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WO2016066571A1 - Process for producing liquid hydrogen - Google Patents

Process for producing liquid hydrogen Download PDF

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Publication number
WO2016066571A1
WO2016066571A1 PCT/EP2015/074712 EP2015074712W WO2016066571A1 WO 2016066571 A1 WO2016066571 A1 WO 2016066571A1 EP 2015074712 W EP2015074712 W EP 2015074712W WO 2016066571 A1 WO2016066571 A1 WO 2016066571A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrogen
electricity
energy
electrolysis
metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2015/074712
Other languages
French (fr)
Inventor
Nikunj Gupta
Thomas Alexander Pasfield
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
Shell USA Inc
Original Assignee
Shell Internationale Research Maatschappij BV
Shell Oil Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij BV, Shell Oil Co filed Critical Shell Internationale Research Maatschappij BV
Priority to BR112017007390A priority Critical patent/BR112017007390A2/en
Priority to US15/522,308 priority patent/US20170321332A1/en
Priority to CN201580058397.2A priority patent/CN107074538A/en
Priority to ES201790014A priority patent/ES2643558B1/en
Priority to AU2015340752A priority patent/AU2015340752B2/en
Publication of WO2016066571A1 publication Critical patent/WO2016066571A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/08—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents with metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/22—Inorganic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/50—Processes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B5/00—Electrogenerative processes, i.e. processes for producing compounds in which electricity is generated simultaneously
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0005—Light or noble gases
    • F25J1/001—Hydrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0228—Coupling of the liquefaction unit to other units or processes, so-called integrated processes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0244—Operation; Control and regulation; Instrumentation
    • F25J1/0245—Different modes, i.e. 'runs', of operation; Process control
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
    • F25J1/0279—Compression of refrigerant or internal recycle fluid, e.g. kind of compressor, accumulator, suction drum etc.
    • F25J1/0281—Compression of refrigerant or internal recycle fluid, e.g. kind of compressor, accumulator, suction drum etc. characterised by the type of prime driver, e.g. hot gas expander
    • F25J1/0284—Electrical motor as the prime mechanical driver
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2260/00—Coupling of processes or apparatus to other units; Integrated schemes
    • F25J2260/30—Integration in an installation using renewable energy
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/62—Details of storing a fluid in a tank
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Definitions

