A system and container for storage and transport of gaseous substances

Abstract

Provided is a gas storage system. Provides is a gas storage system and gas storage container for safely and efficiently storing gaseous substances, for transporting to a location for use, and for storage in-use for static and mobile applications. Provided is a gas storage system comprising an adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material.

Description

ENTITLEMENT

[0001] The application is related to and claimed the benefit of and priority to Australian Provisional Application 2024904339 filed 30 December 2024 entitled “A system and container for storage and transport of gaseous substances”, which is incorporated in its entirety by reference. FIELD

[0002] The present invention relates to a gas storage system. The present invention relates to use of gaseous substances. The invention further relates to a gas storage system and gas storage container for safely and efficiently storing gaseous substances, for transporting to a location for use, and for storage in-use for static and mobile applications. The invention further relates to a gas storage system comprising an adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material.

[0003] The invention has been developed for use in all types of gas storage containers. For example, ISO certified intermodal containers and for all types of gases including hydrogen, carbon dioxide, methane, natural gas, ammonia, oxygen, helium, argon, neon, nitrogen, medical gases, refrigerant gases, hospitality and food / beverage gas mixtures, welding gas mixtures, laser gas mixtures, acetylene, and others, and will be described hereinafter with reference to these applications. However, it will be appreciated that the invention is not limited to this field of use and may also be employed in other storage and transport applications and with other gases as set out below.

[0004] There is a need for a gas storage system comprising a gas storage container filled with an adsorbent material that can absorb volatile liquids such as ammonia and gases such as hydrogen, for example, at improved volumetric and gravimetric densities (for a given temperature and pressure) than possible at present through conventional gas compression, cryo-compression or liquefaction. The gas storage system should comprise enabling sub-systems to support energy efficient gas charging into the adsorbent-enabled gas storage container and enabling sub-systems to support energy efficient discharging of the adsorbent material-enabled gas storage container to downstream end-users at end-user proscribed pressure, temperature and gas purity grade conditions. The gas adsorbed upon the surface area of the pores of the 2 adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, results in an inherently safe gas storage system which, as discussed below, is critically important. BACKGROUND

[0005] Gaseous substances (gases) are very useful in society today and used extensively in a wide range of applications and are critical to innumerable industries, for example, as energy carriers including natural energy in the form of natural or fracked fossil gas, biomethane, biogas, natural hydrogen, stimulated hydrogen, or synthetically manufactured e-fuels such as green hydrogen from electrolysis or pyrolysis, and emethanol, e-methane or e-ammonia using green hydrogen. Additionally, some gasses are important feedstocks, for example, carbon-dioxide captured from direct-air-carbon-capture or industrial processes can be used as feedstock for the production of e-fuels such as e-methanol or e-methane, e-kerosene, e-diesel, or for food and beverage industry and other industrial processes. Many gases however are flammable, explosive, corrosive and / or unstable, so care is needed when processing, transporting, storing and using them. Most gases require storing under high pressure (compressed) or low temperature (liquefaction or supercritical), which is energy intensive.

[0006] Accordingly, storage and transport of gases is economically crucial. In addition, many gasses are flammable, explosive, corrosive and / or unstable, such that considerable care is required in their production, storage, transport and use. Most gases require storage under high pressure (compressed) or low temperature (liquefaction or supercritical), which is energy intensive.

[0007] It is common for gas to be transported in pipelines over long distances. These pipelines are typically made from carbon steel material or advanced plastic material and a coating to prevent corrosion or the like is applied. These gas pipelines are also typically highly pressurized from 100 bar to 150 bar compressed natural gas pipelines, and between 50 bar to 100 bar pressure for compressed hydrogen gas pipelines.

[0008] When pipelines cannot be used, gas is typically transported in a high-density state, typically as liquefied gas. For example, Liquefied Natural Gas (LNG) is stored at temperatures below -161 degrees Celsius and less than 1.25 bar pressure. LNG is transported by tanker ships and / or trucks / trains. An LNG tank typically includes a metallic outer vessel surrounding an inner metallic vessel and having a vacuum therebetween. A refrigeration system maintains low temperature. The gas storage 3 container usually includes gas filling and extraction systems and safety systems such as pressure relief valves for rapid release and decompression of the stored gas in an emergency. The most important aspect of gas transport is safety, as significant damage to human life and infrastructure can occur if there is a gas leak and / or explosion.

[0009] To facilitate easier trade of LNG, specialized “packaged gas” containers, in the form of ISO “tanktainers” or “ISO gas storage containers” (generally defined as systems which fit within a 8ft, 10ft, 20ft, 30ft, 40ft, or 45ft shipping container format, and are designed for intermodal bulk transport (road, rail and sea), and certified to multiple transport and geographic safety standards), have been developed. Packaged gas ISO gas storage containers also exist for liquid oxygen, liquid nitrogen, liquid argon, and liquid carbon dioxide.

[0010] Several challenges exist with existing gas storage technologies: (1) liquefaction is extremely energy intensive and adds significant cost to the gas storing process; (2) liquefied gas containers are typically actively cooled systems, requiring energy to maintain cold temperatures; (3) these systems have relatively short dormancy or dwell time should their active cooling systems fail creating safety hazards; (4) such systems are not commonly used for some gases such as hydrogen where high boil-off and short dormancy present a major hazard preventing safe autonomous (without human intervention) operation for road, rail and maritime applications; (5) boiloff for liquefied gases like LNG pose major environmental hazard.

[0011] Where liquefaction is not practical, high compression to 250 bar is presently utilised to store and transport natural gas, biogas / biomethane in the form of compressed natural gas (CNG) or compressed biogas / biomethane (CBG) , or extreme compression to 250 - 950 bar pressure, or cryo-compression (low temperature of 77 K, and extreme pressure to 400 bar) is being trialled, for some gases such as hydrogen, however, these high pressures limit the size of the pressure vessel that can operate safely, thereby limiting the total volume of gas which can be transported per tank or gas storage container, and high to extreme pressurisation is hazardous and energy intensive.

[0012] The limitations on the size of the tank or gas storage container prevents the potential to develop tanks or gas storage containers larger than 30 Litres, or 350 Litres or 700 Litres or 3000 Litres, or 4000 Litres in liquid volume which prevents the development of larger containment, such as bulk packaged gas storage containers, as limited by international safety and certification standards, and larger gas storage systems certifiable for static long duration storage, refuelling, bunkering and industrial 4 storage, and storage for road, rail and maritime vehicles and vessels, for other gases that cannot be liquefied easily, and where the only existing alternative is compression at extreme pressures at or greater than 250 bar pressure.

[0013] It is problematic that there are no certifiable intermodal containers for many gases for bulk storage and transport, such as hydrogen for intermodal (road, rail and maritime) bulk transport and distribution use that comply with international safety and certification standards.

[0014] At present, the storage and transport of ultra-high compressed gases, for example, hydrogen, is above 350 bar pressure, and is safely done at present only in small cylinders that are racked and manifolded into a ultra-high-pressure multi-elementgas-container (MEGC), for example in a 40 (4x10) or 65 (5x13) tank configuration, (depending on the liquid volume of the smaller tanks) to fit inside a larger container within a 8ft, or 10ft, or 20ft, or 30ft, or 40ft or 45ft ISO dimension. Importantly, these multi-element-gas containers are not certifiable for intermodal (road, rail and marine) transport. The MEGCs have significant safety drawbacks as reported by multiple major explosion incidents in the last few years, including high risk of leaks from the many valve points and piping manifolds that form part of the gas storage system, the overall pressure of the system (greater than 350 bar pressure), and resulting in additional loading / unloading time and expense. Reducing system pressure is key for safety.

[0015] At present, the storage and transport of compressed gases such as hydrogen at ultra-high pressures are not commercially viable given the low volumetric density (kg / m3) that can be stored and the cost and energy requirements of compression. For example, an extreme compressed MEGC of hydrogen gas at 350 bar pressure results in a maximum volumetric density of about 20 kg / m3. Storage at high or extreme compression is also difficult to scale the size or diameter of the pressure vessel of a gas storage container, because the wall thickness required for compression limits the size or diameter of the pressure vessel component which can be manufactured and transported.

[0016] The storage and transport of gases in liquefied form also presents safety challenges, has high cost and energy requirements. Additional energy is required for active cooling to maintain cold temperatures for long periods during storage and transport.

[0017] Where gases are stored and transported in large volumes in compressed or liquefied form, additional safety systems are required as well as continuous monitoring, increasing their expense and complexity. The existing international standards for transport by rail, road and sea also have requirements for the safe performance of the gas storage container and related materials to ensure safety. The safety profile of existing gas storage does not meet industry acceptance for some gases, for example, for hydrogen, there is no RID (International Carriage of Dangerous Goods by Rail) certified bulk-transporter railcar which has been successfully developed and certified globally to date, due to the safety hazards current solutions present.

[0018] For gases stored at extremely low, cryogenic temperatures, for example below -100 degrees Celsius, presently, additional active cooling systems are required to maintain the low temperatures because these systems have “short dormancy”. This means that when unpowered, the gas storage container will warm up over 2-3 days for large format 21,000 - 50,000 Litre gas storage container. This causes the pressure in the gas storage container to increase as the gas expands, increasing the likelihood of an explosion. The energy requirements to maintain the cold temperatures are significant. For example, for hydrogen, energy required for cooling to -253 degrees Celsius is approximately 15 kWh / kg of hydrogen stored, which is 45% of the energy value of liquefied hydrogen gas stored. Further energy on top of this is required to maintain extremely cold temperatures, increasing risk and decreasing commercial viability. An additional concern in the case of hydrogen is that spontaneous gasification occurs even when liquid hydrogen is below its liquefaction temperature causing boiloff of between 1-6% per day. Other gases such as liquid oxygen, helium, argon, and carbon dioxide, for example, also have short holding or dwell or dormancy time.

[0019] Furthermore, gas storage containers designed for large-scale terrestrial or bulk super-carrier storage for ship-based tankers only exist for a few gases including methane / LNG, ammonia, and acetylene. Trial shipping tankers for liquefied hydrogen gas have been tested but are prohibitively expensive and continue to suffer large boil-off of between 1-6% per day. The best large scale gas storage containment systems for LNG have managed to reduce boil-off to 0.07% unit Volume per day, however, even at large scale with cutting edge technology, boiloff is still present, a key source of economic losses and fire risk for gas transporters.

[0020] The materials used in high pressure gas storage systems, including systems operating at very low temperatures, are also subject to corrosion and metal embrittlement. For example, the inner vessel or pressure vessel component in gas storage containers made of carbon-steels that are used to store hydrogen, can embrittle 6 over time, with microcracking fractures, that can reduce the useful life of the inner pressure vessel component in the gas storage container, and cause gas leaks and possible catastrophic failure and loss of containment of the gas stored from the gas storage container, and result in explosions.

[0021] Accordingly, there is a need for safe gas storage systems for the storage and transport via all types of transport systems, including ships, rail and truck carriers, for gases such as hydrogen, carbon dioxide, methane (including biomethane), natural gas, biogas, ammonia, oxygen, helium, neon, argon, nitrogen, medical gases, refrigerant gases, hospitality and food / beverage gas mixtures, welding gas mixtures, laser gas mixtures, acetylene, and other such gases.

[0022] For cryo-gas storage, such a gas storage container would ideally remain safe without human intervention, operate autonomously or without human intervention, be passively cooled, maintaining hold or dwell or dormancy temperature for at least 3 days and up to 60+ days at a time, which means 60+ days dormancy / dwell time / hold time. Such a container should also be safely constructed so that it can withstand impacts without opening and releasing the contents. The stored gas would not exhibit boiloff during this hold or dwell or dormancy period, and would be able to maintain its temperature, potentially passively. Such a container would operate at lower pressures less than 100 bar pressure, or less than 50 bar pressure, while maintaining high volumetric densities greater than 20 kg / m3 in the case of hydrogen storage.

[0023] For ambient temperature pressurised gas storage, such a gas storage container would ideally remain safe without human intervention and operate at pressures of less than 60 bar while maintaining a high volumetric density greater than 150 kg / m3 in the case of biomethane storage.

[0024] For the avoidance of doubt, reference to any prior art in the specification is not an acknowledgement or suggestion that this prior art forms part of the common general knowledge in any jurisdiction or that this prior art could reasonably be expected to be combined with any other piece of prior art by a skilled person in the art. SUMMARY

[0025] It is an object of the present invention to substantially overcome, or at least ameliorate, one or more of the disadvantages of existing systems / products, or at least provide a useful alternative.

[0026] There is disclosed herein a gas storage system comprising: a gas storage container (e.g. tank, vessel, inner vessel / shell and outer shell for refrigerated / cryogenic gas storage containers, and the like) comprising, consisting of, or containing one or more adsorbent materials, including one or more nanoporous, microporous, or mesoporous adsorbent materials. There is further disclosed herein a system for storing hydrogen gas comprising: a gas storage container comprising at least one adsorbent material configured to induce a switch from ortho-hydrogen to para-hydrogen, and maintain the para-hydrogen spin-state, once switched.

[0027] The adsorbent material may comprise one or more nanoporous, microporous, or mesoporous adsorbent materials. A “nanoporous adsorbent material” as used herein refers to an adsorbent material in which the pore width is greater than or equal to 0.1 nm to 100 nm. A microporous adsorbent material as used herein refers to an adsorbent material in which the pore width is less than or equal to 2 nm. A mesoporous adsorbent material as used herein refers to an adsorbent material in which the pore width is greater than 2 nm to 50 nm.

