaded liquid substrate is available for combustion to maintain the dehydrogenation process at carbon neutral operating conditions.

24. The method of claim 1 further comprising combusting up to the target blend fraction of the unloaded liquid substrate in air to generate thermal energy for vaporizing and heating the recyclable LOHC to the dehydrogenation temperature and for maintaining the dehydrogenation temperature of the dehydrogenation reaction zone.

25. The method of claim 1 further comprising purifying the gaseous hydrogen recovered from the dehydrogenation reaction zone, prior to the step of converting at least a portion of the gaseous hydrogen in the electrochemical conversion device.

26. The method of claim 25 wherein the gaseous hydrogen recovered from the dehydrogenation reaction zone is chilled by refrigeration prior to passing the hydrogen to a PEM electrochemical conversion device.

27. The method of claim 25 wherein the gaseous hydrogen is cooled by refrigeration to â10Â° C. or lower to liquify contaminants remaining in the gaseous hydrogen and to isolate purified gaseous hydrogen having a purity of at least 99.9 weight %, for passing to the electrochemical conversion device.

28. The method of claim 25 wherein the gaseous hydrogen is further purified by use of a membrane capable of separating gaseous hydrogen from vapor phase toluene.

29. The method of claim 1 , wherein the electrochemical conversion device is a PEMFC and the target blend fraction is in a range from 1-10 weight %.

30. The method of claim 1 , wherein the electrochemical conversion device is a SOFC and the target blend fraction is in a range from 0.5-5 weight %.

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