WO2023193119A1 - Systems and methods for storing, transporting, and supplying hydrogen - Google Patents

Systems and methods for storing, transporting, and supplying hydrogen Download PDF

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Publication number
WO2023193119A1
WO2023193119A1 PCT/CA2023/050487 CA2023050487W WO2023193119A1 WO 2023193119 A1 WO2023193119 A1 WO 2023193119A1 CA 2023050487 W CA2023050487 W CA 2023050487W WO 2023193119 A1 WO2023193119 A1 WO 2023193119A1
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Prior art keywords
hydrogen
ethanol
acetic acid
ethyl acetate
hydrogenation
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PCT/CA2023/050487
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French (fr)
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Chris Qun MAO
Stephen DADSON
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Hyten Energy Corp.
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Publication of WO2023193119A1 publication Critical patent/WO2023193119A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0015—Organic compounds; Solutions thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1217—Alcohols
    • C01B2203/1229—Ethanol

Definitions

  • the present invention relates to systems and methods for storing, transporting, and supplying hydrogen, and, in particular, to systems and methods that use acetic acid (AcOH) and ethanol (EtOH) as a liquid organic hydrogen carrier (LOHC) pair to store, transport, and supply hydrogen.
  • AcOH acetic acid
  • EtOH ethanol
  • LOHC liquid organic hydrogen carrier
  • Hydrogen is a clean fuel because its combustion product is water vapor, without emitting any CO2.
  • Green or blue hydrogen obtained from renewable energy or low-carbon footprint fossil resources is expected to be an important element in achieving global carbon- neutrality and carbon-zero goals.
  • Hydrogen is the lightest element on earth. Although it has the highest caloric value (142 MJ/kg) in comparison with other fuels (such as gasoline at a caloric value of about 46.4 MJ/kg and diesel at a caloric value of about 45.6 MJ/kg), storing and transporting hydrogen is a challenge.
  • hydrogen is stored or transported in a compressed gas phase or cryogenic liquid phase under extremely high pressures (350-700 bar) or at extremely low temperature (-253°C), constrained in expensive pressure cylinders or cryogenic tanks, with high hazardous risks. Due to safety and economic reasons, compressed hydrogen and liquid hydrogen are not suitable for large-scale storage and long-distance transportation, which will be required as the shift to a hydrogen economy advances.
  • LOHC-based hydrogen storage systems are still in an evolving phase. Only a small number of technology developers worldwide have commercialization activities using LOHCs, including Chiyoda Corporation, Hydrogenious GmbH, and Hynertech. Their LOHCs are typically unsaturated aromatics (organic molecules with C-C double or triple bonds) and cyclic hydrocarbons, such as toluene/methyl-cyclohexane (TOL/MCH) and perhydrodibenzyl toluene/ dibenzyltoluene (PDBT/DBT). Both TOL/MCH and PDBT/DBT LOHCs have hydrogen storing and releasing capacity of approximately 6.2 wt%.
  • a method for storing and delivering hydrogen comprises the steps of reacting acetic acid with hydrogen to produce ethanol and water, with the acetic acid and the ethanol being a liquid organic hydrogen carrier (LOHC) pair, with the acetic acid as a hydrogen-lean organic compound, and with the ethanol is a hydrogen-rich organic compound; storing the ethanol as a storage form for the hydrogen; transporting the ethanol as a transportation form for the hydrogen; and using the ethanol and water to produce hydrogen via an ethanol dehydrogenation reaction and an ethyl acetate hydrolysis reaction, coproducing the acetic acid for reuse as the hydrogen-lean organic compound to produce the ethanol as the hydrogen-rich compound via acetic acid hydrogenation.
  • LOHC liquid organic hydrogen carrier
  • a system for storing and delivering hydrogen comprises an acetic acid to ethanol (ATE) apparatus and an ethanol to hydrogen (ETH2) apparatus.
  • the ATE apparatus is configured to generate ethanol using acetic acid hydrogenation, with the ethanol being used as a storage form for the hydrogen.
  • the ETH2 apparatus is configured to re-generate the hydrogen using dehydrogenation of at least a portion of the ethanol, with acetic acid produced as a co-product.
  • the ATE apparatus is located remote from the ETH2 apparatus.
  • system further comprises one or more hydrogen production facilities for producing at least a portion of the hydrogen for use by the ATE apparatus.
  • system further comprises one or more bioethanol production facilities for producing at least a portion of the ethanol for use by the ETH2 apparatus.
  • system further comprises one or more ethanol transporter configured to transport at least a portion of the ethanol from the ATE apparatus to the ETH2 apparatus.
  • system further comprises one or more hydrogen supplying facilities configured to supply hydrogen produced from the ETH2 apparatus.
  • system further comprises one or more acetic acid transporters configured to transport at least a portion of the acetic acid produced by the ETHa apparatus to the ATE apparatus.
  • the ATE apparatus comprises a dehydration unit and a hydrogenation unit.
  • the dehydration unit is configured to carry out ethanol and acetic acid dehydration to generate ethyl acetate and water.
  • the hydrogenation unit is configured to carry out ethyl acetate hydrogenation to generate the ethanol, with at least a portion of the ethyl acetate produced by the dehydration unit being used by the hydrogenation unit for the ethyl acetate hydrogenation.
  • the dehydration unit receives the acetic acid from one or both of the ETH2 apparatus and one or more acetic acid production facilities.
  • the dehydration unit receives the ethanol from one or both of the hydrogenation unit and the one or more bioethanol production facilities.
  • At least a portion of the water produced by the dehydration unit is used for utility use.
  • the ethanol and acetic acid dehydration occurs in the presence of catalysts under temperature conditions of approximately 60 to 100 °C and pressure conditions of approximately 1 to 5 bar.
  • the ethyl acetate hydrogenation occurs in the presence of a copper-based catalyst under temperature conditions of 100 to 300 °C and pressure conditions of 1 to 30 bar.
  • the hydrogen used by the hydrogenation unit is produced by one or more of the following: via water electrolysis powered by renewable energy, and via reforming or gasifying fossil fuels.
  • the ethanol produced by the hydrogenation unit is used for one or both of the following: as a hydrogen carrier for hydrogen storage and transportation and as feedstock for the dehydration unit.