[0028] The adsorbent material may comprise one or more Metal-Organic-Framework (MOF) materials, Covalent-Organic-Framework (COF) materials, MOF-composite materials, MOF-hybrid materials, and / or MOF-hybrid-composite materials. As used herein, a “MOF-composite material” comprises one or more MOF materials, or one or more MOF materials and one or more COF materials. As used herein, a “MOF-hybrid material” comprises one or more MOF materials and one or more advanced carbon allotropic dopants, particles of carbon allotropes, graphene, graphene oxides, carbon nanotubes, and fullerenes. The MOF-hybrid material may comprise or consist of one or more MOF materials and one or more advanced carbon allotropic dopants. As used herein, a “MOF-hybrid-composite material” comprises one or more MOF materials, one or more COF materials, and one or more advanced carbon allotropic dopants, graphene, graphene oxides, carbon nanotubes, and fullerenes. The MOF-hybrid-composite material may comprise one or more MOF materials, one or more COF materials, and one or more advanced carbon allotropic dopants.

[0029] The nanoporous, microporous, or mesoporous absorbent material may comprise one or more MOF materials, COF materials, MOF-composite-material, MOF-hybrid materials, and / or MOF-hybrid-composite materials.

[0030] The adsorbent material may be a nanoporous absorbent material. The nanoporous absorbent material may comprise one or more MOF materials, COF materials, MOF-composite-material, MOF-hybrid materials, and / or MOF-hybrid-composite materials. The nanoporous absorbent material may comprise one or more MOF materials.

[0031] There is disclosed herein a gas storage system including a gas storage container comprising an outer shell surrounding an inner shell, a vacuum and / or insulation there between, the outer shell made of either metal or a carbon fibre composite material and the inner shell comprising either metal alloy that inhibit corrosion or embrittlement over time metal (Type-I) or metal wrapped with carbon-fibre composite (Type-II or Type-III), or polymer wrapped with carbon-fibre composite (Type-IV) or carbon-fibre composite material (Type-V), the gas storage container being filled with one or more adsorbent materials, including one or more nanoporous, microporous, or mesoporous adsorbent materials. The one or more adsorbent materials, including one or more nanoporous, microporous, or mesoporous adsorbent materials, may comprise one or more one or more Metal-Organic-Framework (MOF) materials, Covalent-Organic-Framework (COF) materials, MOF-composite materials, MOF-hybrid materials, and / or MOF-hybrid-composite materials.

[0032] There is disclosed herein a gas storage system including a gas storage container comprising an outer shell surrounding an inner shell, a vacuum and / or insulation there between, the outer shell made of either metal or a carbon fibre composite material and the inner shell comprising either metal alloy that inhibit corrosion or embrittlement over time metal (Type-I) or metal wrapped with carbon-fibre composite (Type-II or Type-III), or polymer wrapped with carbon-fibre composite (Type-IV) or carbon-fibre composite material (Type-V), the gas storage container being filled with a Metal-Organic-Framework (MOF) nanoporous material, a MOF-hybrid nanoporous material, MOF-composite nanoporous material, or a MOF-hybrid-composite nanoporous material which is highly adsorbent (high adsorbent corresponding to adsorbent thresholds for the gas at > 37.5 to>77.5 g(hydrogen) / L at 85 - 25 K respectively and 30 bar pressure charge conditions for hydrogen, or an adsorbent threshold of >140 g(methane / biomethane / natural gas / biogas) / L to 240 g(methane / biomethane / natural gas / biogas) / L at 298 K and 50 bar pressure, or around greater than >155 g(methane / biomethane / natural gas / biogas) / L at 298 K and 50 bar pressure for methane / biomethane / natural gas / biogas), the adsorbent material being adapted in use to adsorb and release gas upon operation of the system by a user.

[0033] There is disclosed herein a gas storage system including a gas storage container comprising an outer shell surrounding an inner shell, a vacuum and / or insulation there 9 between, the outer shell made of either metal or a carbon fibre composite material and the inner shell comprising either metal alloy that inhibit corrosion or embrittlement over time metal (Type-I) or metal wrapped with carbon-fibre composite (Type-II or Type-III), or polymer wrapped with carbon-fibre composite (Type-IV) or carbon-fibre composite material (Type-V), the gas storage container being filled with an adsorbent material.

[0034] Different types of materials of the inner shell (Types-I, II, III, IV, or V) can be combined with different types of materials of the outer shell (made of either metallic or carbon-fibre composite materials), in various combinations, to form a part of the gas storage system.

[0035] There is further disclosed herein a gas storage system including a gas storage container comprising a single wall, double wall or triple wall. The single wall, double wall or triple wall may be made, for example of 304 or 316 stainless steel, aluminium, titanium alloy, or other metal alloys. The single wall, double wall or triple wall may be made of Type-I materials. The single wall, double wall or triple wall may be made of 304 or 316 stainless steel, aluminium, or titanium alloy. The single wall, double wall or triple wall may be made of other metal alloys that inhibit corrosion or embrittlement over time. The single wall, double wall or triple wall may be made of metal wrapped with carbonfibre composite (Type-II or Type-III). The single wall, double wall or triple wall may be made of polymer wrapped with carbon-fibre composite (Type-IV). The single wall, double wall or triple wall may be made of carbon-fibre composite material (Type-V). The gas storage container may be filled with a nanoporous, microporous or mesoporous adsorbent material, which may comprise one or more Metal-Organic-Framework (MOF) materials, Covalent-Organic-Framework (COF) materials, MOF-composite materials, MOF-hybrid materials, and / or MOF-hybrid-composite materials. See FIG. 1 and FIG. 2.

[0036] There is further disclosed herein a gas storage system including a gas storage container comprising a single wall, made of 316 stainless steel or other metal alloys that inhibit corrosion or embrittlement over time (Type-I), or metal wrapped with carbonfibre composite (Type-II or Type-III), or polymer wrapped with carbon-fibre composite (Type-IV), or carbon-fibre composite material (Type-V), the gas storage container being filled with a nanoporous MOF material, a nanoporous MOF-hybrid material, a nanoporous MOF-composite material, or a nanoporous MOF-hybrid-composite materials, which is highly adsorbent, the adsorbent material being adapted in use to adsorb and release gas upon operation of the system by a user.

[0037] The gas storage container may comprise a single wall, double wall or triple wall.

[0038] The gas storage container may be made of 316 stainless steel, or aluminium, titanium alloy, or other metal alloy that inhibits corrosion or embrittlement. The gas storage container may be made of 316 stainless steel, or aluminium, or titanium alloy.

[0039] There is further disclosed herein a method for charging gas to a container comprising one or more adsorbent materials, comprising recirculating the gas through the container via a recirculation loop, wherein the gas is cooled in the recirculation loop.

[0040] There is further disclosed herein a method for decanting gas from a container comprising one or more adsorbent materials, comprising recirculating the gas through the container via a recirculation loop, wherein the gas is heated in the recirculation loop.

[0041] There is further disclosed herein a method for activating an absorbent material for use in a gas storage container, comprising: a first stage whereby the adsorbent material is heated to a first activation temperature configured to evacuate solvents and other contaminants from activation sites of the adsorbent material under a flow of hot dry nitrogen, or a flow of hot dry air, and / or under a vacuum of hardness of about 10-3 mbar, conducted ex-situ, prior to loading the adsorbent material into the gas storage container; and a second stage whereby the adsorbent material is subjected to a second activation temperature in-situ after loading the adsorbent material into the gas storage container, at around 120oC under a flow of hot dry nitrogen, or a flow of hot dry air, and / or under vacuum of hardness of about 10-3 mbar.

[0042] There is further disclosed herein a system for storing hydrogen gas comprising a gas storage container comprising at least one adsorbent material configured to induce a switch from ortho-hydrogen to para-hydrogen, and maintain the para-hydrogen spinstate, once switched.

[0043] Without being bound by theory, the inventor believes adsorbent material, including the nanoporous, microporous or mesoporous adsorbent material, may adsorb the gas molecule upon the inner surface of the porous materials without any change in chemical structure of the gas molecule itself. The binding energies may be relatively small (e.g. a fraction of a chemical bond), may be easily reversible with up to 100% recovery with small changes in temperature and / or pressure, enabling the release of the gas when required. BRIEF DESCRIPTION OF DRAWINGS

[0044] The disclosure will now be described by way of example only and with reference to the accompanying drawings.

[0045] FIG. 1 is a section view of a double wall gas storage container containing nanoporous, microporous or mesoporous adsorbent material.

[0046] FIG. 2 is a section view of a double wall gas storage container containing nanoporous, microporous or mesoporous physisorption material.

[0047] FIG. 3 is a front view of a double walled vertical gas storage container containing nanoporous, microporous or mesoporous physisorption material.

[0048] FIG. 4 is a top view of the gas storage container of FIG. 3.

[0049] FIG. 5 is an example process and instrumentation diagram for the double wall gas storage container of FIG. 3.

[0050] FIG. 6 is an example process and instrumentation diagram of a double walled vacuum insulated horizontal gas storage container containing nanoporous, microporous or mesoporous adsorbent material.

[0051] FIG. 7 is a process flow diagram of an example charging subsystem for the gas storage system.

[0052] FIG. 8 is a process and instrumentation diagram of an example charging subsystem for the gas storage system.

[0053] FIG: 9 is a process flow diagram of an example charging subsystem for the gas storage system.

[0054] FIG. 10 is a process and instrumentation diagram of an example decanting subsystem for the gas storage system.

[0055] FIG. 11 is a process and instrumentation diagram of an alternative example decanting subsystem for the gas storage system.

[0056] FIG. 12 is a process and instrumentation diagram of an alternative example decanting subsystem for the gas storage system.

[0057] FIG. 13 is a process flow diagram of an example activation subsystem for the gas storage system.

[0058] FIG. 14 is a process and instrumentation diagram of an example activation subsystem for the gas storage system.

[0059] FIG. 15 is a process and instrumentation diagram of an example decanting subsystem for the gas storage system involving multiple gas storage containers.

[0060] FIG. 16 is a process and instrumentation diagram of an alternative example decanting subsystem for the gas storage system involving multiple gas storage containers.

[0061] FIG. 17 is a plot of the Dual-Langmuir model fitted to measured isotherms for [Cu3BTC2].

[0062] FIG. 18 is a plot of the Dual-Langmuir model fitted to measured isotherms for CuII3[CoIII(CN6)]2.

[0063] FIG. 19 is a plot of the Virial model fitted to measured isotherms for [Cu3BTC2.]

[0064] FIG. 20 is a plot of the Virial model fitted to measured isotherms for CuII3[CoIII(CN6)]2;

[0065] FIG. 21 is a plot of the Virial heat of charging for [Cu3BTC2.].

[0066] FIG. 22 is a plot of the Virial heat of charging for CuII3[CoIII(CN6)]2.

[0067] FIG. 23 shows the results of physically validated thermal modelling using Computational Fluid Dynamics for a 20,000 Litre adsorbent material-filled gas storage container. FIG. 23 (A) shows an dynamic fill operating mode where pressure is allowed to slowly reach target pressure over 360 minutes. FIG. 23 (B) shows a static fill mode where pressure is reached in about 20 minutes, and after this, the gas storage container reaches equilibrium adiabatically.

[0068] FIG. 24 is a plot of a modelled charging profile.

[0069] FIG. 25 is a plot of a modelled decanting profile.

[0070] FIG. 26 is a plot of a modelled decanting profile.

[0071] FIG. 27 is a plot of a modelled decanting profile.

[0072] FIG. 28 (A) is a plot of gas storage and dormancy as a function of charge pressure for a 1000 L gas storage container, FIG28 (B) is the plot for a 20,000L gas storage container.

[0073] FIG. 29 (A) is a plot of gas storage and dormancy as a function of charge pressure for a 1000 L gas storage container, FIG29 (B) is the plot for a 20,000L gas storage container.

[0074] FIG. 30 (A) is a plot of gas storage and dormancy as a function of charge temperature for a 1000 L gas storage container, FIG 30 (B) is the plot for a 20,000L gas storage container.

[0075] FIG. 31 is a plot of the Dul-Langmuir model of pure component isotherms for methane and hydrogen on CuII3[CoIII(CN6)]2.

[0076] FIG. 32 is a binary IAST selection curve as a function of pressure for methane and hydrogen on CuII3[CoIII(CN6)]2;

[0077] FIG. 33 is a binary IAST selection curve as a function of pressure for methane and hydrogen on CuII3[CoIII(CN6)]2 at an alternative gas composition to FIG. 32.

[0078] FIG. 34 is a binary IAST selection curve as a function of methane composition for methane and hydrogen on CuII3[CoIII(CN6)]2.

[0079] FIG. 35 is a binary IAST selection curve as a function of hydrogen composition for methane and hydrogen on CuII3[CoIII(CN6)]2.

[0080] FIG. 36 is a plot of adsorbed phase for methane and hydrogen on CuII3[CoIII(CN6)]2.

[0081] FIG. 37 is a plot of packing fraction as a function of coarse particle volume fraction.

[0082] FIG. 38 is a plot of packing fraction as a function of size ratio.

[0083] FIG. 39 is a plot comparing storage capacity of the gas storage system to a bare gas storage container at different pressures.

[0084] FIG. 40 is a plot comparing storage capacity of the gas storage system to a bare gas storage container at different temperatures.

[0085] FIG. 41 is a plot of a field trial decanting profile.