  • the invention relates to a process for producing liquid hydrogen and a system for said process.
  • Hydrogen is an important industrial gas used in oil refining and fertilizer industries and in several other chemical processes. It is expected that hydrogen may additionally play a significant role as an energy carrier, in particular in the transportation sector.
  • SOEC's polymer electrolyte membrane cells
  • PEM polymer electrolyte membrane cells
  • AEC's alkaline electrolysis cells
  • SOEC's operate at high temperatures, typically around 800 °C.
  • PEM electrolysis cells typically operate below 100 °C and are becoming increasingly available commercially. These cells have the advantage of being comparatively simple and can be designed to accept widely varying voltage inputs which makes them ideal for use with renewable sources of energy such as solar PV.
  • AEC's optimally operate at high concentrations electrolyte (KOH or potassium carbonate) and at high temperatures, often near 200 °C.
  • electrolysable metal is chosen from zinc, nickel,
  • renewable power at (usually) remote locations is expected to be more affordable than close to markets, principally due to availability of appropriate land and better availability of the energy resource (solar, wind etc.) itself.
  • Such remote renewable power may be a very good fit for electrolysis to produce hydrogen as it
  • renewable energy molecule generates an affordable renewable energy molecule.
  • power from conventional sources e.g. power generated by gas turbines and delivered through the grid
  • the present invention provides a solution to the problem of under-utilization of hydrogen production and hydrogen liquefaction plants, in particular in remote locations with unstable power supply. Further the present invention solves the problems of intermittency in hydrogen production and liquefaction plants at locations where power supply comes, at least in part, from renewable energy sources, and in particular from wind and solar energy.
  • the present invention provides an integrated process for continuous production of liquid hydrogen, comprising
  • liquefaction unit which liquefaction unit is powered by energy essentially (i.e. at least 80%, preferably at least 90%, most preferred 100%) from renewable sources; and, (c) when additional power is needed, using electrical energy generated in a process in which electrical energy and hydrogen are co-generated by an integrated electrolysis process comprising:
  • step (e) wherein at least part of the gaseous hydrogen generated in step (e) is used in step (b) of the process.
  • This process of the present invention is ideally suited for liquid hydrogen manufacturing by allowing the expensive liquefaction unit to run on a continuous basis while providing hydrogen and additional electricity on demand basis, despite the fact that the basic renewable energy source is only intermittently available.
  • the integration of the electrolysis process can advantageously be done at one or more locations in the production and liquefaction process.
  • the power generated in the electrolysis may provide (part of) the power needed in the liquefaction cycle.
  • the process comprises first feeding renewable (wind, solar etc.) intermittent
  • the integrated electrolysis process is defined as an electrolysis process comprising two distinct steps:
  • a metal salt or mixture of metal salts (the metal salt being selected from ZnSC>4, MgSC , MgCl 2 , and the like; preferably the metal salt is ZnSC ) is reacted with water to deposit metal on the electrode and to form acid (H 2 SO 4 , HC1 etc.) while releasing oxygen, which reaction is driven by intermittent, optionally renewable, electricity;
  • step (e) a regeneration step wherein the deposited metal on the electrode is reacted with the acid produced in step (d) to release hydrogen and re-synthesize the original metal salt (s) , which may be done in the presence of a suitable catalyst.
  • the stored energy can be regenerated as electricity (in addition to hydrogen) .
  • step (d) from discharging
  • step (regeneration) step (e) the energy and hydrogen storage capability provides an additional source of electricity and hydrogen when compared to conventional electrolysis processes whereby hydrogen is released
  • both the hydrogen and electricity product of step (e) can be individually produced as needed "on- demand”.
  • the equipment can be arranged in such a way that hydrogen may be produced all day and electricity only when needed, for example at night-time (for example in case of a solar power fed system) .
  • the produced hydrogen and/or electricity is subsequently fed to the hydrogen liquefaction unit, favourably co- located with the integrated electrolyser .
  • electricity is needed as an input to drive the compressors and the cooling units which form the core of liquefaction process.
  • the hydrogen liquefaction unit will run on renewable electricity when available, while electricity regenerated from the electrolyser in step (e) is used as a back-up in the intermittent periods (i.e. in case of solar electricity during night time or bad weather conditions) .
  • renewable electricity is the only source of electricity, optionally also
  • additional sources of electricity supply may be used as back-up when the renewable power source is not available and/or electricity regenerated from the electrolyser is not enough for supplying sufficient power to the hydrogen liquefaction unit.
  • gaseous hydrogen is optionally stored in a hydrogen storage unit in between the electrolyser (i.e. after step (e) ) and the hydrogen liquefaction unit (i.e. before liquefying the hydrogen) to manage a stable hydrogen supply to the liquefaction unit.
  • Liquefaction of hydrogen and liquefaction cycles suitable for hydrogen liquefaction are known in the art. Any suitable liquefaction cycle known in the art may be used, including the Claude cycle, Brayton cycle, Joule Thompson cycle and any modifications or combinations thereof .
  • hydrogen comprising an energy inlet for feeding energy from renewable sources into an electrolysis system for co- generation of electrical energy and hydrogen, which
  • the system may advantageously comprise a hydrogen storage unit for intermittent storage of gaseous hydrogen. Further, the system may favourably comprise a battery for storage of power for providing additional power at moments of very high demand.
  • an energy (e ⁇ ) essentially from renewable sources, is fed via an inlet (1) into an integrated electrolysis system (2), which comprises an energy storage part (3) and a
  • electricity may also be stored in a battery (10) for use to supply to the hydrogen liquefaction unit (7) in high demand situations or to supplement in case of low
  • liquid hydrogen (LH 2 ) is exported from the system via line (11) .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

The invention relates to an integrated process for continuous production of liquid hydrogen, comprising (a) producing gaseous hydrogen by electrolysis; and (b) liquefying said gaseous hydrogen in a hydrogen liquefaction unit, which liquefaction unit is powered by energy essentially from renewable sources; and, (c) when additional power is needed, using electrical energy generated in a process in which electrical energy and hydrogen are co-generated by an integrated electrolysis process comprising: (d) electrolysing a metal salt or mixture of metal salts and water into the corresponding metal or metals, acid or acids, and oxygen (electricity storage phase), and (e) producing gaseous hydrogen and recovering electricity in a regeneration reaction of the metal (s) and acid(s) of step (d) (regeneration phase); wherein at least part of the gaseous hydrogen generated in step (e) is used in step (b) of the process.