  • the acetic acid hydrogenation by the ATE apparatus to form the ethanol occurs directly in the presence of non-noble metal based catalysts, without ethyl acetate as an intermediate.
  • the ETH2 apparatus comprises a dehydrogenation unit and a hydrolysis unit.
  • the dehydrogenation unit is configured to carry out ethanol dehydrogenation to produce the hydrogen and ethyl acetate.
  • the hydrolysis unit is configured to carry out ethyl acetate hydrolysis to generate acetic acid, with at least a portion of the ethyl acetate produced by the dehydrogenation unit being used by the hydrolysis unit for the ethyl acetate hydrolysis.
  • the dehydrogenation unit is further configured to receive the ethanol from one or both of the ATE apparatus and the hydrolysis unit.
  • the acetic acid generated by the hydrolysis unit is used for one or both of the following: as a hydrogen-lean organic compound for transport back to the ATE apparatus and as a chemical for industrial use.
  • the ethanol dehydrogenation occurs in the presence of copper-based catalysts under temperature conditions of approximately 100 to 300 °C and pressure conditions of approximately 1 to 50 bar.
  • the ethyl acetate hydrolysis occurs in the presence of catalysts under temperature conditions of approximately 60 to 100 °C and pressure conditions of approximately 1 to 5 bar.
  • FIG. 1 is a schematic diagram depicting a system for storing, transporting, and supplying hydrogen according to one embodiment of the present invention.
  • FIG. 2 is a schematic diagram of an acetic acid to ethanol apparatus for the hydrogenation of acetic acid (AcOH) to produce ethanol (EtOH) according to another embodiment of the present invention
  • FIG. 3 is a schematic diagram of an ethanol to hydrogen apparatus for the dehydrogenation of ethanol (EtOH) to produce hydrogen with co-product acetic acid according to another embodiment of the present invention.
  • the present invention discloses systems and methods of using acetic acid (AcOH)Zethanol (EtOH) as a LOHC pair, with acetic acid as the hydrogen-lean organic compound and ethanol as the hydrogen-rich organic compound, and with an estimated hydrogen storing and releasing capacity of 8.7 wt%.
  • acetic acid and ethanol are bulk chemicals, with existing storage and transportation infrastructure available.
  • acetic acid and ethanol are less expensive than the unsaturated aromatic and cyclic hydrocarbons such as TOL/MCH and PDBT/DBT typically used by other LOHC designs.
  • systems and methods for storing, transporting, and supplying hydrogen comprising: renewable hydrogen and/or low carbon intensity hydrogen sources, bioethanol and/or ethanol sources, acetic acid sources, acetic acid hydrogenation to form ethanol apparatus, ethanol transportation, ethanol dehydrogenation to produce hydrogen and acetic acid apparatus, hydrogen distribution to end-users and acetic acid transportation.
  • Both acetic acid and ethanol are widely used bulk chemical commodities.
  • the system disclosed in the present invention is a safe and affordable way to store and transport more hydrogen that’s compatible with existing infrastructure for the storage and transportation of acetic acid and ethanol.
  • the hydrogen storing and releasing capacity is expected to be 8.7 wt%.
  • 8.7 kg hydrogen can be obtained using 100 kg ethanol as the hydrogen carrier followed with ethanol dehydrogenation to release hydrogen, with acetic acid as co-product that can be returned as a hydrogen-lean organic compound to again produce ethanol via acetic acid hydrogenation.
  • an acetic acid to ethanol (ATE) apparatus for loading hydrogen via acetic acid hydrogenation, receiving hydrogen and acetic acid as feedstocks to produce ethanol.
  • Hydrogen may be obtained via water electrolysis powered by renewable energy such as solar, wind, hydro, and geothermal, or produced from fossil fuels such as natural gas, crude oil, and coal, with or without CO2 capture, utilization, and sequestration (CCUS) processing.
  • Acetic acid is regenerated and transported from the ethanol dehydrogenation apparatus of the present system of this invention, and/or obtained from acetic acid production facilities.
  • an acetic acid to ethanol (ATE) apparatus comprising a two-step process or a one-step process.
  • the ATE two-step process comprises an acetic acid and ethanol dehydration unit to produce ethyl acetate and water, followed by an ethyl acetate hydrogenation unit to produce ethanol in the presence of copper-based catalyst under the conditions of temperatures of approximately 100 to 300 °C and pressure of approximately 1 to 30 bar, with half of the ethanol product as hydrogen carrier for hydrogen storing, transporting, and supplying to the end-users, and another half of the ethanol product as feedstock recycled back to the acetic acid and ethanol dehydration unit to produce ethyl acetate.
  • the ATE one-step process comprises the process of acetic acid hydrogenation to form ethanol may take place directly in the presence of non-noble metal-based catalysts, without the step of ethyl acetate as an intermediate product to produce ethanol via ethyl acetate hydrogenation, which may however, require using anti-corrosion material for the process equipment.
  • ETH2 ethanol to hydrogen
  • an ethanol to hydrogen (ETH2) apparatus comprising: an ethanol dehydrogenation unit to produce hydrogen and ethyl acetate in the presence of copper-based catalysts under the conditions of temperatures of approximately 100 to 300 °C and pressure of approximately 1 to 50 bar, and an ethyl acetate hydrolysis unit to produce ethanol and acetic acid, with the ethanol product recycled back to the ethanol dehydrogenation unit as feedstock to produce more hydrogen, and with the acetic acid product transported back to the ATE apparatus of the present system of this invention.
  • ETH2 ethanol to hydrogen
  • the ethanol may be transported from bioethanol production facilities or low carbon intensity ethanol plants, and the acetic acid generated in the ETH2 apparatus is not necessary to be transported back for reuse as hydrogen-lean organic compound to form ethanol as liquid organic hydrogen carrier via hydrogenation.
  • the hydrogen producers may use the ATE process (acetic acid hydrogenation) described above to form ethanol as a hydrogen-rich liquid organic compound for hydrogen storing and transporting, while the acetic acid may be produced at local facilities close to the hydrogen production plants, instead of transporting back the acetic acid from the ETH2 apparatus to the ATE apparatus.
  • a system may use acetic acid (AcOH) as a hydrogen-lean organic compound for hydrogen loading via a hydrogenation process and ethanol (EtOH) as a hydrogen-rich organic compound for hydrogen releasing via a dehydrogenation process.