[0086] FIG. 42 is a plot comparing deliverable gas capacity for the gas storage system to a bare gas storage container.

[0087] FIG. 43 is a plot of deliverable capacity as a function of packing fraction.

[0088] FIG. 44 is a plot of deliverable capacity as a function of discharge temperature.

[0089] FIG. 45 is a plot comparing deliverable capacity as a function of discharge temperature for the gas storage system and a bare gas storage container.

[0090] FIG. 46 is a plot of deliverable capacity as a function of packing fraction and discharge temperature.

[0091] FIG. 47 is thermogravimetric analysis (TGA) demonstrating experimental results of activation of an adsorbent.

[0092] FIG. 48 is thermogravimetric analysis (TGA) demonstrating experimental results of activation of an adsorbent.

[0093] FIG. 49 is thermogravimetric analysis (TGA) demonstrating experimental results of activation of an adsorbent.

[0094] FIG. 50 is a plot of adsorbent uptake cycles, 100 cycles conducted between 1 and 30 bar pressure at 298 K, with a single evacuation reactivation cycle before the 50th cycle (conducted at 10-3 mbar). The cycling shows that performance is restored using just evacuation at 10-3 mbar, and that impurities which are trapped in the adsorbent do not affect the adsorbent performance for the target gas, in this case, hydrogen.

[0095] FIG. 51 Two stage activation protocol using thermogravimetric analysis. FIG. 51 (A) shows the first stage ex-situ activation of adsorbent materials with high activation temperatures, using [(Fem2FeH(j3-O))2(ABTC)3] as an exemplar adsorbent material with high activation temperature. FIG. 51 (B) shows the adsorbent material behaviour when exposed to air for 6000 minutes. FIG. 51 (C) shows the efficacy of the second stage insitu activation

[0096] FIG. 52 Gravimetric hydrogen uptake for (a) [Cu2(ABTC)] (b) [Cu3BTC2] (c) [(Al"I3(|J3-O))2(ABTC)3].|(NO3)2| (d) cubic CuII3[CoIII(CN6)]; all at 77 K, and between 0 -100 bar pressure.

[0097] FIG. 53 Volumetric hydrogen uptake for (a) [Cu3BTC2] and (b) cubic CuII3[CoIII(CN6)] (c) bare gas storage container without adsorbent; at 77 K, and between 0 - 100 bar pressure.

[0098] FIG. 54 Volumetric methane uptake for (a) [Cu3BTC2] and (b) cubic CuII3[CoIII(CN6)] (c) bare gas storage container without adsorbent; at 298 K, and between 0 - 100 bar pressure.

[0099] FIG. 55 is a flowchart of a method for charging gas to a gas storage container comprising one or more adsorbent materials.

[0100] FIG. 56 is a flowchart of a method for decanting gas from a gas storage container comprising one or more adsorbent materials.

[0101] FIG. 57 is a flowchart of a method for activating one or more adsorbent materials for use in a gas storage container. DETAILED DESCRIPTION

[0102] This disclosure may also be said broadly to consist in the parts, elements and features referred to or indicated in the specification of the application, individually or collectively, and any or all combinations of any two or more said parts, elements or features. Where specific integers are mentioned herein which have known equivalents in the art to which this disclosure relates, such known equivalents are deemed to be incorporated herein as if individually described.

[0103] The words “comprise,” “comprises” and “comprising” are to be interpreted inclusively rather than exclusively. Likewise, the terms “include,” “including”, “contain”, “containing”, “have”, “having” and “or” should all be construed to be inclusive, unless such a construction is clearly prohibited from the context. Nevertheless, the compositions and methods disclosed herein may lack any element that is not 15 specifically disclosed herein. Thus, a disclosure using the term “comprising” includes a disclosure of “consisting essentially of” and “consisting of” the components or steps identified. The phrase “consisting of” is understood to be exclusive in that it excludes any element not specified in the claim or disclosure and the phrase “consisting essentially of” is understood as including additional elements that do not materially alter a characteristic of a composition or process.

[0104] The terms “a” and “an” used herein are intended to be understood as meaning one or more unless explicitly stated otherwise.

[0105] It is intended that reference to a range of numbers disclosed herein (for example, 1 to 10) also incorporates reference to all rational numbers within that range and any range of rational numbers within that range (for example, 1 to 6, 1.5 to 5.5 and 3.1 to 10). Therefore, all sub-ranges of all ranges expressly disclosed herein are hereby expressly disclosed.

[0106] As used herein the term ‘(s)’ following a noun means the plural and / or singular form of that noun.

[0107] As used herein, “about” is understood to refer to numbers in a range of numerals, for example, at most the range of -10% to +10% of the referenced number. The range of numerals may be -5% to +5% of the referenced number, may be -1% to +1% of the referenced number, or may be -0.1% to +0.1% of the referenced number. For the avoidance of doubt, when a numeral is referred to herein with “about” also disclosed is the reference numeral. For example, “about 20” includes a disclosure of “20”.

[0108] As used herein, “approximately” is understood to refer to numbers in a range of numerals, for example, at most the range of -5% to +5% of the referenced number. The range of numerals may be -1% to +1% of the referenced number, or may be -0.1% to +0.1% of the referenced number. For the avoidance of doubt, when a numeral is referred to herein with “approximately” also disclosed is the reference numeral. For example, “approximately 20” includes a disclosure of “20”.

[0109] The term “and / or” used in the context of “X and / or Y” should be interpreted as “X,” or “Y,” or “X and Y.” Similarly, “at least one of X or Y” should be interpreted as “X,” or “Y,” or “X and Y.” For example, “MOF material and / or COF material” should be interpreted as “MOF material” or “COF material,” or “both MOF material and COF material.”

[0110] Where used herein, the terms “example” and “such as,” particularly when followed by a listing of terms, are merely exemplary and illustrative and should not be deemed to be exclusive or comprehensive.

[0111] As used herein, the term “storage container” as used herein refers to and includes a “gas storage container”, a “gas storage tank”, a “gas storage vessel”. Accordingly, as will be understood by the skilled person the term “container” may be used interchangeably with the terms understood by the skilled person to be for example, a container, a tank, or a vessel. No difference is intended or to be understood by these terms. Accordingly, a disclosure relating to “storage container” applies equally to a container, a tank, a vessel, a gas storage container, a gas storage tank, or a gas storage vessel.

[0112] There is disclosed herein a gas storage system comprising: a gas storage container comprising, consisting of, or containing one or more adsorbent materials. The one or more adsorbent materials may comprise one or more nanoporous, microporous, or mesoporous adsorbent materials. Adsorbent Materials

[0113] The one or more adsorbent materials may comprise one or more Metal-Organic-Framework (MOF) materials, Covalent-Organic-Framework (COF) materials, MOF-composite materials, MOF-hybrid materials, and / or MOF-hybrid-composite materials.

[0114] The nanoporous, microporous, or mesoporous absorbent material may comprise one or more MOF materials, COF materials, MOF-composite-material, MOF-hybrid materials, and / or MOF-hybrid-composite materials.

[0115] The adsorbent material may be a nanoporous absorbent material. The nanoporous absorbent material may comprise one or more MOF materials, COF materials, MOF-composite-material, MOF-hybrid materials, and / or MOF-hybrid-composite materials. The nanoporous absorbent material may comprise one or more MOF materials.

[0116] The absorbent material may comprise one or more nanoporous, microporous, and / or mesoporous MOF materials, nanoporous, microporous, and / or mesoporous COF materials, nanoporous, microporous, and / or mesoporous MOF-composite materials, nanoporous, microporous, and / or mesoporous MOF-hybrid materials, and nanoporous, microporous, and / or mesoporous MOF-hybrid-composite materials. The adsorbent 17 material may comprise two or more MOF materials. The two or more MOFs may be combined during or after synthesis.

[0117] Many such adsorbent materials are known and continue to be developed. Disclosed are methods to design the gas storage system for any suitable adsorbent materials or adsorbents for a target gas or gases. Examples 1 to 4 provide a method to characterise an adsorbent and predict the charging, decanting and dormancy behaviour of a gas storage system, allowing the gas storage system to be designed in accordance with that behaviour as well as user requirements.

[0118] The adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may be a pressed pellet, monolith, megalith or macroscopic single crystal powder. As used herein a “megalith” refers to a MOF that is greater than about 3 mm across its smallest dimension. As used herein a “monolith” refers to a MOF that is 3 mm or less across its smallest dimension. The adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may be formed as regular 3D polygons. The regular 3D polygons may be cubes and / or spheres. The regular 3D polygons may be of a single size. The regular 3D polygons may be of two differing sizes. The regular 3D polygons may be of three differing sizes. The regular 3D polygons may be of more than three differing sizes. The size ratio between differing sizes may be less than 0.16. The size ratio between differing sizes may be less than 0.159. The size ratio between differing sizes may be less than 0.158. The size ratio between differing sizes may be less than 0.157. The size ratio between differing sizes may be less than 0.156. The size ratio between differing sizes may be less than 0.155. The size ratio between differing sizes may be less than 0.154. The size ratio between differing sizes may be less than 0.153. The size ratio between differing sizes may be less than 0.152. The size ratio between differing sizes may be less than 0.151. The size ratio between differing sizes may be less than 0.15. The size ratio between differing sizes from about 0.05 to about 0.5, or from about 0.08 to about 0.3, or from about 0.1 to about 0.2.

[0119] The adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may be highly porous. Highly porous as used herein is refers to a surface area of at least about 700 m2 / g, or at least about 1,600 m2 / g to adsorb gas.

[0120] The adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may have a surface area of at least about 800 m2 / g to about 7900 m2 / g to absorb gas.

[0121] The adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may have at least about 700 m2 / g of surface area or more, at least about 1000 m2 / g of surface area or more, at least about 1,300 m2 / g of surface area or more, at least about 1,500 m2 / g of surface area or more, at least about 1,600 m2 / g of surface area or more, at least about 1,700 m2 / g of surface area or more, at least about 1,800 m2 / g of surface area or more, or at least about 1,900 m2 / g of surface area or more to adsorb gas. The adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may have at least about 2,000 m2 / g of surface area or more, at least about 2,100 m2 / g of surface area or more, at least about 2,200 m2 / g of surface area or more, at least about 2,300 m2 / g of surface area or more, at least about 2,400 m2 / g of surface area or more, at least about 2,500 m2 / g of surface area or more, at least about 2,600 m2 / g of surface area or more, at least about 2,700 m2 / g of surface area or more, at least about 2,800 m2 / g of surface area or more, at least about 2,900 m2 / g of surface area or more to adsorb gas.

[0122] The adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may have at least about 3000 m2 / g of surface area or more, at least about 3100 m2 / g of surface area or more, at least about 3200 m2 / g of surface area or more, at least about 3300 m2 / g of surface area or more, at least about 3400 m2 / g of surface area or more, at least about 3500 m2 / g of surface area or more, at least about 3600 m2 / g of surface area or more, at least about 3700 m2 / g of surface area or more, at least about 3800 m2 / g of surface area or more, at least about 3900 m2 / g of surface area or more to adsorb gas.

[0123] The adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may have at least about 4000 m2 / g of surface area or more, at least about 4100 m2 / g of surface area or more, at least about 4200 m2 / g of surface area or more, at least about 4300 m2 / g of surface area or more, at least about 4400 m2 / g of surface area or more, at least about 4500 m2 / g of surface area or more, at least about 4600 m2 / g of surface area or more, at least about 4700 m2 / g of surface area or more, at least about 4800 m2 / g of surface area or more, at least about 4900 m2 / g of surface area or more to adsorb gas.

[0124] The adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may have at least about 5000 m2 / g of surface area or more, at least about 5100 m2 / g of surface area or more, at least about 5200 m2 / g of surface area or more, at least about 5300 m2 / g of surface area or more, at least about 5400 m2 / g of 19 surface area or more, at least about 5500 m2 / g of surface area or more, at least about 5600 m2 / g of surface area or more, at least about 5700 m2 / g of surface area or more, at least about 5800 m2 / g of surface area or more, at least about 5900 m2 / g of surface area or more to adsorb gas.

[0125] The adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may have at least about 6000 m2 / g of surface area or more, at least about 6100 m2 / g of surface area or more, at least about 6200 m2 / g of surface area or more, at least about 6300 m2 / g of surface area or more, at least about 6400 m2 / g of surface area or more, at least about 6500 m2 / g of surface area or more, at least about 6600 m2 / g of surface area or more, at least about 6700 m2 / g of surface area or more, at least about 6800 m2 / g of surface area or more, at least about 6900 m2 / g of surface area or more to adsorb gas.

[0126] The adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may have at least about 7000 m2 / g of surface area or more, at least about 7100 m2 / g of surface area or more, at least about 7200 m2 / g of surface area or more, at least about 7300 m2 / g of surface area or more, at least about 7400 m2 / g of surface area or more, at least about 7500 m2 / g of surface area or more, at least about 7600 m2 / g of surface area or more, at least about 7700 m2 / g of surface area or more, at least about 7800 m2 / g of surface area or more, at least about 7900 m2 / g of surface area or more to adsorb gas.

[0127] The adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may have a heat of adsorption of less than 0 kJ / mol. By this arrangement, adsorption of gas molecules on the surface of the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may be an exothermic process.

[0128] The adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may have a heat of desorption of greater than 0 kJ / mol. By this arrangement, desorption of gas molecules from the surface of the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may be an endothermic process.