Description

PROCESS FOR PRODUCING LIQUID HYDROGEN
Field of the invention
The invention relates to a process for producing liquid hydrogen and a system for said process.
Background to the invention
Hydrogen is an important industrial gas used in oil refining and fertilizer industries and in several other chemical processes. It is expected that hydrogen may additionally play a significant role as an energy carrier, in particular in the transportation sector.
In the absence of a domestic pipeline network, or for imports, it is expected that hydrogen in liquid form will be one of the most effective ways for its supply and distribution. However, at present hydrogen liquefaction is still expensive as well as energy intensive. Liquefaction of hydrogen involves compressing of feed hydrogen gas, several cooling steps and finally liquefaction through expansion. At present, a lot of research is being done on improving the economics of the hydrogen liquefaction process (see e.g. the European sponsored IDEALHY project which in Dec. 2013 reported on the recently developed
"Preferred Process", see www . idealh . eu) .
Most hydrogen is currently produced via steam
reforming of hydrocarbons, in particular natural gas, due to the relatively low costs of the process. Steam reforming is a strongly endothermic process. The heat needed for the process is typically provided by combusting part of the natural gas feed in a furnace. Also other methods to produce hydrogen are known, for example by electrolysis. There are three main types of electrolysis cells, solid oxide electrolysis cells
(SOEC's), polymer electrolyte membrane cells (PEM) and alkaline electrolysis cells (AEC's). SOEC's operate at high temperatures, typically around 800 °C. PEM electrolysis cells typically operate below 100 °C and are becoming increasingly available commercially. These cells have the advantage of being comparatively simple and can be designed to accept widely varying voltage inputs which makes them ideal for use with renewable sources of energy such as solar PV. AEC's optimally operate at high concentrations electrolyte (KOH or potassium carbonate) and at high temperatures, often near 200 °C.
In addition, methods are known for simultaneous co- generation of hydrogen and electrical energy by totally electrochemical means, which methods for example include an electricity storage phase by electrolysis of metal salts in presence of water, to metals and acids, and thereby
releasing oxygen, and a generation phase whereby the produced metal & acids in storage phase are reacted to produce hydrogen and optionally electricity. The
electrolysable metal is chosen from zinc, nickel,
manganese. See for example US 8,617,766.
Renewable power at (usually) remote locations is expected to be more affordable than close to markets, principally due to availability of appropriate land and better availability of the energy resource (solar, wind etc.) itself. Such remote renewable power may be a very good fit for electrolysis to produce hydrogen as it
generates an affordable renewable energy molecule. Where renewable power supply is not sufficiently available, power from conventional sources (e.g. power generated by gas turbines and delivered through the grid) may also, or in addition, be used.
In particular renewable power generated from wind and solar sources suffers from the intermittent availability of these natural resources. At such locations with unstable power supply the production of hydrogen, and in particular the liquefaction of hydrogen, is not as effective as at locations where the production and liquefaction processes can continuously be run and the expensive liquefaction plant as a result can be highly utilized.
The present invention provides a solution to the problem of under-utilization of hydrogen production and hydrogen liquefaction plants, in particular in remote locations with unstable power supply. Further the present invention solves the problems of intermittency in hydrogen production and liquefaction plants at locations where power supply comes, at least in part, from renewable energy sources, and in particular from wind and solar energy.
Summary of the invention
It has now been found that by integrating at remote locations hydrogen production and liquefaction processes with a method that allows intermittent hydrogen and
electricity storage, a solution is provided to the above mentioned problems. Accordingly, the present invention provides an integrated process for continuous production of liquid hydrogen, comprising
(a) producing gaseous hydrogen by electrolysis; and
(b) liquefying said gaseous hydrogen in a hydrogen
liquefaction unit, which liquefaction unit is powered by energy essentially (i.e. at least 80%, preferably at least 90%, most preferred 100%) from renewable sources; and, (c) when additional power is needed, using electrical energy generated in a process in which electrical energy and hydrogen are co-generated by an integrated electrolysis process comprising:
(d) electrolysing a metal salt or mixture of metal salts and water into the corresponding metal or metals, acid or acids, and oxygen (electricity storage phase) , and
(e) producing gaseous hydrogen and recovering
electricity in a regeneration reaction of the metal (s) and acid(s) of step (d) (regeneration phase);
wherein at least part of the gaseous hydrogen generated in step (e) is used in step (b) of the process.
This process of the present invention is ideally suited for liquid hydrogen manufacturing by allowing the expensive liquefaction unit to run on a continuous basis while providing hydrogen and additional electricity on demand basis, despite the fact that the basic renewable energy source is only intermittently available.
Moreover, the integration of the electrolysis process can advantageously be done at one or more locations in the production and liquefaction process. For example, the power generated in the electrolysis may provide (part of) the power needed in the liquefaction cycle.
Brief description of the drawings
In Figure 1, a process according to the invention is schematically shown.
Detailed description of the invention
According to the invention the process comprises first feeding renewable (wind, solar etc.) intermittent
electricity to an integrated electrolysis process set-up. The integrated electrolysis process is defined as an electrolysis process comprising two distinct steps:
(d) an electricity storage step wherein a metal salt or mixture of metal salts (the metal salt being selected from ZnSC>4, MgSC , MgCl2, and the like; preferably the metal salt is ZnSC ) is reacted with water to deposit metal on the electrode and to form acid (H2SO4, HC1 etc.) while releasing oxygen, which reaction is driven by intermittent, optionally renewable, electricity;
(e) a regeneration step wherein the deposited metal on the electrode is reacted with the acid produced in step (d) to release hydrogen and re-synthesize the original metal salt (s) , which may be done in the presence of a suitable catalyst. Optionally, in this step (part of) the stored energy can be regenerated as electricity (in addition to hydrogen) .
Methods for co-generation of electric energy and hydrogen by a two-step electrolysis process as described here are known in the art, e.g. as disclosed in US 8,617,766.
By pursuing the above two step integrated electrolysis process, it is possible to separate the charging
(electricity storage) step (d) from discharging
(regeneration) step (e) . In this way, the energy and hydrogen storage capability provides an additional source of electricity and hydrogen when compared to conventional electrolysis processes whereby hydrogen is released
simultaneously when feeding power to an electrolyser .
Additionally, as an advantage of the process according to the invention, both the hydrogen and electricity product of step (e) can be individually produced as needed "on- demand". The process of the present invention thus
advantageously allows that the equipment can be arranged in such a way that hydrogen may be produced all day and electricity only when needed, for example at night-time (for example in case of a solar power fed system) .
After the first step of feeding renewable intermittent electricity to the integrated electrolysis process set-up, the produced hydrogen and/or electricity is subsequently fed to the hydrogen liquefaction unit, favourably co- located with the integrated electrolyser . In the hydrogen liquefaction unit, electricity is needed as an input to drive the compressors and the cooling units which form the core of liquefaction process.
By using the integrated process of the invention, it is possible to run the expensive hydrogen liquefaction unit in a stable and continuous operation mode, which is desired in order to make the best use of this capital investment. This would otherwise not be possible with only direct feed of intermittent electricity and/or intermittent hydrogen feed.
Typically, the hydrogen liquefaction unit will run on renewable electricity when available, while electricity regenerated from the electrolyser in step (e) is used as a back-up in the intermittent periods (i.e. in case of solar electricity during night time or bad weather conditions) .
In a further embodiment, in case renewable electricity is the only source of electricity, optionally also
additional sources of electricity supply (for example electric storage devices such as batteries) may be used as back-up when the renewable power source is not available and/or electricity regenerated from the electrolyser is not enough for supplying sufficient power to the hydrogen liquefaction unit.
In an embodiment of the invention, in the process comprising the integrated electrolysis process and hydrogen liquefaction process, gaseous hydrogen is optionally stored in a hydrogen storage unit in between the electrolyser (i.e. after step (e) ) and the hydrogen liquefaction unit (i.e. before liquefying the hydrogen) to manage a stable hydrogen supply to the liquefaction unit.
Liquefaction of hydrogen and liquefaction cycles suitable for hydrogen liquefaction are known in the art. Any suitable liquefaction cycle known in the art may be used, including the Claude cycle, Brayton cycle, Joule Thompson cycle and any modifications or combinations thereof .
A further embodiment of the invention relates an integrated system for continuously producing liquid
hydrogen, comprising an energy inlet for feeding energy from renewable sources into an electrolysis system for co- generation of electrical energy and hydrogen, which
comprises an energy storage part and a regeneration part, wherein the regeneration part of the electrolysis system has an outlet for hydrogen that is connected to a hydrogen liquefaction unit and wherein the regeneration part of the electrolysis system has an outlet for electricity produced in the electrolysis system that is connected to an energy inlet into the hydrogen liquefaction unit for power supply. The system may advantageously comprise a hydrogen storage unit for intermittent storage of gaseous hydrogen. Further, the system may favourably comprise a battery for storage of power for providing additional power at moments of very high demand.
It is to be noted that a person skilled in the art will understand that for a designated liquid hydrogen production facility the above discussed electrolyser process
integration options will need to be optimized depending on the site location, infrastructure and specific application. Thus, multiple process schemes can be constructed around the basic building blocks of a hydrogen liquefaction facility fed by the process comprising an integrated electrolyser according to the present invention.
Detailed description of the drawings
In Figure 1, an example of the process according to the invention is schematically shown, which should not be interpreted as limiting the invention:
energy (e~) , essentially from renewable sources, is fed via an inlet (1) into an integrated electrolysis system (2), which comprises an energy storage part (3) and a
regeneration part (4); in the energy storage part of the electrolysis system a metal salt (MX) and water are
converted into the corresponding metal (M) , the
corresponding acid (HX) and oxygen; when needed ("on demand"), in the regeneration part (4) the metal salt is formed again and gaseous hydrogen (GH2) is released via outlet (5) , while optionally also producing electricity; the gaseous hydrogen is introduced via inlet (6) into the hydrogen liquefaction unit (7); the electricity from the electrolysis system may on demand be released via outlet
(8) to be used in the hydrogen liquefaction unit (7);
energy (e~) , essentially from renewable sources, is also used to power the hydrogen liquefaction unit (7) via inlet
(9) ; electricity may also be stored in a battery (10) for use to supply to the hydrogen liquefaction unit (7) in high demand situations or to supplement in case of low
availability of the renewable energy; liquid hydrogen (LH2) is exported from the system via line (11) .