  • AcOH acetic acid
  • EtOH ethanol
  • Both acetic acid and ethanol are relatively inexpensive bulk chemicals, with their own existing storage and transportation infrastructure.
  • acetic acid hydrogenation comprises processes of acetic acid and ethanol dehydration to ethyl acetate (EtOAc) and ethyl acetate hydrogenation to ethanol, which are represented by the chemical reactions (1) and (2) below:
  • Reaction (1) comprises an esterification process, taking place in the presence of catalysts, such as concentrated sulfuric acid, under the conditions of temperatures of approximately 60 to 100 °C (and preferably approximately 70 °C) and ambient pressure, with ethyl acetate and water (H2O) as its products.
  • Reaction (2) comprises an ethyl acetate hydrogenation to ethanol process, which is an exothermic reaction, taking place in the presence of a copper-based catalyst under the conditions of temperatures of approximately 100 to 300 °C and pressure of approximately 1 to 30 bar.
  • reaction (3) the overall reaction is represented by reaction (3); one mole acetic acid reacts with two moles hydrogen to produce one mole ethanol and one mole byproduct of water.
  • acetic acid hydrogenation takes place directly to form ethanol in the presence of non-noble metal based catalysts, represented by the chemical reaction (3) above.
  • ethanol dehydrogenation for hydrogen production includes a process of ethanol dehydrogenation to produce hydrogen and ethyl acetate, followed by a process of ethyl acetate hydrolysis, as represented by chemical reactions (4) and (5) below:
  • Reaction (4) is endothermic, occurring in the presence of copper-based catalysts under the conditions of temperatures of approximately 100 to 300 °C and pressure of approximately 1 to 50 bar.
  • Reaction (5) occurs under the conditions of temperature of approximately 60 to 100 °C (and preferably approximately 70 °C) and ambient pressure, in the presence of catalysts, such as dilute sulfuric acid.
  • Ethanol the product of ethyl acetate hydrolysis in reaction (5), is recycled back as the feedstock of reaction (4), to increase hydrogen production.
  • Acetic acid, the co-product of ethyl acetate hydrolysis in reaction (5) is reused as a hydrogen-lean organic compound for hydrogen loading via the process of acetic acid hydrogenation to form ethanol (as discussed earlier).
  • the overall chemical reactions (4) and (5) may be represented by reaction (6) above, i.e., one mole ethanol reacts with one mole water to produce one mole acetic acid and two mole hydrogen.
  • reaction (6) i.e., one mole ethanol reacts with one mole water to produce one mole acetic acid and two mole hydrogen.
  • 8.7 kg of hydrogen can be obtained via 100 kg of ethanol dehydrogenation, with acetic acid as co-product, i.e., theoretically, the hydrogen storing and releasing capacity of the acetic acid (AcOH)Zethanol (EtOH) LOHC is 8.7 wt%.
  • system 10 may comprises one or more hydrogen generation facilities 12 (which may comprise, for example, facilities with renewable hydrogen or low carbon intensity (CI) hydrogen sources) configured for generating hydrogen.
  • the system 10 comprises an acetic acid to ethanol (ATE) apparatus 14 configured to generate ethanol from acetic acid and hydrogen, and an ethanol to hydrogen (ETH2) apparatus 18 configured to convert the ethanol to acetic acid and hydrogen.
  • ATE acetic acid to ethanol
  • ETH2 ethanol to hydrogen
  • the ATE apparatus 14 and the ETH2 apparatus 18 may be located at a distance from, or are remote from, each other.
  • the system 10 may comprise one or more ethanol transporters 16 configured to transport the ethanol generated from the ATE apparatus 14 to the ETH2 apparatus 18.
  • the ETH2 apparatus 18 may accept the ethanol transported by the ethanol transporters 16.
  • the ethanol transporters 16 may utilize transportation via truck, rail, boat, or any combination of these.
  • the system 10 may further comprise one or more hydrogen fueling stations 20 that use the hydrogen generated by the ETH2 apparatus 18.
  • the hydrogen generated may also be used by other hydrogen users.
  • the system 10 may further comprise one or more acetic acid industrial users 22 that may utilize the acetic acid generated by the ETH2 apparatus 18 as feedstock for industrial applications.
  • the system 10 may further comprise one or more acetic acid transporters 24 configured to transport the acetic acid generated by the ETH2 apparatus 18.
  • the acetic acid transporters 24 may utilize transportation via truck, rail, boat, or any combination of these.
  • the acetic acid transporters 24 may transport the acetic acid generated by the ETH2 apparatus 18 to the ATE apparatus 14 for use in generating ethanol.
  • the ethanol transporters 16 may be the same as the acetic acid transporters 24.
  • the system 10 may also comprise one or more bioethanol production facilities 26 configured to generate ethanol for use by the ATE apparatus 14.
  • the ATE apparatus 14 receives hydrogen from the hydrogen generation facilities 12 and acetic acid from the ETH2 apparatus 18. Alternatively, or in addition, the ATE apparatus 14 may receive ethanol from the bioethanol production facilities 26.
  • the ATE apparatus 14 preferably comprises a dehydration unit 28 configured to dehydrate acetic acid and ethanol, and a hydrogenation unit 30 configured to hydrogenate ethyl acetate.
  • Ethyl acetate with water as a by-product, is formed via acetic acid and ethanol dehydration.
  • Hydrogen is loaded and stored in the form of ethanol via ethyl acetate hydrogenation. At least a portion of the ethanol produced in the hydrogenation unit 30 may be recycled back to the dehydration unit 28 as feedstock for the production of ethyl acetate.
  • the ETH2 apparatus 18 may receive ethanol from the ATE apparatus 14 (such as through the ethanol transporters 16), and produces hydrogen via ethanol dehydrogenation.
  • Acetic acid is another product of the ETH2 apparatus 18.
  • the acetic acid may be transported back to the ATE apparatus 14 (such as by the acetic acid transporters 24) and reused for the next cycle of hydrogenation to produce ethanol for hydrogen storing, transporting, etc.
  • the acetic acid for the ATE apparatus may come from one or more acetic acid production facilities.