[0129] The adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may have a heat of desorption of from about 0 kJ / mol to about -51 kJ / mol. In general, selecting or configuring adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, with a relatively low Heat of Adsorption may promote energy efficiency of the gas storage system. The gas storage container may be used to store gases a low temperature. For example, adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, for use in a gas storage system at low-pressure gas storage cryogenic conditions may have a Heat of Adsorption of less than about -10 kJ / mol. The adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, for use in a gas storage system at low-pressure gas storage at cryogenic conditions may have a heat of adsorption of from about -3 kJ / mol to about -10 kJ / mol, from about -4 kJ / mol to about -10 kJ / mol, from about -5 kJ / mol to about -10 kJ / mol, from about -6 kJ / mol to about -10 kJ / mol, from about -7 kJ / mol to about -10 kJ / mol, from about -8 kJ / mol to about -10 kJ / mol, from about -9 kJ / mol to about -10 kJ / mol, from about -3 kJ / mol to about -9 kJ / mol, from about -3 kJ / mol to about -8 kJ / mol, from about -3 kJ / mol to about - 7 kJ / mol, from about -3 kJ / mol to about -6 kJ / mol, from about -3 kJ / mol to about -5 kJ / mol, from about -3 kJ / mol to about -4 kJ / mol, from about -4 kJ / mol to about -8 kJ / mol, from about -5 kJ / mol to -7 kJ / mol.

[0130] The adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may be selected from a mechanically robust material. A mechanically robust material may substantially maintain pore structure when exposed to external shock, shaking and / or vibrations (e.g. those conditions the materials may be typically exposed to during transport) and / or in high volumes (e.g. multiple tons of adsorbent material within a single gas storage container), and withstand up to 70 N of compressive force. Substantially maintaining pore structure of the adsorbent material is understood to mean that at least about 85%, at least about 90%, or at least about 95% of the pore structure of the adsorbent material is maintained in comparison to the pore structure of the adsorbent material prior to exposure to external shock, shaking and / or vibrations. A person skilled in the art will understand that gas storage containers can be used in a wide variety of applications including for terrestrial large-scale industrial storage, and for bulk transport both as carrier transporters and as on-ship or on-vehicle or on-rail fuel tanks, and as such. All components of these tanks are generally mechanically robust to withstand shock and vibration, as a safety critical asset, especially for highly flammable gases such as methane and hydrogen. The gas storage container disclosed herein are suitable for such uses. The adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, within the gas storage container may withstand external shock and vibrational forces, including being 21 mechanically robust enough to hold its own pore structure under its own weight both statically, and when moving (when the gas storage container is being used as a bulk transporter, or installed on a vehicles (such as light commercial vehicles or trucks), locomotives and other rail based vehicles, marine vehicles and other maritime craft, or aircraft. For example, within the context of a gas storage container that may be a 20ft ISO bulk gas transporter, between 8 and 17 tonnes of the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may be required to fill the volume inside the gas storage container. The pore volume of the adsorbent material at the bottom of the gas storage container may be retained under the weight of adsorbent material above it.

[0131] The adsorbent material may be a chemically robust material. A chemically robust material may maintain surface area, pore volume, and / or active sites of adsorption, and sorption performance for a target gas, even when exposed to gases with impurities. A person skilled in the art will understand that gas storage containers can be exposed to a wide variety of gas purities, and that all materials which come into contact with gas impurities within input gases should retain their surface area, their pore volume and / or their activity of their sites of adsorption. The gas storage container disclosed herein are suitable for such uses, including adsorption of gas with impurities. Impurities may include water, CO2, CH4, O2, CO, NH3, and / or H2S. For example, under hydrogen fuel cell grade standards, gas transporter must minimise the presence of common impurities such as water, CO2, CH4, O2, and uncommon impurities such as CO, NH3, H2S and other sulphurous gaseous impurities, and other gases typical in gas streams. An improvement of the systems disclosed herein may be that if gas impurities are present in the inbound gas during charging, those gases may be trapped by the adsorbent material without impacting the activity of sites of adsorption, shown in FIG. 5 and FIG. 6. Furthermore, removal of these trapped impurities can be done by simply applying a low-grade industrial vacuum, for example at about 10-3 mbar, on the gas storage container during gas storage container maintenance. The vacuum may be up to about 12 hours, up to about 6 hours, up to about 3 hours, or up to about 1 hour. The vacuum may be for at least about 1 hour. As impurities may be trapped and removed, the systems disclosed herein can act as a gas purification system. Purification of a gas may protect devices which are exposed to the gas downstream of transport.

[0132] The structure of the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, can be designed using crystal engineering at the point of crystal synthesis to optimise the adsorption of specific gases. A specific adsorbent material may be selected for a specific gas storage. The adsorbent materials may show multi-gas storage properties, and in this case, these multi-gas adsorbent materials may be selected for gas storage containers which can be used for different gases at different times. The adsorbent materials may show selectivity for one gas over others, and in this case, these selective gas adsorbents may be selected for gas separation containers as well as gas storage containers, or alternatively, these selective gas adsorbents may be selected for a gas container designed for both separation and storage simultaneously.

[0133] Understanding that adsorbent material gas sorption properties may be tuned using crystal engineering at the point of crystal synthesis, in order to achieve the desired systemwide gas storage container benefits, the adsorbent material itself should be designed for optimal adsorption preferably at lower pressures below 150 bar pressure, or below 135 bar pressure, or below 100 bar pressure, or below 80 bar pressure, below 65 bar pressure, or below 60 bar pressure, or below 50 bar pressure, or below 40 bar pressure, or below 30 bar pressure, or below 20 bar pressure or below 10 bar pressure, to minimise energy requirements for charging, and to maximise safety of the overall system.

[0134] The crystalline properties of the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, can be engineered using specific synthesis methods specific to those materials or material classes to achieve properties specific to the end-use case. For example, for cryogenic low-pressure hydrogen bulk storage and transport, the properties which may be considered are maximising surface area, gravimetric uptake at the charging temperature and pressure, and / or tuning the material to have a Heat of Adsorption (Qst) between -3 and -10 kj / mol. The adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, with a Heat of Adsorption of -10 to -25 kJ / mol erodes the ultimate energy efficiency of the gas storage container for refrigerated or cryogenic systems, driving up cost to industrial end-users, which is undesirable. For example, the MOF CuII3[CoIII(CN6)]2 achieves a surface area of 716 m2 / g, pore volume of 0.4 cm3 / g and a Head of Adsorption of about -6.5 kJ / mol, resulting in a volumetric energy density of 29.3 g(hydrogen) / L systemwide at 75% packing fraction at 80 K and 50 bar. In another example, the MOF [CuII3(BTC)2] (where BTC = 1,3,5-benzenetricarboxylate) achieves a surface area of 1740 m2 / g, a porosity of 0.64 cm3 / g and a Head of Adsorption of about -6 kJ / mol, resulting in a deliverable volumetric energy density of 40.8 g(hydrogen) / L systemwide at 75% packing fraction at 80 K and 50 bar, which is volumetrically competitive with 700 bar ultra-high compressed hydrogen gas storage systems. These examples demonstrate the relationship between maximising volumetric density and maximising energy efficiency, since energy efficiency degrades significantly as the Heat of Adsorption, Qst, increases. FIG. 22 and FIG. 21 have similar Qst at low gas loading, but the smaller pore volume and surface area of CuII3[CoIII(CN6)]2 (FIG. 22) limits total adsorption capacity compared with [CuII3(BTC)2] (FIG. 21) which demonstrates superior adsorption capacity. FIG. 22 and FIG. 21 show the above-mentioned competitive comparisons for hydrogen charged into a system at 50 bar pressure and 80 K. For ambient temperature pressurised systems filled with nanoporous, microporous, or mesoporous adsorbent material, a Heat of Adsorption of -10 to -25 kJ / mol is appropriate. For ambient temperature systems, Heat of Adsorptions with magnitude greater than -25 kJ / mol will be less energy efficient than convention non-material based high compression up to 250 bar pressure (typical for compressed natural gas (CNG)). There may be specific use cases where Heat of Adsorptions of magnitude up to -51 kJ / mol may be required by the end user, for example for safety reasons. The present invention enables a person skilled in the art to make the appropriate decision to select the right adsorbent to the right gas or gas mix, using the described enabling systems to functionalise charging, storing and discharging of the gas storage container, tailored to end-user requirements.

[0135] The adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, with a gas storage container may be mechanically robust enough to maintain its structure. Entrainment is result from the breakdown of the adsorbent material into fine nanoparticle powders in the gas storage container which may cause entrainment during discharge. This mechanically robust crystal-engineering to prevent entrainment may be achieved by selecting materials with coordination environments selected from hard metal ions (for example Mg2+, Fe3+, Al3+ ions), and coordinating them into a MOF with ligands with hard coordinating moieties (such as ligands with cynaido-moieties such as cyanido or nitroprusside bridging ligands, or carboxylato- moieties such as trimesic acid (benzene-1,3-5-tricarboxylic acid, H3BTC, and also referred to in its deprotonated ligand form as benzenetricarboxylate or BTC), comprising an aryl core and three carboxylic acid coordinating groups, or 3,3',5,5'-azobenzenetetracarboxylic acid ((E)-5,5’-(diazene-1,2-diyl)disophthalic acid, H3ABTC, and also referred to in its deprotonated ligand form as azobenzenetetracarboxylate or ABTC), or Meso-tetra(4-carboxyphenyl)porphine (TCPP), or 4,4',4''-benzene-1,3,5-triyl-tribenzoix acid, or 24 bis(1H-1,2,3-triazolo[4,5-b],[4‘,5‘-i])dibenzo[1,4]dioxin, or 4,4’-stilbenedicarboxylic acid, or 3,3",5,5"-tetrakis(4-carboxyphenyl)-p-terphenyl, or 4,4',4",4m-(1,4-phenylene)bis(pyridine-4,2-6-triyl))-tetrabenzoic acid, 4,4',4'',4'''-(4,4'-(1,4-Phenylene)bis(pyridine-6,4,2-triyl))tetrabenzoic acid, or 2,5-Dihydroxy-1,4-benzenedicarboxylic acid (2,5-dioxido-1,4-benzenedicarboxylate(dobdc4-)), or 1,3,5-Tris(2H-tetrazol-5-yl)benzene, Formic acid (methanoic acid), or benzochalcogenadiazole linker where the chalcogen can be oxygen, sulfur, or selenium, or terphenyltetracarboxylate ([1,1':4',1"]Terphenyl- 3,3",5,5"-tetracarboxylic acid, NOTT), or 5,5'-benzo[c][1,2,5]thiadiazole-4,7-diyldiisophthalic acid (H4L; polarized benzothiadiazole; dibenzoisopthalate) , or 5,5'-benzo[c][1,2,5]thiadiazole-4,7-diylbis(ethyne-2,1-diyl)diisophthalic acid (H4btadpa).

[0136] Entrainment may be prevented by installing 5 pm, 10 pm, 20 pm, 50 pm, or 100 pm filters in the outlet of the gas storage container, and in the decant system The optimal selection of filter may be the largest pore sized filter which prevents entrainment, as the smaller pore size filters create larger pressure drops which erodes the energy efficiency of the gas storage container. Correct selection of filter may depend on the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, and will be apparent to the skilled person. For example, harder, more mechanically robust materials formed into large macromorphic adsorbent bodies may be more unlikely to cause entrainment than adsorbent powders.

[0137] The packing fraction of the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, in the gas storage container may be from about 0.55 to about 0.95. The packing fraction of the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material may be at least 0.55. The packing fraction of the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may be from about 0.55 to about 0.9. The packing fraction of the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may be from about 0.6 to about 0.85. The packing fraction of the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material may be from about 0.6 to about 0.80. The packing fraction of the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may be from about 0.6 and 0.75. The packing fraction of the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may be from about 0.6 to about 0.7. The packing fraction of the adsorbent material, including a nanoporous, 25 microporous, or mesoporous adsorbent material, may be from about 0.6 to about 0.65. The packing fraction of the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may be from about 0.65 to about 0.9. The packing fraction of the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may be from about 0.7 to about 0.9. The packing fraction of the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may be from about 0.8 to about 0.9. The packing fraction of the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may be from about 0.85 to about 0.9. The packing fraction of the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may be from about 0.65 to about 0.85. The packing fraction of the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may be from about 0.7 to 0.8. The remaining interstitial space between the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may be filled with free non-adsorbed gas.

[0138] The packing fraction for any given gas storage system may consider the use case in addition to the specific gas, gases, and adsorbents being used. Disclosed herein are methods of designing systems for conditions and use cases. Counterintuitively, it may not always be preferred to maximise packing fraction in order to maximise storage capacity. This is because, as shown in FIG. 29, as the packing fraction increases, this increases the adsorbent bulk material density within the gas storage container on a kg(adsorbent) / L basis, and this displaces the void volume. Some void volume is required to allow a space for gas to desorb into. The void volume is many times less volumetrically efficient at holding gas compared to the material, so if there is little void volume remaining, as the gas storage container starts to desorb, the void space fills very quickly and the pressure rises. Thus a very high packing fraction, reduces dormancy even if there is only a very small desorption of gas, as it has few void spaces to fill. There is a trade-off between packing fraction and dormancy, which FIG. 29 shows for [CuII3(BTC)2], assuming the gas is hydrogen and the loading conditions are between 80 K and 120 K charge temperature and between 1 bar and 45 bar charge pressure. Similar trade-off calculations can be generated using the surface area, pore volume, heat of adsorption, and material bulk density, using Equations as described in the Examples. The packing fraction of the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may be from about 0.75 and 0.88, or may be from about 0.75 to about 0.85. The packing fraction of the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may be about 0.85.