Claims

C L A I M S
An integrated process for continuous production of liquid hydrogen, comprising (a) producing gaseous hydrogen by electrolysis; and
(b) liquefying said gaseous hydrogen in a hydrogen liquefaction unit, which liquefaction unit is powered by energy essentially from renewable sources; and,
(c) when additional power is needed, using electrical energy generated in a process in which electrical energy and hydrogen are co-generated by an integrated
electrolysis process comprising:
(d) electrolysing a metal salt or mixture of metal salts and water into the corresponding metal or metals, acid or acids, and oxygen
(electricity storage phase) , and
(e) producing gaseous hydrogen and recovering electricity in a regeneration reaction of the metal (s) and acid(s) of step (d) (regeneration phase) ; wherein at least part of the gaseous hydrogen generated in step (e) is used in step (b) of the process.
The process of claim 1, wherein the metal salt (s) is/are selected from ZnSC , MgSC , MgCl2, and the like.
The process of claim 2, wherein the metal salt is ZnSC .
The process of any one of claims 1-3, wherein the hydrogen and electricity products of step (e) are individually produced as needed "on-demand".
5. The process of any one of claims 1-4, wherein additional sources of electricity supply are used as back-up when the renewable power source is not available and/or electricity regenerated in step (e) is not enough.
6. The process of any one of claims 1-5, wherein gaseous hydrogen is stored after step (e) and before liquefying the hydrogen.
7. An integrated system for continuously producing liquid hydrogen, comprising an energy inlet for feeding energy from renewable sources into an electrolysis system for co-generation of electrical energy and hydrogen, which comprises an energy storage part and a regeneration part, wherein the regeneration part of the electrolysis system has an outlet for hydrogen that is connected to a hydrogen liquefaction unit and wherein the regeneration part of the electrolysis system has an outlet for electricity produced in the electrolysis system that is connected to an energy inlet into the hydrogen
liquefaction unit for power supply.
PCT/EP2015/074712 2014-10-28 2015-10-26 Process for producing liquid hydrogen Ceased WO2016066571A1 (en)

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BR112017007390A BR112017007390A2 (en) 2014-10-28 2015-10-26 integrated process and system for continuous production of liquid hydrogen.
US15/522,308 US20170321332A1 (en) 2014-10-28 2015-10-26 Process for producing liquid hydrogen
CN201580058397.2A CN107074538A (en) 2014-10-28 2015-10-26 Method for producing liquified hydrogen
ES201790014A ES2643558B1 (en) 2014-10-28 2015-10-26 PROCESS TO PRODUCE LIQUID HYDROGEN
AU2015340752A AU2015340752B2 (en) 2014-10-28 2015-10-26 Process for producing liquid hydrogen

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AU2015340752A1 (en) 2017-04-20
CL2017000975A1 (en) 2018-01-12
ES2643558B1 (en) 2018-09-19
ES2643558R1 (en) 2017-12-13
CN107074538A (en) 2017-08-18
US20170321332A1 (en) 2017-11-09
ES2643558A2 (en) 2017-11-23
BR112017007390A2 (en) 2018-02-14

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