  • the ETH2 apparatus 18 preferably comprises a dehydrogenation unit 32 configured to dehydrogenate ethanol, and a hydrolysis unit 34 configured to hydrolyze ethyl acetate. Hydrogen, with a co-product ethyl acetate, is produced via ethanol dehydrogenation. With the addition of water, ethanol and acetic acid are formed via ethyl acetate hydrolysis, with ethanol cycled to the dehydrogenation unit 32 to form ethyl acetate and to produce more hydrogen, with the acetic acid transported back to the ATE apparatus 14 and reused for the next cycle of hydrogenation to ethanol for hydrogen storing and transporting.
  • ethanol as feedstock, is transported from the bioethanol production facilities 26 or low carbon intensity ethanol plants to the ETH2 apparatus 18, and hydrogen is produced via ethanol dehydrogenation.
  • the acetic acid generated by the ETH2 apparatus 18 may be used for industrial applications, eliminating the need to return the acetic acid back to the ATE apparatus 14.

Abstract

This invention relates to systems and methods for storing, transporting, and supplying hydrogen, using acetic acid (AcOH)/ ethanol (EtOH) as a liquid organic hydrogen carrier (LOHC) pair, with AcOH as hydrogen-lean organic compound, and with EtOH as hydrogen- rich organic compound. The hydrogen loading is realized via AcOH hydrogenation to produce EtOH, and hydrogen releasing via EtOH dehydrogenation to produce hydrogen and AcOH. Both AcOH and EtOH are bulk chemical commodities, which can be stored and transported safely and economically by using existing infrastructure. The system consists of hydrogen sources, bioethanol/ ethanol sources, acetic acid sources, AcOH to EtOH (ATE) apparatus, EtOH transportation, EtOH to hydrogen (ETH2) apparatus, AcOH transportation, and hydrogen end-users. Through this system, alternatively, ethanol can be used as feedstock to produce hydrogen via ETH2 apparatus, with AcOH as by-product for industrial use.

Description

TITLE OF INVENTION
Systems And Methods For Storing, Transporting,
And Supplying Hydrogen
TECHNICAL FIELD
[0001] The present invention relates to systems and methods for storing, transporting, and supplying hydrogen, and, in particular, to systems and methods that use acetic acid (AcOH) and ethanol (EtOH) as a liquid organic hydrogen carrier (LOHC) pair to store, transport, and supply hydrogen.
BACKGROUND OF THE INVENTION
[0002] Hydrogen is a clean fuel because its combustion product is water vapor, without emitting any CO2. Green or blue hydrogen obtained from renewable energy or low-carbon footprint fossil resources is expected to be an important element in achieving global carbon- neutrality and carbon-zero goals.
[0003] Hydrogen is the lightest element on earth. Although it has the highest caloric value (142 MJ/kg) in comparison with other fuels (such as gasoline at a caloric value of about 46.4 MJ/kg and diesel at a caloric value of about 45.6 MJ/kg), storing and transporting hydrogen is a challenge. Up to now, normally, hydrogen is stored or transported in a compressed gas phase or cryogenic liquid phase under extremely high pressures (350-700 bar) or at extremely low temperature (-253°C), constrained in expensive pressure cylinders or cryogenic tanks, with high hazardous risks. Due to safety and economic reasons, compressed hydrogen and liquid hydrogen are not suitable for large-scale storage and long-distance transportation, which will be required as the shift to a hydrogen economy advances.
[0004] An alternative method of hydrogen storage via solid hydrides has not shown sufficient potential due to factors such as low hydrogen storage capacity, slow reaction kinetics, variable metallic hydride costs, and poor reversibility. If hydrogen is to fulfill its promise as a global clean energy source, large-scale hydrogen storage and safe transportation methods are essential. Therefore, liquid organic hydrogen carriers (LOHCs) have emerged as favorable storing and delivery media because of their desirable properties, such as relatively low cost and compatibility with existing transport infrastructure. [0005] Hydrogen storage via liquid organic molecules involves two reversible reaction steps: hydrogenation of hydrogen-lean organic molecules and dehydrogenation of hydrogen-rich organic molecules. Liquid hydrogen-lean organic molecules are reusable in the process of reversible hydrogenation and dehydrogenation. LOHCs store hydrogen through hydrogenation and release hydrogen via dehydrogenation. They also can be stored for extended periods on a large scale without any toss and transported over a tong distance using existing infrastructure for liquid fuels and chemicals.
[0006] LOHC-based hydrogen storage systems are still in an evolving phase. Only a small number of technology developers worldwide have commercialization activities using LOHCs, including Chiyoda Corporation, Hydrogenious GmbH, and Hynertech. Their LOHCs are typically unsaturated aromatics (organic molecules with C-C double or triple bonds) and cyclic hydrocarbons, such as toluene/methyl-cyclohexane (TOL/MCH) and perhydrodibenzyl toluene/ dibenzyltoluene (PDBT/DBT). Both TOL/MCH and PDBT/DBT LOHCs have hydrogen storing and releasing capacity of approximately 6.2 wt%.
[0007] There are certain deficiencies associated with these LOHCs, such as high heat demand for the dehydrogenation process, poor reversibility of the organic hydrogen carriers, and toxic characteristics of the materials. To date, of the several LOHCs that have been developed, none are ideal as their practical usages are still in their infancy. There remains a need for further development in LOHC technologies.
[0008] Ba L. Tran et al., Ethanol as a Liquid Organic Hydrogen Carrier for Seasonal Microgrid Application: Catalysis, Theory, and Engineering Feasibility, ACS Sustainable Chem. Eng. 2021, 9, 20, 7130-7138, disclosed using ethyl acetate (EtOAc)Zethanol (EtOH) as a liquid organic hydrogen carrier pair for seasonal microgrid application. An evaluation of the cycling efficiency of 1) hydrogen’s release from ethanol to form ethyl acetate as the spent LOHC (hydrogen-lean organic compound); and 2) the subsequent regeneration of ethanol from ethyl acetate via hydrogenation of ethyl acetate found the hydrogen storing and releasing capacity to be relatively tow at 4.3 wt%, based on the chemical reaction stoichiometry of ethanol dehydrogenation to ethyl acetate.