[0139] Optimising the packing fraction may include controlling the shape and size of macromorphs of a MOF body (whether as pressed pellet, monolith or megalith) into regular 3-D polygons. The 3-D polygons may be cubes or spheres. The cubes or spheres may be a single sized cube or sphere. Packing fractions of about 0.75 may be produced by packing cubes or spheres of two different lengths or diameters respectively, as exemplified in FIG. 37 and FIG. 38. Further packing fraction of up to 0.85 may be produced through blending of three different lengths or cubes or diameters of spheres.

[0140] The adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, incorporated into the gas storage container can have different macromorphologies, either as powder, or pressed pellets, or densified monolithic pellets, or densified megalithic pellets or densified megalithic blocks, whereby pellets and blocks can form a rigid body within the gas storage container and achieve packing fractions of >93%, >91%, >87%, >85%, >80%, or >75% or >65% or >60% or >58% or >55% or >50%, or whereby megalithic blocks are hard enough and large enough to be machined to form precise 3D tessellating segments which fill the void of the gas storage container to achieve packing densities of >99%, or >98%, or >97, or >95%, or >90% or > 85% or >80% or >75% packing fraction, or whereby megalithic blocks can be made hard enough and large enough to form a single shape precisely the dimension of the gas storage container void space, such that the adsorbent material can act as a mandrel during the manufacture of Type-V carbon-composite pressurised gas storage containers, enabling both improved packing fraction of adsorbent to >99%, or >98%, or >97, or >95%, or >90% or > 85% or >80% or >75% of void volume, as well as simplifying systemwide manufacturing processes. The adsorbent material may be a nanoporous absorbent material.

[0141] Different macromorphologies of the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may be incorporated into the gas storage container for example powder, or pressed pellets, or densified monolithic pellets, or densified megalithic pellets or densified megalithic blocks. Increasing the packing fraction increases the amount of MOF material in the gas storage container and 27 therefore the amount of gas that can be adsorbed. The adsorbent material may be a nanoporous absorbent material.

[0142] The adsorbent macromorphologies of pressed pellets, or densified monolithic pellets, or densified megalithic pellets or densified megalithic blocks, the pellets or blocks may interlock with each other to form a rigid body of mass within the gas storage container, with material packing densities of >93%, >91%, >87%, >85%, >80%, or >75% or >65% or >50% through control of pellet or block dimensions. The desired level of packing fraction of adsorbent is dependent on the overall performance of the gas storage system and the specific user requirements, and packing fraction can be used to modulate said performance to meet these requirements.

[0143] The adsorbent macromorphologies of densified megalithic blocks, the blocks may be hard enough and large enough to be machined to form precise 3D tessellating segments which fill the void of the gas storage container to achieve packing densities of >99%, or >98%, or >97, or >95%, or >90% packing fraction. The desired level of packing fraction of adsorbent may be dependent on the overall performance of the gas storage system and the specific user requirements, and packing fraction can be used to modulate said performance to meet these requirements.

[0144] As understood by the person skilled in the art, nanoporous, microporous or mesoporous adsorbent materials including Metal-Organic-Framework (MOF) materials, Covalent-Organic-Framework (COF) materials, MOF-composite materials, MOF-hybrid materials, and / or MOF-hybrid-composite materials can be modified or “tuned” to optimize the storage of various types of gases at various temperatures and pressures. Tuning may be achieved with multivariate analysis leveraging the tunability of multifunctional gas-selectivity and thermal behaviour of adsorbent nanoporous materials with temperature and pressure. That is, their gas volumetric uplift and thermal behaviour (including thermal conductivity and coefficient of thermal expansion) at different temperatures and pressures can be adjusted for optimal storage efficiency, safety and to reduce cost. More than one type of adsorbent material can be combined with other nanoporous adsorbent materials. By using the method of Examples 1 to 4 to model adsorbent behaviour and system design, preferred adsorbent properties can be ascertained and then the thermal mass and thermal conductivity of the adsorbent material can be tuned pre-synthetically through crystal design and engineering or post-synthetically modified through composite blending or hybridizing with other advanced 28 materials of differing thermal conductivities, enabling tuneable and longer dormancy / dwell / hold time.

[0145] For example, when the adsorbent material comprises a MOF-Hybrids where MOFs are post-synthetically blended with carbon allotropes, such as graphene or graphene oxide, or expanded graphene oxides, or with carbon-nanotubes, and others, to produce hybrid materials with improved gas adsorption properties, higher-thermalconductivities, and augmented thermo-mechanical properties such as augmented negative or zero coefficient of thermal expansion, may be desirably required to tune gas selectivity and gas storage systemwide performance.

[0146] The adsorbent micromorphology of densified megalithic block can be made hard enough and large enough to form a single shape precisely the dimension of the gas storage container void space, such that the adsorbent can act as a mandrel during the manufacture of Type-V carbon-composite pressure gas storage containers, enabling both improved packing fraction of adsorbent to >99%, or >98%, or >97, or >95%, or >90% of void volume, as well as simplifying systemwide manufacturing processes.

[0147] The dormancy of the of the adsorbent material in the gas storage system may enable gas storage of greater than 3 days, >7 days, >14 days, >20 days; >30 days, >35 days, >60 days >65 days, > 90 days, >110 days, >120 days, or >130 days, or >140 days, or > 150 days, or >160 days. The dormancy of the adsorbent material in the gas storage system may enable gas storage of at least 160 days.

[0148] The dormancy of the adsorbent material may enable, for example, storage of hydrogen that may be tuned to achieve up to 160 days dormancy, through cooperative utilisation of multi-layer-insulation (MLI) as well as through selection of MOF adsorbent, as shown in FIG. 28, FIG. 29 and FIG. 30. FIG. 28 shows that the system dormancy can be increased by reducing charge pressure, but this has a trade-off of reducing the total amount of gas stored. FIG. 29 shows that dormancy can also be tuned by changing packing fraction, and again, there is a small trade-off with very high packing fractions reducing dormancy. FIG. 30 shows the relationship between dormancy and charge temperature, with lower temperatures decreasing dormancy but achieving higher gas storage densities. Using these parameters shown, an engineer may design for the required specifications of the end-user. Gas Storage Container

[0149] The gas storage container may comprise an outer shell surrounding an inner shell. Techniques to inhibit heat transfer may be applied between the inner shell and the outer shell. Space between the inner shell and the outer shell may be under vacuum to inhibit heat transfer. Space between the inner shell and outer shell may be insulated to inhibit heat transfer. Space between the inner shell and outer shell may both be insulated and under vacuum. The outer shell may be formed of metal. The outer shell may be formed of carbon-fibre composite. The inner shell may be formed of a metal alloy that inhibits corrosion or embrittlement over time (Type-I). The inner shell may be formed of metal wrapped with carbon-fibre composite (Type-II or Type-III). The inner shell may be formed of polymer wrapped with carbon fibre composite (Type-IV). The inner shell may be formed of carbon-fibre composite material (Type-V).

[0150] The gas storage container may comprise a single shell for gases stored at ambient temperature. The single shell may be formed of Type-I, Type-II, Type-III, Type-IV or Type-V material.

[0151] The adsorbent material-filled gas storage container, when fully charged / loaded, may have a high volumetric density of gas compared with compressed or cryocompressed gas at an equivalent temperature and pressure. The improvement factor in volumetric density may be at least greater than about 2.5x up to about 20x. For example, when the gas is hydrogen, the improvement factor in volumetric density at 77 K temperature may be greater than 2.5x, greater than 3x, greater than 4x, greater than 5x, greater than 6x, greater than 7x, greater than 8x, greater than 9x, greater than 10x, greater than 11x, greater than 12x, greater than 15x, greater than 17x, or greater than 20x, as shown in FIG. 39, FIG. 40 and FIG. 45.

[0152] The adsorbent material-filled gas storage container, when fully charged / loaded, may have a high volumetric density of gas compared with liquefied gas. For example, for hydrogen, the improvement factor in volumetric density at 77 K temperature is between 63% to 85% of liquefaction volumetric density depending on pressure, and with an energy saving of between to 53 - 83% (corresponding to 7 - 2.6 kWh / kgh2) compared to liquefaction of hydrogen (12-15 kWh / kgh2), and with elimination of boil-off losses. Very high volumetric densities of gases compared with liquefied gas, may be achieved at cryogenic temperatures between 20 K and 77 K and up to 50 bar pressure, for example for hydrogen, the improvement factor in volumetric density between 25 K and 70 K at 50 bar pressure is 122% to 75% respectively, with densities greater than liquefied densities, when using an adsorbent with high surface area and para-active metal cluster such as [Cu3(BTC)2] (leveraging the para-switching behaviour of the adsorbent to drive ordering of gas molecules within the pores at very low cryogenic temperatures.

[0153] The adsorption process is exceptionally energy efficient, with few losses in the uptake (adsorption) and release (desorption) of gas molecules from the pores of the material.

[0154] The gas storage container may be ISO certified for intermodal transport. The intermodal transport may be road, rail and / or marine. The gas storage container may be certified under ADR codes. The gas storage container may be certified under RID codes. The gas storage container may be certified under IMDG codes. The gas storage container may be certified under IGC codes. The gas storage container may be certified under IGF codes.

[0155] The gas storage container may be ISO certified compliant gas storage system for intermodal shipping between 8ft to 45ft.

[0156] The gas storage container may be any size. The gas storage container may be less than about 30 litres. The gas storage container may be from about 30 Litres to about 266,000,000 Litres. The gas storage container may be from about 30 Litres to about 500 Litres. The gas storage container may be from about 100 Litres to about 400 Litres. The gas storage container may be from about 300 Litres to about 500 Litres. The gas storage container may be from about 350 Litres to about 1000 Litres. The gas storage container may be from about 350 Litres to about 20,000 Litres. The gas storage container may be from about 950 Litres to about 2500 Litres. The gas storage container may be from about 950 Litres to about 4,000 Litres. The gas storage container may be from about 950 Litres to about 9,000 Litres. The gas storage container may be from about 7,000 Litres to about 18,500 Litres. The gas storage container may be from about 17,500 Litres to about 20,000 Litres. A typical sized for 20ft ISO gas storage container is about 17,500 Litres to about 20,000 Litres. The gas storage container may be about 30,000 Litres to about 33,000 Litres. A 30ft ISO gas storage container is generally about 30,000 Litres to about 33,000 Litres. The gas storage container may be about 40,000 Litres to about 44,000 Litres. A 40ft ISO gas storage container is generally about 40,000 Litres to about 44,000 Litres. The gas storage container may be up to about 12,300,000 Litres, or up to 266,000,000 Litres. Type-C tanks used as gas storage containers are typically up to about 12,300,000 Litres, or up to about 31 266,000,000 Litres. An example of a detailed computer aided drawing of a nanoporous, microporous, or mesoporous adsorbent-enabled 1000 Litre gas storage container is shown in FIG. 3 (side on view) and FIG. 4 (top view). An example of a process and instrumentation diagram (P&ID) for a vertical nanoporous, microporous, or mesoporous adsorbent-enabled 1,000 Litre storage container is shown in FIG. 5. An example of a process and instrumentation diagram (P&ID) for a horizontal 20,000 Litre gas storage container for a 20ft ISO gas storage container nanoporous, microporous, or mesoporous adsorbent-enabled bulk transport application is shown in FIG. 6. Gas Storage System

[0157] The gas storage system may use the gas being stored as a heat transfer fluid to affect the charging of the gas storage container by circulating gas fed to the gas storage container back to the feed gas for recirculation back through a heat exchanger for return to the gas storage container. By this arrangement, a charging loop is formed whereby heat released by gas being adsorbed by the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, is extracted by gas leaving the gas storage container, with said gas being cooled to the target storage temperature before recirculating back to the gas storage container. Using a recirculation loop thereby simultaneously cools the feed gas, the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, and the gas storage container to the target storage temperature.

[0158] The gas storage system may comprise a charging subsystem comprising a charging loop. The charging loop may comprise a heat exchanger. The heat exchanger may be a cryocooler. The heat exchanger may be a cooling system. Liquid nitrogen may be used as the cooling medium. Mixed refrigerant gases (for example mixtures of nitrogen, helium and neon) may be used as the cooling medium. The cryocooler or cooling system may be located in a housing under vacuum. The charging system may comprise a blower. The charging system may comprise a cryogenic blower.

[0159] In general, the charging loop may be adapted to connect with an inlet to the gas storage container and an outlet to the gas storage container to facilitate recirculation of gas through the gas storage container during the charging process of adding gas to storage in the gas storage container. The charging loop may gas supply line for introduction of feed gas to the charging loop and storage container. The gas supply line 32 may be upstream of the heat exchanger. The gas supply line may be downstream of the heat exchanger, for example, if the feed gas is already at storage temperature.

[0160] The charging subsystem may include a further heat exchanger to cool the feed gas before introduction to the charging loop or gas storage container. The decanting loop may comprise a heat exchanger.

[0161] In general, the decanting loop is adapted to connect with an inlet to the gas storage container and an outlet to the gas storage container to facilitate recirculation of gas through the gas storage container during the decanting process of removing gas from storage. The decanting loop may be configured to operate under natural convention with gas circulating in the decanting loop via thermosiphon. The decanting loop may be configured to operate under forced convection. The decanting loop may comprise a blower to circulate gas. The decanting loop may comprise a cryo-blower to circulate gas.