SUMMARY OF THE INVENTION
[0009] In accordance with one embodiment of the invention, a method for storing and delivering hydrogen comprises the steps of reacting acetic acid with hydrogen to produce ethanol and water, with the acetic acid and the ethanol being a liquid organic hydrogen carrier (LOHC) pair, with the acetic acid as a hydrogen-lean organic compound, and with the ethanol is a hydrogen-rich organic compound; storing the ethanol as a storage form for the hydrogen; transporting the ethanol as a transportation form for the hydrogen; and using the ethanol and water to produce hydrogen via an ethanol dehydrogenation reaction and an ethyl acetate hydrolysis reaction, coproducing the acetic acid for reuse as the hydrogen-lean organic compound to produce the ethanol as the hydrogen-rich compound via acetic acid hydrogenation.
[0010] In another embodiment, a system for storing and delivering hydrogen comprises an acetic acid to ethanol (ATE) apparatus and an ethanol to hydrogen (ETH2) apparatus. The ATE apparatus is configured to generate ethanol using acetic acid hydrogenation, with the ethanol being used as a storage form for the hydrogen. The ETH2 apparatus is configured to re-generate the hydrogen using dehydrogenation of at least a portion of the ethanol, with acetic acid produced as a co-product.
[0011] In still another embodiment, the ATE apparatus is located remote from the ETH2 apparatus.
[0012] In yet another embodiment, the system further comprises one or more hydrogen production facilities for producing at least a portion of the hydrogen for use by the ATE apparatus.
[0013] In still another embodiment, the system further comprises one or more bioethanol production facilities for producing at least a portion of the ethanol for use by the ETH2 apparatus.
[0014] In still yet another embodiment, the system further comprises one or more ethanol transporter configured to transport at least a portion of the ethanol from the ATE apparatus to the ETH2 apparatus.
[0015] In a further embodiment, the system further comprises one or more hydrogen supplying facilities configured to supply hydrogen produced from the ETH2 apparatus.
[0016] In still a further embodiment, the system further comprises one or more acetic acid transporters configured to transport at least a portion of the acetic acid produced by the ETHa apparatus to the ATE apparatus.
[0017] In yet still a further embodiment, the ATE apparatus comprises a dehydration unit and a hydrogenation unit. The dehydration unit is configured to carry out ethanol and acetic acid dehydration to generate ethyl acetate and water. The hydrogenation unit is configured to carry out ethyl acetate hydrogenation to generate the ethanol, with at least a portion of the ethyl acetate produced by the dehydration unit being used by the hydrogenation unit for the ethyl acetate hydrogenation.
[0018] In another embodiment, the dehydration unit receives the acetic acid from one or both of the ETH2 apparatus and one or more acetic acid production facilities. The dehydration unit receives the ethanol from one or both of the hydrogenation unit and the one or more bioethanol production facilities.
[0019] In yet another embodiment, at least a portion of the water produced by the dehydration unit is used for utility use.
[0020] In yet another embodiment, the ethanol and acetic acid dehydration occurs in the presence of catalysts under temperature conditions of approximately 60 to 100 °C and pressure conditions of approximately 1 to 5 bar.
[0021] In a further embodiment, the ethyl acetate hydrogenation occurs in the presence of a copper-based catalyst under temperature conditions of 100 to 300 °C and pressure conditions of 1 to 30 bar.
[0022] In still a further embodiment, the hydrogen used by the hydrogenation unit is produced by one or more of the following: via water electrolysis powered by renewable energy, and via reforming or gasifying fossil fuels.
[0023] In yet still a further embodiment, the ethanol produced by the hydrogenation unit is used for one or both of the following: as a hydrogen carrier for hydrogen storage and transportation and as feedstock for the dehydration unit.
[0024] In another embodiment, the acetic acid hydrogenation by the ATE apparatus to form the ethanol occurs directly in the presence of non-noble metal based catalysts, without ethyl acetate as an intermediate.
[0025] In yet another embodiment, the ETH2 apparatus comprises a dehydrogenation unit and a hydrolysis unit. The dehydrogenation unit is configured to carry out ethanol dehydrogenation to produce the hydrogen and ethyl acetate. The hydrolysis unit is configured to carry out ethyl acetate hydrolysis to generate acetic acid, with at least a portion of the ethyl acetate produced by the dehydrogenation unit being used by the hydrolysis unit for the ethyl acetate hydrolysis. [0026] In still yet another embodiment, the dehydrogenation unit is further configured to receive the ethanol from one or both of the ATE apparatus and the hydrolysis unit.
[0027] In still a further embodiment, the acetic acid generated by the hydrolysis unit is used for one or both of the following: as a hydrogen-lean organic compound for transport back to the ATE apparatus and as a chemical for industrial use.
[0028] In still yet a further embodiment, the ethanol dehydrogenation occurs in the presence of copper-based catalysts under temperature conditions of approximately 100 to 300 °C and pressure conditions of approximately 1 to 50 bar.
[0029] In another embodiment, the ethyl acetate hydrolysis occurs in the presence of catalysts under temperature conditions of approximately 60 to 100 °C and pressure conditions of approximately 1 to 5 bar.
[0030] It should be understood that other aspects of the present invention will become apparent to those skilled in the art based on the following detailed description, in which various embodiments of the invention are shown and described by way of illustration. As will be realized, the present invention is capable of other and different embodiments and its several details are capable of modification in various other respects, all of which are within the present invention. Furthermore, the various embodiments described may be combined, mutatis mutandis, with other embodiments described herein. Therefore, the drawings and detailed description are to be regarded as illustrative in nature and not restrictive.
BRIEF DESCRIPTION OF THE DRAWINGS
[0031] With reference to the accompanying drawings, several aspects of the present invention are illustrated by way of example, and not by way of limitation, in detail in the figures, wherein:
(a) Fig. 1 is a schematic diagram depicting a system for storing, transporting, and supplying hydrogen according to one embodiment of the present invention; and
(b) Fig. 2 is a schematic diagram of an acetic acid to ethanol apparatus for the hydrogenation of acetic acid (AcOH) to produce ethanol (EtOH) according to another embodiment of the present invention, and
(c) Fig. 3 is a schematic diagram of an ethanol to hydrogen apparatus for the dehydrogenation of ethanol (EtOH) to produce hydrogen with co-product acetic acid according to another embodiment of the present invention. DETAILED DESCRIPTION
[0032] The detailed description set forth below in conjunction with the accompanying drawings is intended as a description of various embodiments of the present invention and is not intended to represent the only embodiments contemplated by the inventor. The detailed description includes specific details for the purpose of providing a comprehensive understanding of the present invention. However, it will be apparent to those skilled in the art that the present invention may be practiced without these specific details.
[0033] The present invention discloses systems and methods of using acetic acid (AcOH)Zethanol (EtOH) as a LOHC pair, with acetic acid as the hydrogen-lean organic compound and ethanol as the hydrogen-rich organic compound, and with an estimated hydrogen storing and releasing capacity of 8.7 wt%.
[0034] Both acetic acid and ethanol are bulk chemicals, with existing storage and transportation infrastructure available. In addition, acetic acid and ethanol are less expensive than the unsaturated aromatic and cyclic hydrocarbons such as TOL/MCH and PDBT/DBT typically used by other LOHC designs.
[0035] There are provided systems and methods for storing, transporting, and supplying hydrogen, comprising: renewable hydrogen and/or low carbon intensity hydrogen sources, bioethanol and/or ethanol sources, acetic acid sources, acetic acid hydrogenation to form ethanol apparatus, ethanol transportation, ethanol dehydrogenation to produce hydrogen and acetic acid apparatus, hydrogen distribution to end-users and acetic acid transportation.
[0036] There are provided methods for storing and releasing hydrogen, based on hydrogenation of acetic acid to form ethanol and dehydrogenation of ethanol to produce hydrogen and acetic acid. More especially, this invention relates to using acetic acid and ethanol as a liquid organic hydrogen carrier (LOHC) pair.
[0037] Both acetic acid and ethanol are widely used bulk chemical commodities. The system disclosed in the present invention is a safe and affordable way to store and transport more hydrogen that’s compatible with existing infrastructure for the storage and transportation of acetic acid and ethanol. According to the chemical reaction mass balance of ethanol dehydrogenation to produce hydrogen and acetic acid chemical reactions, the hydrogen storing and releasing capacity is expected to be 8.7 wt%. For example, 8.7 kg hydrogen can be obtained using 100 kg ethanol as the hydrogen carrier followed with ethanol dehydrogenation to release hydrogen, with acetic acid as co-product that can be returned as a hydrogen-lean organic compound to again produce ethanol via acetic acid hydrogenation.
[0038] There is provided an acetic acid to ethanol (ATE) apparatus for loading hydrogen via acetic acid hydrogenation, receiving hydrogen and acetic acid as feedstocks to produce ethanol. Hydrogen may be obtained via water electrolysis powered by renewable energy such as solar, wind, hydro, and geothermal, or produced from fossil fuels such as natural gas, crude oil, and coal, with or without CO2 capture, utilization, and sequestration (CCUS) processing. Acetic acid is regenerated and transported from the ethanol dehydrogenation apparatus of the present system of this invention, and/or obtained from acetic acid production facilities.
[0039] There is provided an acetic acid to ethanol (ATE) apparatus, comprising a two-step process or a one-step process. The ATE two-step process comprises an acetic acid and ethanol dehydration unit to produce ethyl acetate and water, followed by an ethyl acetate hydrogenation unit to produce ethanol in the presence of copper-based catalyst under the conditions of temperatures of approximately 100 to 300 °C and pressure of approximately 1 to 30 bar, with half of the ethanol product as hydrogen carrier for hydrogen storing, transporting, and supplying to the end-users, and another half of the ethanol product as feedstock recycled back to the acetic acid and ethanol dehydration unit to produce ethyl acetate. Alternatively, the ATE one-step process comprises the process of acetic acid hydrogenation to form ethanol may take place directly in the presence of non-noble metal-based catalysts, without the step of ethyl acetate as an intermediate product to produce ethanol via ethyl acetate hydrogenation, which may however, require using anti-corrosion material for the process equipment.
[0040] There is provided an ethanol to hydrogen (ETH2) apparatus for releasing hydrogen via ethanol dehydrogenation, receiving ethanol and water as feedstocks to produce hydrogen and acetic acid. Ethanol is transported from the ATE apparatus of the present system of this invention.
[0041] There is provided an ethanol to hydrogen (ETH2) apparatus, comprising: an ethanol dehydrogenation unit to produce hydrogen and ethyl acetate in the presence of copper-based catalysts under the conditions of temperatures of approximately 100 to 300 °C and pressure of approximately 1 to 50 bar, and an ethyl acetate hydrolysis unit to produce ethanol and acetic acid, with the ethanol product recycled back to the ethanol dehydrogenation unit as feedstock to produce more hydrogen, and with the acetic acid product transported back to the ATE apparatus of the present system of this invention. [0042] There is provided a method for using ethanol as feedstock to produce hydrogen for consumers, with acetate acid as a by-product for industrial use. In this case, the ethanol may be transported from bioethanol production facilities or low carbon intensity ethanol plants, and the acetic acid generated in the ETH2 apparatus is not necessary to be transported back for reuse as hydrogen-lean organic compound to form ethanol as liquid organic hydrogen carrier via hydrogenation. Or, in this case, the hydrogen producers may use the ATE process (acetic acid hydrogenation) described above to form ethanol as a hydrogen-rich liquid organic compound for hydrogen storing and transporting, while the acetic acid may be produced at local facilities close to the hydrogen production plants, instead of transporting back the acetic acid from the ETH2 apparatus to the ATE apparatus.
[0043] System and methods for the storing, delivering, and supplying of hydrogen are provided. In one embodiment of the present invention, a system may use acetic acid (AcOH) as a hydrogen-lean organic compound for hydrogen loading via a hydrogenation process and ethanol (EtOH) as a hydrogen-rich organic compound for hydrogen releasing via a dehydrogenation process. Both acetic acid and ethanol are relatively inexpensive bulk chemicals, with their own existing storage and transportation infrastructure.