[0162] The decanting loop heat exchange may be electric. The decanting loop heat exchanger may comprise a glycol-water closed loop. The decanting loop heat exchanger may utilise a waste heat source. A fuel cell system may provide the waste heat source. An internal combustion engine may provide the waste heat source. A turbine may provide the waste heat source. A boiler may provide the waste heat source. Industrial process waste heat may provide the waste heat source. Data centre waste heat may provide the waste heat source. The decanting loop heat exchanger may utilise ambient air as a heat transfer fluid. The decanting loop heat exchanger may utilise the stored gas as its own heat transfer fluid.

[0163] The decanting subsystem may be in situ with the gas storage container for colocation with the gas storage container during transport. The decanting subsystem may be ex situ with the gas storage container.

[0164] The gas storage system may comprise activation subsystem. The activation subsystem may comprise a heater configured to heat inert gas to an activation temperature.

[0165] The activation system may comprise a vacuum inducing device configured to place the gas storage container under vacuum. The vacuum inducing device may be a vacuum pump.

[0166] The activation subsystem may comprise an activation loop adapted to connect with an inlet to the gas storage container and an outlet to the gas storage container to facilitate recirculation of inert gas during the activation process. The heater may be 33 located in the activation loop upstream of the gas storage container inlet. The activation loop may comprise a dehydrator downstream of the gas storage container outlet to remove moisture from the inert gas before recirculation back to the heater.

[0167] The activation subsystem may be in situ with the gas storage container for colocation with the gas storage container during transport. The decanting subsystem may be ex situ with the gas storage container.

[0168] There is further disclosed herein a gas storage container having the gas storage system as described herein throughout the disclosure, the gas storage container may be used for intermodal (road, rail and marine) bulk transport as a gas transport tank, or used as a fuel tank for road, rail and marine or aircraft transport, or for large tanks for industrial static storage, or used as a gas capture tank for static gas capture application or gas capture applications for bulk gas carriers (as ancillary boil-off prevention on liquefied gas carriers) or gas capture applications as ancillary boil-off prevention equipment for liquefied gas fuel systems for when liquefied gases are used as fuels in heavy transport. The incorporation of the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, into the gas storage container enables higher storage densities at a given temperature and pressure, enabling a lowering of pressures, or an increasing in volumetric density of gas for gas storage and gas capture applications. The gas storage container may be specifically designed to allow filling with the porous adsorbent material, and even distribution of the gas through the system throughout its operation (including during charging and loader, storage and decanting and discharging). For example, a possible optimal 1000 Litre double-walled steel cryogenic gas storage container designed for an adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, enabled hydrogen storage is shown in FIG. 3 (side view) and FIG. 4 (top view), with corresponding process and instrumentation diagram shown in FIG. 5. The gas storage principle and gas storage container design can be applied for any gas storage container of any size including smaller gas storage container of less than 30 Litres, and larger gas storage containers of 30 Litres to about 500 Litres, and larger gas storage containers of 100 Litres to about 400 Litres, and larger gas storage containers of 300 Litres to about 500 Litres and larger gas storage containers of about 350 Litres to about 1000 Litres, and larger gas storage containers of about 350 Litres to about 20,000 Litres, and larger gas storage containers of about 950 Litres to about 2500 Litres, and larger gas storage containers of about 950 Litres to about 4,000 Litres, and larger gas storage containers of about 950 Litres to about 9,000 Litres, and larger gas storage containers of about 7,000 Litres to about 18,500 Litres, and larger gas storage containers of 17,500 Litres and 20,000 Litres, typically sized for 20ft ISO gas storage container, and larger 30,000 Litres to about 33,000 Litre gas storage containers typically sized for 30ft ISO gas storage containers, and larger 40,000 Litres to about 44,000 Litres gas storage containers typically sized for 40ft ISO gas storage container, and giga-scalable for larger Type-C tanks used as gas storage containers of up to 12,300,000 Litres, or up to 266,000,000 Litres. An example of a process and instrumentation diagram for a 20,000 Litre gas storage container for a 20ft ISO gas storage container bulk transport application is shown in FIG. 6.

[0169] The gas storage container may be adapted to address specific considerations such as ability to: withstand tens of thousands of thermal and pressure cycles as gases are adsorbed and desorbed; resistance to impact damage, resistance to microcracking and gas permeability and gas leaks; fire resistance; lightning resistance; exposure to the environment; and / or to withstand embrittlement in the case of hydrogen storage in steel gas storage containers; and resistance to other safety hazards, especially for flammable gases or oxidising gases.

[0170] Gas which may be loaded into adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material-filled gas storage container, is theorized to load into the pores of the adsorbent material at sites with the highest Heat of Adsorption (Qst) first, followed by further adsorption and loading at sites with lower Heat of Adsorption (Qst). The inventor notes that a further corollary of the above loading principle is that as the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material-filled gas storage container is loaded, the free space volume of the adsorbent material-filled gas storage container has no sites for adsorption, so will be filled with gas at a lower volumetric density than gas adsorbed within the pores of the material.

[0171] When the nanoporous, microporous, or mesoporous material-filled gas storage container is fully loaded with the target gas, the “free gas” within the interstitial space between the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, crystallites may be less than about 40%, less than about 35%, less than about 30%, less than about 25%, less than about 20%, less than about 15%, less than about 12.5%, less than about 10%, less than about 7.5%, less than about 5%, less than about 2.5%, less than about 2%, less than about 1.5%, or less than about 1%. As shown in FIG. 24, for a hydrogen cryo-gas storage container, charged at 82 K temperature and 30 bar pressure, the hydrogen “free gas” in the void space rises from about 45 kg(hydrogen) (5.6% of total gas within the gas container) to about 65 kg(hydrogen)(8.1% of total gas within the gas container), as the gas storage container gradually warms up over 38 days of dormancy, reflecting a slow desorption of hydrogen from the adsorbent material into the void space.

[0172] In addition to increasing the volumetric capacity and energy efficiency compared to conventional gas storage systems, the gas storage system herein described may be inherently safe, as in the unlikely event of a loss of containment from a gas storage container rupture, only the free gas will be immediately released while the remaining gas remain adsorbed, with this adsorbed gas releasing slowly over many hours, as shown in FIG. 41. For flammable gases, the consequent fire or explosion would be significantly (10x to 500x) smaller as the adsorbed gas would be released slowly over many hours. Additionally in this unlikely event of a loss of containment from a gas storage container rupture, the porous material adsorbent may act as a fire retardant to further reduce consequence of a fire within a ruptured flammable gas storage container, for example the MOFs with carboxylato or cyanido bridging moieties, the products of combustion being CO2 and NOx can suppress a fire by excluding oxygen from the fuel. For example, for [(Fem2FeH(p3-O))2(ABTC)3] the combustion will produce CO2, NOx and iron oxides, thus acting as a fire retardant, extinguishing live flames. Other adsorbent materials with carboxylato or cyanido moieties will be suitable for selection for fire retardant properties.

[0173] Without being bound by theory, the inventor believes that the absorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, may contribute significant thermal mass to the gas storage container. The gas, when adsorbed in adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, within the gas storage container, may establish an equilibrium, when the system is closed. This equilibrium may resist changes in temperature. Increases in temperature from external heat applied to a closed gas storage container drives gas off the material, which is an endothermic process, thus during desorption, the material cools down, and re-sorbs the gas to re-establish the temperature pressure equilibrium, Le Chatelier’s Principle. Paired with the large thermal mass of the material in the gas storage container these two features work cooperatively to increase the dormancy of conventional refrigerated or cryogenic gas storage containers, reducing or 36 eliminating the need for active refrigeration or cryocooling systems for these gas storage containers during operation. This provides a major energy saving to the gas storage system. For cryo-gas transport of fuels such as helium, neon, nitrogen, oxygen, carbon dioxide, methane or hydrogen, this can significantly decrease the cost of bulk transportation of the gas (by between 3x and 20x), particularly over long distance, through improvement or elimination of parasitic energy losses during transit. As evident from FIG. 28, FIG. 29, and FIG. 30, cryo-compressed hydrogen storage systems show long dormancy is possible without additional cooling, significantly longer than current mature liquefied gas systems, which must be actively cooled, and even with active cooling, have dormancy of just a few days.

[0174] The gas storage system, when operated as a refrigerated or cryogenic temperature gas storage system, may store gas greater than 3 days, >7 days, >14 days, >20 days; >30 days, >35 days, >60 days >65 days, > 90 days, >110 days, >120 days, >130 days, or > 160 days. The gas storage system may store gas from greater than 3 days to about 30 days, from greater than 3 days to about 60 days; from greater than 3 days to about 90 days, from greater than 3 days to about 110 days, or from greater than 3 days to about 130 days, or from greater than 3 days to about 160 days. The refrigerated or cryogenic gas storage system may store gas greater than 3 days and up to 160 days, as shown in FIG. 28. A person skilled in the art would understand that an ambient temperature gas storage system would not need to consider dormancy as its temperature remains similar to the temperature of the ambient environment.

[0175] The gas storage system and the comprised gas storage container may be optimized for gas uptake and end-to-end energy efficiency, within a temperature and pressure envelope, for the specific gas to be stored and transported. The gas storage container may be passive (e.g. no active cooling applied) and may have zero boiloff during normal operation. Such a gas storage container would be understood to be energy efficient, as minimal energy is required for initial compression, or cooling, or cryocooling, or liquefaction and no energy is required to maintain the temperature and pressure during storage and transport.

[0176] The gas storage system may utilise available free gas to facilitate energy efficient desorption at the point of use through a decanting system. The decanting system may be installed as part of the integrated gas storage container system or installed as a fixed system at the delivery site or installed as a fixed system on a road or rail vehicle / marine vessel / aircraft if used as a gas storage container for a transport fuel. The decanting system uses the free gas as the heat transfer fluid to minimise the requirement for additional heat transfer fluids and associated additional energy in the process. This feature enables a maximising of the volumetric density potential for a fixed volume of gas storage container, by minimising balance of plant inside the gas storage container. For increased flow rates, some energy input may be required to warm the free gas to a higher temperature than the equilibrium temperature of the gas storage container. This warmer gas is then returned to the gas storage container to shift the equilibrium of the gas storage container to higher temperature and thus drive faster desorption of sorbed gas from the nanoporous, microporous or mesoporous material. Warming this gas can be done passively for cryogenic systems, using a conventional air-heat-exchanger (or passive liquefied-gas-vapourisers) as the ambient temperature differential is significant enough to impute required energy. Warming this gas can be done passively for ambient temperature pressurised gas container systems, using a conventional air-heatexchanger as the heat released is relatively small at ambient temperature, owing to a relatively low Heat of Adsorption.

[0177] For higher flow rates, for cryogenic systems, warming the gas may be achieved with a conventional electric heater, hot-water, hot-steam, hot-oil, or other hot-heat-transfer fluid system. For example, for a 20ft ISO sized gas storage container, warming the gas may increase flow rates for example, up to 1000 kg of gas per hour for hydrogen, or 10,000 kg of gas per hour for methane / biogas / biomethane. This may require only about 0.4 to 1 kWh / kgh2 of input energy for a maximum flow rate for the 20ft ISO 20,000 Litres gas storage container operating between about 80 K and about 160 K temperature, and between about 1 bar 31 bar pressure, as demonstrated through field-trial-validated computational-fluid-dynamics modelling shown in FIG. 25, showing an operating mode whereby an increasing gas recirculation rate is used to increase the speed of desorption, thereby resulting in a constant pressure in the gas storage container of about 30 bar during the majority of decant. In a different example, the same system can be operated with constant gas circulation rate, which results in a gradual fall in pressure from about 31 bar to about 1 bar over the decanting period as shown in FIG. 26. In another example, in FIG. 27, a 1000 Litre gas storage container operating between about 80 K and about 160 K temperature, and about 31 bar pressure about 1 bar pressure, was modelled using a similar principle to FIG. 25, where gas storage container pressure was maintained to 31 bar during the decanting process (but allowing the system temperature to rise by gradually increasing the gas recirculation rate), and then when the system reached 160 K internal temperature, was allowed to decant without further recirculation, causing the system pressure to fall logarithmically. The examples show that the decanting whether using a thermosyphon or using a forced convection are scalable for any tank size or any gas storage container size.

[0178] An actively warmed decanting system may use waste hot water or hot steam. Waste hot water or hot steam may be from a fuel cell, combustion engine, or steam turbine. For example, from a hydrogen fuel cell (e.g. hot-water between 55°C and 85°C) or generated as waste hot water or hot steam from a hydrogen internal-combustion engine (which typically generate hot-water between 65°C and 85°C), or generated as waste hot water or hot steam from a hydrogen steam turbines (which typically generate hot-water / steam between 65°C and 120°C), or generated as waste hot water from a data centre (e.g. hot-water between 45°C and 75°C), or generated as waste hot water or hot steam from industrial processes (e.g. hot-water / steam between 55°C and 125°C), a bypassing the hot-water / steam through a heat exchanger to warm a secondary heat transfer fluid, such as ethylene glycol, which is then used to warm cryohydrogen at the appropriate rate to achieve precise flow rates required by the end user. This process is advantageous for the end user of hydrogen as the end-user has precise quantitative control over how much hydrogen is released, and how much hydrogen stays adsorbed to the material in the gas storage container, thereby maximising safety, the energy efficiency, and utility of the system. Furthermore, advantageous, for cryogases generally, the systems cold energy can be recovered and utilised to improve the efficiency of downstream equipment and maximise exergy of the overall system.

[0179] The gas storage system, having uniquely long dormancy and operating energy efficiently, may enable flexible supply and distribution models including many-to-many distribution networks. For example, in the case of hydrogen, small to large producers can distribute to many small to large users, without the need to aggregate the gas in a centralised distribution centre or hub, as there are no parasitic energy losses once the gas container is charged. One-to-many distribution networks are also possible where one medium to large producer of hydrogen can distribute to the full range of hydrogen end-users. Many-to-one distribution modes are also possible where many small to medium and some large producers of hydrogen can distribute to a single or few major users of hydrogen cost effectively, and with similar midstream costs. The gas storage system enables transport and international export of gases such as hydrogen without the need of a dedicated purpose-built ship, or truck or train.

[0180] This flexibility of supply chain optionality provided by the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, and gas storage system is unique and important to the storage and transport of gases. For example, in the case of hydrogen, novel production methods including Waste-to-Hydrogen pyrolysis and electrolytic hydrogen production are possible at small scale, low-cost interoperable solutions to store and transport the hydrogen from production to end use sites, are required. The gas storage system will enable small producers to compete with very large-scale producers and increase the uptake of gases such as hydrogen gas as a zero-carbon energy carrier and source.

[0181] Digital algorithms and software can be built as a virtual layer on the gas storage system, leveraging its desirable “packaged” nature, and leveraging the quantised, measurable, gas grade guarantee certifiable, long dormancy and zero boil-off properties afforded by the incorporation of these adsorbent materials, including a nanoporous, microporous, or mesoporous adsorbent materials, in the gas storage container. Where the storage system is used for gases such as hydrogen, supply chain network software may enable efficient storage and distribution from both small and large producers to a range of small to large energy users. This supply chain software combined with engineering design of the gas storage system facilitating zero-boil-off, long dormancy / dwell / hold time, high density, and high energy efficiency, will enable the container to be financialized as a standard energy vector asset and traded in real time within many-to-many, one-to-many and many-to-one supply ecosystems, with onboard telemetry enabling faster transactions, and multivariate real time cost optimization. The elimination of boiloff losses facilitates the value of any software which leverages real time data flows from the gas storage system, as monetising the value of the gas relies on a guaranteeing that every gas molecule loaded into the gas storage system can be delivered to the end customer, with measurable quantised precision (measuring both volume and quality of gas stored and transported). Third party software can be written for the gas storage container, or to be installed on the gas storage container, to enable tracking of hydrogen and automation in the calculation of carbon abatement and other energy transition incentives. This innovation solves major challenges in industry regarding how to trade different grades of gases (such as hydrogen or CO2) via pipeline, where a high grade of gas may be spoilt by injection of lower grades gas downstream. Furthermore, presently precise unquantifiable boil-off from existing cryo gas packaged systems inhibits the building of packaged gas supply chain software as there is no way of knowing precisely how much was loaded and unloaded.

[0182] The gas storage system facilitates gases, such as hydrogen, being stored and transported in gas storage containers, for example, via rail, road and ocean freight. For example, where the adsorbent material is a nanoporous adsorbent material and gas storage systems may be optimized for hydrogen, the performance may be, for example for an intermodal 20ft ISO container could be: • volumetric density 37.5-77.5 g(hydrogen) / L within the gas storage container (by liquid volume of 17,500 L - 21,000 L, at 30 bar pressure, and at charge temperatures of 85 K and 25 K) ; • dormancy of the unpowered system greater than 3 days, >7 days, >14 days, >20 days; >30 days, >35 days, or >60 days or >65 days, or > 90 days, or >110 days or >120 days or >130 days or >160 days; •    Zero boil-off or boil-off <0.01% per day, or boil-off <0.1% per day; •    Roundtrip energy efficiency (defined as total energy stored minus total energy required for all gas charging, holding and gas discharging steps, where the gas is an energy vector) >95%. or >93% or >90%, or >85%, or >80%; • Operating pressures between 0-3 bar or 0-5 bar or 0-8 bar, or 0-10 bar, or 0-20, or 0-22 bar, or 0-24 bar, or 0-28 bar, or 0-30 bar pressure, or 0-35 bar, or 0-40 bar, or 0-50 bar pressure; or 0-60 bar, or 0-70 bar, or 0-80 bar, or 0-100 bar, or 0-135 bar or 0-200 bar, or 0-250 bar, or 0-300 bar, or 0-350 bar, or 0-380 bar, or 0-385 bar, or 0-400 bar, or 0-450 bar or 0-500 bar, or 0-550 bar or 0-700 bar, or 0-950 pressure; • Very high cyclability (>50,000 cycles without degradation of storage capacity); • Slow release of hydrogen desorbing from the surface area of the adsorbent (including Metal-Organic-Framework (MOF) materials, Covalent-Organic-Framework (COF) materials, MOF-hybrid materials, materials comprises two or more MOFs, and MOF-hybrid-composite materials). Thus, in the unlikely event of a gas storage container rupture, reduces the likelihood of a gas explosion (where the gas is flammable or explosive, for example where the gas hydrogen), demonstrating inherent safety.

[0183] There may be other desirable features of the gas storage system (e.g. the adsorbent material-enabled gas storage container) including deployment of other gases other than hydrogen. The skilled person will understand that off the shelf components and valves fittings may need to be replaced to recommission the gas storage container for service with gasses other than hydrogen. Gas storage systems as described herein may have an operational lifetime greater than 20 years’ lifespan, >25 years’ lifespan, or >30 years’ lifespan.

[0184] Advantageously, the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, in the gas storage container can be replaced at any time without loss of performance and without change of certification of the gas storage container enabling the container to be augmented and updated, enabling longer lifespan, and future proofing. The principle may be applied to all types of gas storage containers for storage and transport, regardless of size. Suitable gas storage containers include ISO gas storage container, such as including 8ft, 10ft, 20ft, 30ft, 40ft, or 45ft ISO intermodal gas storage containers. For super carrier gas transport ships, any size of gas storage container may be suitable. Exemplary super carrier sizes suitable include from small ships with liquid volume of 167 m3 to the largest gas transport ships on earth with a liquid volume of 266,000 m3 and many other sizes larger and smaller and in-between.

[0185] The gas storage system may address the challenge of safe and cost-effective bulk gas storage and distribution, both locally and internationally. In the case of hydrogen, it may lower the cost of hydrogen to the end customer through a system which can be used to store and transport hydrogen by more trucks, railcars and ships, without specific modification.

[0186] The gas storage system may increase the volumetric density of stored gases, such as hydrogen, within the gas storage container, increasing the temperaturedormancy of the systems without additional energy inputs (e.g. the system remains cold for longer periods), increased roundtrip storage and energy efficiency (because the gases adsorb to the inner surface of the adsorbent nanoporous material, packing into the pores more densely at a given temperature and pressure, than if the gas were the compressed or cooled equivalent at any given temperature and pressure, requiring lower storage pressures than currently in-use and which increases safety. The overall mass of the container on a hydrogen wt.% basis (hydrogen gravimetric efficiency; increasing from 4 wt.% to 6 wt.% and up to 12 wt.%).

[0187] The gas storage system may enable storage of higher densities of gases. For example, hydrogen, in the same container volume, and at more moderate temperatures and lower pressures compared to the compressed or liquefied form. Consequently, this may be a cost effective, safe and efficient solution.

[0188] The gas storage system may enable storage of the same density of gas but at a fraction of the pressure at the same temperature. For example, biomethane and biogas, may attain 155 g(biomethane / biogas) / L at 50 bar pressure and 25 degrees Celsius in a nanoporous, microporous or mesoporous adsorbent material-filled gas storage container, which is same volumetric gas density achievable at 250 bar pressure at 25 degrees Celsius for biomethane / biogas without adsorbent material.

[0189] The gas storage system may enable medium and long duration storage of gases. For example, the gas storage system may be used as a modular unit at industrial or transport hub sites and to enable intermodal bulk transport using existing freight infrastructure, via road, rail and sea across all modes.

[0190] The gas storage system may find application in bulk storage, bulk distribution, bulk transport, including from where the gas is produced (including small scale producers) to where the gas is being used (including ports, transport refuelling hubs, power stations, pipeline nodes, industrial sites, agricultural sites, airfields, intermodal hubs, and other places which have a demand for bulk gas. The gas storage system may be designed according to the principles set out herein to facilitate very long-distance bulk transporting of various gases including international shipping.

[0191] The gas storage system may also be deployed for remote operations. For example, if the gas is hydrogen or biomethane or natural gas or LNG or biogas or air or oxygen or carbon dioxide or helium, in mining applications for remote power, in military applications for expeditionary energy and forward deployment of military force, and for emergency energy deployments to support first responders’ energy or gas requirements during a natural disaster response.

[0192] The gas storage system may also be used to support different gas transported within a single gas storage container. For example, the gas storage system could be utilised to bulk transport hydrogen in gas storage containers (e.g. bulk gas storage containers) from one location to another, and for carbon dioxide to be bulk transported in the same system on the return journey. The bulk gas storage container could be utilised to bulk transport methane or biogas from one location to another, and for carbon dioxide or another gas to be bulk transported in the same system on a return journey. Or in another example, the bulk container could be utilised to transport different gases on different legs of a multi-leg journey.

[0193] The gas storage system may also be used to support and supply gases such as hydrogen to refuelling centres or to supply hydrogen for off road equipment, to provide a source of renewable energy to remote and rural communities, to supply hydrogen to mining operations including refuelling large electric or hydrogen powered mining trucks and to supply hydrogen or hydrogen powered electricity to construction and off-grid equipment used in agriculture, to supply hydrogen for industrial heat applications and to supply hydrogen as an input chemical for synthesis of other derivative molecules like eFuels and Sustainable Aviation Fuels (SAFs), methanol and chemicals like ammonia, or where hydrogen is used as a reductant in steelmaking.

[0194] The gas storage system can be used to capture hydrogen or methane gas from other liquefied hydrogen or liquefied natural gas carriers or bulk transporters, respectively, to drastically reduce or entirely eliminate boil-off emissions and increase dormancy, energy efficiently utilising the recovered cold energy of the cryogenic gases to drive favourable adsorption at low pressures in the adsorbents, ensuring zero gas loss from boil-off and minimal to zero energy input for adsorption, and increasing the exergy of the overall system. In the specific example of hydrogen, the gas storage system can be designed to utilise the para-spin switching behaviour of some MOFs with a para-active metal-cluster such as those MOFs with at least 1 and up to 5 unpaired electrons in d-orbitals of transition metal ions, to increase the dormancy and reduce or eliminate boil-off from liquefied hydrogen gas containers.

[0195] The gas storage system and / or the gas storage containers can be used to capture, separate and store natural gas, biogas, methane, natural hydrogen, stimulated hydrogen from rock formations, natural helium, fugitive methane and other fossil gas emissions, and carbon dioxide from gas streams found in natural resource extraction, and gas streams found in industrial gas processing environments where fugitive emissions may be present, or in capturing, separating storing and transporting naturally occurring gas mixes. This capturing and separating process may utilise the selectivity of a specific adsorbent material to drive favourable capture of one gas molecule over another. The system may separate gas mixtures as well as concentrate and purify gas streams. Additionally, the same system used for gas capture and separation may itself also be the gas storage and transport device. The selective capture of one gas over another in a single system is demonstrated in IAST selectivity in FIG.33, FIG. 34, FIG. 35 and FIG. 36, which shows the separation of methane and hydrogen at different temperatures and pressures, and different gas mix examples, based on the gas isotherms of methane and hydrogen at the target temperature and pressures in FIG. 31 and FIG. 32. The modelling shows, following this method, gas separation of any gas 44 can be undertaken using any adsorbent, once the gas isotherms are known at the target gas separation temperature and pressures.

[0196] The gas storage system may be used to capture, separate, store, and transport gas. Capture of a gas in the context of this disclosure refers to the initial adsorption of gas by the adsorbent. The gas storage system may be used to capture, separate, store, and transport different gases at different times. The gas storage system may be used to capture, separate, store, and transport different gases at different times having characteristics whereby a group of gas storage containers may be used to capture, separate and isolate different gases from a mixed gas stream (typically found emanating from naturally occurring gas wells, or from gas mix streams in industrial gas flows), and the those same gas storage containers may be used as bulk gas storage systems and bulk gas transporters for the captured and separated gases.

[0197] The gas storage system can also be used as a bulk storage for on-vehicle or on-ship energy storage, where the gas is a fuel gas, via a “swap-n-go” model (where empty fuel gas containers are removed and replaced with full fuel gas containers, instead of conducting a bunkering / refuelling operation by the gas supplier), or, as an integrated fixed gas storage container within large vehicles or ships to drive engines, or fuel cells, or turbines or other kinds of fuelled power units for long haul transport for shipping, rail, trucking and aviation applications that require large amounts of energy and where energy storage through batteries is not viable due to weight and recharging requirements.