[0044] In one embodiment of the present invention, acetic acid hydrogenation comprises processes of acetic acid and ethanol dehydration to ethyl acetate (EtOAc) and ethyl acetate hydrogenation to ethanol, which are represented by the chemical reactions (1) and (2) below:
[0045]
CH3COOH (AcOH) + C2H5OH (EtOH) CH3COOC2H5 (EtOAc) + H2O (1)
CH3COOC2H5 (EtOAc) + 2H2 2C2H5OH (EtOH) (2)
CH3COOH (AcOH) + 2H2 C2H5OH (EtOH) + H2O (3)
[0046] Reaction (1) comprises an esterification process, taking place in the presence of catalysts, such as concentrated sulfuric acid, under the conditions of temperatures of approximately 60 to 100 °C (and preferably approximately 70 °C) and ambient pressure, with ethyl acetate and water (H2O) as its products. Reaction (2) comprises an ethyl acetate hydrogenation to ethanol process, which is an exothermic reaction, taking place in the presence of a copper-based catalyst under the conditions of temperatures of approximately 100 to 300 °C and pressure of approximately 1 to 30 bar. Combining reactions (1) and (2), the overall reaction is represented by reaction (3); one mole acetic acid reacts with two moles hydrogen to produce one mole ethanol and one mole byproduct of water. [0047] In another embodiment of the present invention, acetic acid hydrogenation takes place directly to form ethanol in the presence of non-noble metal based catalysts, represented by the chemical reaction (3) above.
[0048] In another embodiment of the present invention, ethanol dehydrogenation for hydrogen production includes a process of ethanol dehydrogenation to produce hydrogen and ethyl acetate, followed by a process of ethyl acetate hydrolysis, as represented by chemical reactions (4) and (5) below:
2C2H5OH (EtOH) CH3COOC2H5 (EtOAc) + 2H2 (4)
CH3COOC2H5 (EtOAc) + H2O C2H5OH (EtOH) + CH3COOH (AcOH)) (5)
C2H5OH (EtOH) + H2O CH3COOH (AcOH) + 2H2 (6)
[0049] Reaction (4) is endothermic, occurring in the presence of copper-based catalysts under the conditions of temperatures of approximately 100 to 300 °C and pressure of approximately 1 to 50 bar. Reaction (5) occurs under the conditions of temperature of approximately 60 to 100 °C (and preferably approximately 70 °C) and ambient pressure, in the presence of catalysts, such as dilute sulfuric acid. Ethanol, the product of ethyl acetate hydrolysis in reaction (5), is recycled back as the feedstock of reaction (4), to increase hydrogen production. Acetic acid, the co-product of ethyl acetate hydrolysis in reaction (5) is reused as a hydrogen-lean organic compound for hydrogen loading via the process of acetic acid hydrogenation to form ethanol (as discussed earlier). The overall chemical reactions (4) and (5) may be represented by reaction (6) above, i.e., one mole ethanol reacts with one mole water to produce one mole acetic acid and two mole hydrogen. According to the mass balance, 8.7 kg of hydrogen can be obtained via 100 kg of ethanol dehydrogenation, with acetic acid as co-product, i.e., theoretically, the hydrogen storing and releasing capacity of the acetic acid (AcOH)Zethanol (EtOH) LOHC is 8.7 wt%.
[0050] Referring to Fig. 1, systems and methods for storing, transporting, and supplying hydrogen are provided, which use acetic acid (AcOH)Zethanol (EtOH) as a liquid organic hydrogen carrier (LOHC) pair. In one embodiment, system 10 may comprises one or more hydrogen generation facilities 12 (which may comprise, for example, facilities with renewable hydrogen or low carbon intensity (CI) hydrogen sources) configured for generating hydrogen. In addition, the system 10 comprises an acetic acid to ethanol (ATE) apparatus 14 configured to generate ethanol from acetic acid and hydrogen, and an ethanol to hydrogen (ETH2) apparatus 18 configured to convert the ethanol to acetic acid and hydrogen. The ATE apparatus 14 and the ETH2 apparatus 18 may be located at a distance from, or are remote from, each other. The system 10 may comprise one or more ethanol transporters 16 configured to transport the ethanol generated from the ATE apparatus 14 to the ETH2 apparatus 18. The ETH2 apparatus 18 may accept the ethanol transported by the ethanol transporters 16. The ethanol transporters 16 may utilize transportation via truck, rail, boat, or any combination of these.
[0051] The system 10 may further comprise one or more hydrogen fueling stations 20 that use the hydrogen generated by the ETH2 apparatus 18. The hydrogen generated may also be used by other hydrogen users. In one embodiment, the system 10 may further comprise one or more acetic acid industrial users 22 that may utilize the acetic acid generated by the ETH2 apparatus 18 as feedstock for industrial applications. Alternatively, or in addition, the system 10 may further comprise one or more acetic acid transporters 24 configured to transport the acetic acid generated by the ETH2 apparatus 18. The acetic acid transporters 24 may utilize transportation via truck, rail, boat, or any combination of these. The acetic acid transporters 24 may transport the acetic acid generated by the ETH2 apparatus 18 to the ATE apparatus 14 for use in generating ethanol. In one embodiment, the ethanol transporters 16 may be the same as the acetic acid transporters 24. The system 10 may also comprise one or more bioethanol production facilities 26 configured to generate ethanol for use by the ATE apparatus 14.
[0052] Referring to Fig. 1, in one embodiment, the ATE apparatus 14 receives hydrogen from the hydrogen generation facilities 12 and acetic acid from the ETH2 apparatus 18. Alternatively, or in addition, the ATE apparatus 14 may receive ethanol from the bioethanol production facilities 26.
[0053] Referring to Fig. 1 and Fig. 2, the ATE apparatus 14 preferably comprises a dehydration unit 28 configured to dehydrate acetic acid and ethanol, and a hydrogenation unit 30 configured to hydrogenate ethyl acetate. Ethyl acetate, with water as a by-product, is formed via acetic acid and ethanol dehydration. Hydrogen is loaded and stored in the form of ethanol via ethyl acetate hydrogenation. At least a portion of the ethanol produced in the hydrogenation unit 30 may be recycled back to the dehydration unit 28 as feedstock for the production of ethyl acetate.
[0054] Referring to Fig. 1, the ETH2 apparatus 18 may receive ethanol from the ATE apparatus 14 (such as through the ethanol transporters 16), and produces hydrogen via ethanol dehydrogenation. Acetic acid is another product of the ETH2 apparatus 18. The acetic acid may be transported back to the ATE apparatus 14 (such as by the acetic acid transporters 24) and reused for the next cycle of hydrogenation to produce ethanol for hydrogen storing, transporting, etc. Alternatively, or in addition, the acetic acid for the ATE apparatus may come from one or more acetic acid production facilities.
[0055] Referring to Fig. 1 and Fig. 3, the ETH2 apparatus 18 preferably comprises a dehydrogenation unit 32 configured to dehydrogenate ethanol, and a hydrolysis unit 34 configured to hydrolyze ethyl acetate. Hydrogen, with a co-product ethyl acetate, is produced via ethanol dehydrogenation. With the addition of water, ethanol and acetic acid are formed via ethyl acetate hydrolysis, with ethanol cycled to the dehydrogenation unit 32 to form ethyl acetate and to produce more hydrogen, with the acetic acid transported back to the ATE apparatus 14 and reused for the next cycle of hydrogenation to ethanol for hydrogen storing and transporting.
[0056] Referring to Fig. 1, alternatively, ethanol, as feedstock, is transported from the bioethanol production facilities 26 or low carbon intensity ethanol plants to the ETH2 apparatus 18, and hydrogen is produced via ethanol dehydrogenation. In this case, the acetic acid generated by the ETH2 apparatus 18 may be used for industrial applications, eliminating the need to return the acetic acid back to the ATE apparatus 14.
[0057] The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to those embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein, but is to be accorded the full scope consistent with the claims, wherein reference to an element in the singular, such as by use of the article "a" or "an" is not intended to mean "one and only one" unless specifically so stated, but rather "one or more". All structural and functional equivalents to the elements of the various embodiments described throughout the disclosure that are known or later come to be known to those of ordinary skill in the art are intended to be encompassed by the elements of the claims. Moreover, nothing disclosed herein is intended to be dedicated to the public regardless of whether such disclosure is explicitly recited in the claims.

Claims

CLAIMS A method of hydrogen storage and delivery, the method comprising the steps of: reacting acetic acid with hydrogen to produce ethanol and water, wherein the acetic acid and the ethanol are a liquid organic hydrogen carrier (LOHC) pair, wherein the acetic acid is a hydrogen-lean organic compound, and wherein the ethanol is a hydrogen-rich organic compound; storing the ethanol as a storage form for the hydrogen; transporting the ethanol as a transportation form for the hydrogen, and using the ethanol and water to produce hydrogen via an ethanol dehydrogenation reaction and an ethyl acetate hydrolysis reaction, coproducing the acetic acid for reuse as the hydrogen-lean organic compound to produce the ethanol as the hydrogen-rich organic compound via acetic acid hydrogenation. A system for storing and delivering hydrogen, the system comprising: an acetic acid to ethanol (ATE) apparatus configured to generate ethanol using acetic acid hydrogenation, wherein the ethanol is used as a storage form for the hydrogen; and an ethanol to hydrogen (ETH2) apparatus configured to re-generate the hydrogen using dehydrogenation of at least a portion of the ethanol, with acetic acid produced as a co-product. The system of claim 2, wherein the ATE apparatus is located remote from the ETH2 apparatus. The system of claim 2, further comprising one or more hydrogen production facilities for producing at least a portion of the hydrogen for use by the ATE apparatus. The system of claim 2, further comprising one or more bioethanol production facilities for producing at least a portion of the ethanol for use by the ETH2 apparatus. The system of claim 3, further comprising one or more ethanol transporters configured to transport at least a portion of the ethanol produced by the ATE apparatus to the ETH2 apparatus. The system of claim 2, further comprising one or more hydrogen supplying facilities configured to supply the hydrogen produced by the ETH2 apparatus. The system of claim 3, further comprising one or more acetic acid transporters configured to transport at least a portion of the acetic acid produced by the ETH2 apparatus to the ATE apparatus. The system of claim 2, wherein the ATE apparatus comprises: a dehydration unit configured to carry out ethanol and acetic acid dehydration to generate ethyl acetate and water; and a hydrogenation unit configured to carry out ethyl acetate hydrogenation to generate the ethanol, wherein at least a portion of the ethyl acetate produced by the dehydration unit is used by the hydrogenation unit for the ethyl acetate hydrogenation. The system of claim 9, wherein the dehydration unit receives the acetic acid from one or both of the ETH2 apparatus and one or more acetic acid production facilities, and wherein the dehydration unit receives the ethanol from one or both of the hydrogenation unit and the one or more bioethanol production facilities. The system of claim 9, wherein at least a portion of the water produced by the dehydration unit is used for utility use. The system of claim 9, wherein the ethanol and acetic acid dehydration occurs in the presence of catalysts under temperature conditions of approximately 60 to 100 °C and pressure conditions of approximately 1 to 5 bar. The system of claim 9, wherein the ethyl acetate hydrogenation occurs in the presence of a copper-based catalyst under temperature conditions of approximately 100 to 300 °C and pressure conditions of approximately 1 to 30 bar. The system of claim 9, wherein the hydrogen used by the hydrogenation unit is produced by one or more of the following: via water electrolysis powered by renewable energy, and via reforming or gasifying fossil fuels. The system of claim 9, wherein the ethanol produced by the hydrogenation unit is used for one or both of the following: as a hydrogen carrier for hydrogen storage and transportation and as feedstock for the dehydration unit. The system of claim 2, wherein the acetic acid hydrogenation by the ATE apparatus to form the ethanol occurs in the presence of non-noble metal based catalysts. The system of claim 2, wherein the ETH2 apparatus comprises: a dehydrogenation unit configured to carry out ethanol dehydrogenation to produce the hydrogen and ethyl acetate; and a hydrolysis unit configured to carry out ethyl acetate hydrolysis to generate acetic acid, wherein at least a portion of the ethyl acetate produced by the dehydrogenation unit is used by the hydrolysis unit for the ethyl acetate hydrolysis. The system of claim 17, wherein the dehydrogenation unit is further configured to receive the ethanol from one or both of the ATE apparatus and the hydrolysis unit. The system of claim 17, wherein the acetic acid generated by the hydrolysis unit is used for one or both of the following: as a hydrogen-lean organic compound for transport back to the ATE apparatus and as a chemical for industrial use. The system of claim 17, wherein the ethanol dehydrogenation occurs in the presence of copper-based catalysts under temperature conditions of approximately 100 to 300 °C and pressure conditions of approximately 1 to 50 bar. The system of claim 17, wherein the ethyl acetate hydrolysis occurs in the presence of catalysts under temperature conditions of approximately 60 to 100 °C and pressure conditions of approximately 1 to 5 bar.
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