[0198] The gas storage system may be inherently safe, as in the unlikely event of a gas storage container rupture, only the free gas will be immediately released. For flammable gases, the consequent fire or explosion would be significantly smaller (between 10x and 500x) as the adsorbed gas would be released slowly over many hours as shown in FIG. 41. Additionally in this unlikely event of gas storage container rupture, the adsorbent material may act as a fire retardant to further reduce consequence of a fire within a ruptured flammable gas storage container, for example the MOFs with carboxylato or cyanido bridging moieties, the products of combustion being CO2 and NOx can suppress a fire by excluding oxygen from the fuel. For example, for [(Fem2FeH(p3-O))2(ABTC)3] the combustion will produce only CO2, NOx and iron oxides, thus acting as a fire retardant, extinguishing live flames. Other adsorbent materials with carboxylato or cyanido moieties will be suitable for selection for fire retardant properties.

[0199] The gas storage system utilises the interstitial volume between adsorbent material crystallites to drive fast charging (fast kinetics of adsorption) when the gas is being loaded, using the gas itself as a heat transfer fluid. This process is also the most energy efficient and achieves the highest volumetric density of gas within the gas storage container which is possible.

[0200] A gas storage system comprising a loading and charging system is also disclosed. A loading and charging system can energy efficiently load a gas storage container, using the gas as a heat transfer fluid to remove heat, which is generated during the exothermic adsorption process. See FIG. 23(A) and FIG. 23 (B) for the outputs of different charging mode examples. This process may be exothermic when the gas-to-material physisorption interaction is less than 0 kJ / mol. For example, for hydrogen, FIG. 22 shows [CuIICoIII(CN)6] has a Heat of Adsorption between -2 and -6 kJ / mol, and as shown in FIG. 21, for Cu3BTC2 a Heat of Adsorption between -4 and -6 kJ / mol.

[0201] Taking advantage of the Heat of Adsorption, the loading and charging system may be designed such that the stored gas, when charging, is only partially retained. A portion of the gas may pass through the gas storage container. The gas may pass out, partially moving through the interstitial space as a heat transfer fluid. The portion of gas which passes out of the gas storage container, carries with it waste heat from exothermic adsorption. This allows the system to reach the final temperature pressure equilibrium as fast as possible, and as energy efficiently as possible. For example, a process and instrumentation diagram for gas storage container filling of cryogenic hydrogen is shown in FIG. 8 whereby hydrogen is cooled by Liquid Nitrogen to cryogenic temperature of 77 K hydrogen, and is then used as both a heat transfer fluid and as the adsorbed gas, simultaneously, with non-adsorbed gas carrying heat released from adsorption back to the cryocooler to be recycled, re-cooled and returned to the gas storage container, such that no hydrogen is lost or blown-off in the process and the system can operate as a closed-loop system to maximise energy efficiency, and eliminate gas losses. This is different to how cryo-gases are presently loaded into liquefied gas tanks or liquefied gas storage containers whereby boil-off gas is blown through and allowed to release to the atmosphere, a major source of thermal energy inefficiency, gas losses, and source of safety hazard (for flammable cryo-gases). Favourably, the process uses both convection and conduction to achieve thermal conditioning. For a adsorbent material filled ambient temperature operation gas storage container designed for a biogas like biomethane, heat generated by adsorption can be similarly removed by passing the ambient temperature biomethane through a passive heat-exchanger and passed back into the gas storage container, using the same principle, enabling rapid and energy efficient charging and loading of biomethane into compressed biomethane gas storage containers.

[0202] As the adsorbent materials are relatively insulating in their thermal conductivity, a person skilled in the art will appreciate that a secondary thermal transfer fluid passed through internal tubes in a gas storage container would be ineffective (utilising conduction only) in providing the thermal conditioning required to cool the system in the case of cryogenic gas containers, as the conduction would be ineffective, in the absence of convection, to cool or re-condition the temperature of the materials. By using the gas to be stored, as its own heat transfer fluid, this enables utilisation of convection support energy efficient heat transfer from the cryogas to recondition the system to the target temperature and pressure.

[0203] Specifically for cryogenic low-pressure storage of hydrogen between 20 K to 150 K temperature and 1 bar to 150 bar pressure, the charging and decanting system leverages the increasing proportion of para spin-state hydrogen to ortho spin-state of hydrogen at decreasing temperature. A person skilled in the art will understand that ortho-hydrogen (where the spin states of each electron on the hydrogen is opposite to each other) is the more stable form at higher temperatures (75% ortho-hydrogen, 25% para-hydrogen at 300 K), while para-hydrogen (where the spin states of each electron on the hydrogen is aligned to the same direction to each other) is the more stable form at lower temperatures, and that there is approximately 50:50 ratio of para to ortho at 77 K, and reaches approximately 99% para spin-state at 20 K. The invention disclosed, uses cold cryogenic hydrogen, at 77 K, or 80 K, or 85 K, or 65 K, or 60 K, or 50 K, or 40 K, or 30 K, or 20 K, to enable energy efficient heat transfer using the “metallic” or para proportion of hydrogen in the inbound gas stream to effectively condition the gas storage container to the target temperature. The high percentage of para-hydrogen in the cryogenic hydrogen, enables a change in hydrogen’s Joule-Thompson coefficient, from negative above 200 K and 1 bara to zero at 200 K and 1 bara, to positive below 200 K at 1 bara, and thus enables a high energy efficiency of charging and decanting at low pressures (between 1 bar and 50 bar pressure) and temperatures between 20 K and 200 K, and therefore fewer losses during charging and decanting. For example for a gas storage container which uses [CuIICoIII(CN)6] as the MOF sorbent within the gas storage container, this system will have a Heat of Adsorption for hydrogen between -2 and -6 kJ / mol (shown in FIG. 22; Qst varying with loading conditions) and resultantly charge with total end-to-end losses of as low as 0.5-1.9 kWh / kgh2 for the system as shown in FIG. 22, which is approximately 7.8x more energy efficient than liquefaction. For example for a gas storage container which uses [Cu3(BTC)2] as the adsorbent material within the gas storage container, this system will have a Heat of Adsorption for hydrogen between -4 and -6 kJ / mol (shown in FIG. 21; Qst varying with loading conditions) and resultantly charge with total end-to-end losses of as low as 1.1-1.9 kWh / kgh2 for the system as shown in FIG. 21.

[0204] When the adsorbent material comprises a MOF, MOF selection can be used to catalyse the spin state switch behaviour of hydrogen, catalysing the switch from orthohydrogen to para-hydrogen, and maintaining the para-hydrogen spin-state, once switched. For example MOFs which specific para-magnetic metal-cluster moieties such as the CuII-CuII paddlewheel within Cu3BTC2 can be utilised both in a gas storage container within the gas storage system, and within the components of the hydrogen cryo-cooler and decant skid to catalyse the hydrogen switching behaviour to increase the proportion of para-hydrogen at a given temperature, thereby increasing the energy efficiency of both the gas storage container, and the system-of-systems which includes the cryo-charging system and the decant system. Without being bound by theory, the inventor theorizes that this principle applies generally to all nanoporous, microporous or mesoporous adsorbent materials (e.g. MOF materials) which comprise a paramagnetic metal-ion cluster or core within the framework. For example, Cu3BTC2 may be used within the gas storage container, and / or, within the charging cooler loop, and / or, within the decant system. The invention’s enabling charging cooler loop and decant systems may also be modified to deliver energy efficiency gains to other kinds of gas storage containers such as conventional liquefied hydrogen gas systems. For example, Cu3BTC2 may be used within a modified gas storage container and / or decant system to act as an ex-situ boil-off control and management system for bulk liquefied hydrogen gas systems to eliminate the significant boil-off losses (currently between 1-6% per day losses) experienced by liquefied hydrogen gas. Boil-off in liquefied hydrogen gas is driven principally by exothermic spin-state switching of para-hydrogen back to orthohydrogen, and thus, utilisation of a nanoporous, microporous adsorbent materials such as Cu3BTC2 may be used to slow or stop this process. Boil-off may also be slowed by including a MOF such as Cu3BTC2 inside a conventional liquefied hydrogen gas system as a para-hydrogen catalyst to slow or eliminate boil-off, delivering energy efficiency and loss-reduction benefits. In the case of Cu3BTC2, Cu2+ has a 3d9 electron configuration, resulting in one unpaired electron in its 3d orbitals, making it paramagnetic. The unique paddlewheel geometry aligns each of these two unpaired electrons to be shared between the two Cu-Cu in the paddlewheel (along the axis of the paddlewheel, along overlapping dz Jahn-Teller-distorted axes). A person skilled in the art would further understand that the Jahn-Teller effect also results in these dz orbitals pointing diffusely into the pore volume space along the same axis of the adsorbent material, making it more strongly paramagnetic than a single Cu2+ on its own. Without being bound by theory, the inventor hypothesises that part of the near doubling of the loading potential for hydrogen by Cu3BTC2 relative to CuII3[CoIII(CN6)]2 as shown in FIG. 21 and FIG. 22, results from the cooperative behaviour of Cu-Cu in the paddlewheel to strengthen the para-spin interaction with hydrogen at cryogenic temperatures. In another example, [(Fem2FeH(p3-O))2(ABTC)3] which has a paramagnetic cluster with a Fe2+ and two Fe3+ in the cluster. The Fe2+ has the electron configuration 3d6, resulting in four unpaired electrons in 3d orbitals and resulting in paramagnetic properties. Fe3+ has five unpaired electrons in its 3d orbitals, making it strongly paramagnetic. Without being bound by theory, these transition metal ion clusters with diffuse and unpaired electrons in diffuse transition metal ion d-orbitals, can interact with the electron orbitals of gases near the adsorbent material pore surface, resulting in electron-orbital overlap and driving the spin-state switching behaviour of hydrogen from ortho-hydrogen to parahydrogen, and maintaining the para-hydrogen spin-state, once switched. This paracatalysing effect of specific para-active adsorbent material increases the effectiveness of gas capture, gas adsorption and reduces / eliminates boiloff from liquefied systems.

[0205] In general terms, adsorbent selection for hydrogen storage at cryogenic temperatures should consider surface area of the material, Heat of Adsorption of the material, pore volume of the material, bulk density of the material, and the potential of metal-cluster within the material structure to catalyse the para-hydrogen spin-state.

[0206] The para-spin catalysing properties of exemplary MOFs such as [(Fem2FeH(p3-O))2(ABTC)3] or Cu3BTC2, may be composited with other nanoporous, microporous adsorbent materials such blending the desirable attributes of both materials.

[0207] The invention describes both an engineered design and an activation protocol which enables utilisation of the widest possible range of adsorbent material, including nanoporous, microporous, or mesoporous materials. A person skilled in the art will 49 understand that, for example, some nanoporous, microporous, or mesoporous adsorbent materials have an activation temperature and pressure of 120 °C under vacuum and other nanoporous, microporous, or mesoporous adsorbent materials have an activation temperature of 200 C under vacuum and others still have activation temperatures in excess of 300 C under vacuum. The invention describes a process whereby nanoporous, microporous, or mesoporous adsorbent materials with activation temperature of 120C and below, can be activated in-situ in the gas storage container at 120 C under hot dry nitrogen, or hot dry air. This reduces the cost of activation, especially at large scale, and is a protocol which protects conventional gas valves, fittings, seals and other enabling equipment from degrading under temperature and pressure conditions for which they are not designed, maximising the safety of the overall system. For example, for Cu3BTC2., which has a literature activation of between 120-140 C under vacuum, successful in-situ gas storage container activation can be achieved under a flow of 120 C of hot nitrogen for 24 hours. For materials with a higher activation temperature than 120 C, we describe a protocol herein whereby ex-situ activation can be conducted at the material, activation temperature, for example, [(Fem2FeH(p3-O))2(ABTC)3] is activated under 200 °C under hot nitrogen for 16 hours, and, then can be vacuum bagged and sealed, with a shelf life in excess of 12 months before being filled into the gas storage containers, at ambient temperature conditions at 20 C with any new moisture or gas impurities removable with an in-situ reactivation at 120 C for 12-24 hours. For example, see FIG. 51 for 2-step activation protocol for [(Fem2FeH(p3-O))2(ABTC)3]. In the example at FIG. 51 (A) initial activation is shown to reach completion, in FIG. 51 (B), the same sample was tracked for mass gain owing to moisture sorption from air over 6000 minutes, and in FIG. 51 (C), the same sample was reactivated at 120 degrees Celsius to verify this universal adsorbent activation and reactivation protocol. For example, a process and instrument diagram is shown in FIG. 14 which enables a combined two-step ex-situ and in-situ or a single-step in-situ activation. For example, effective activation using hot dry nitrogen at 100, 120 and 150 degrees Celsius is given in FIG. 47, FIG. 48 and FIG.49 respectively.

[0208] The gas storage system may comprise activation, charging and loading, and decant systems. The systems of systems comprising the activation, charging and loading system, and decant systems, connected to the adsorbent filled gas storage container system is shown as a process an instrumentation diagram in FIG. 8, and a concept diagram FIG. 13 (activation), FIG. 7 (charging) and FIG. 9 (decanting).

[0209] The gas may be hydrogen, biomethane, biogas, carbon dioxide, methane, natural gas, ammonia, oxygen, helium, neon, argon, nitrogen, medical gases, refrigerant gases, hospitality and food / beverage gas mixtures, welding gas mixtures, laser gas mixtures, acetylene, and / or other gases including gas mixtures. The gas may be hydrogen, carbon dioxide, or methane. The gas may be hydrogen. Any gas including any mixtures of gases may be stored in a container comprising a suitable adsorbent material in accordance with the general principles set out herein.

[0210] The physical properties of the gas storage container include, but are not limited to, thermal and pressure conditions, rates of adsorption / desorption, mechanical strength, thermal conductivity, coefficients of thermal material or super material expansion, are tuneable through post-synthetic modification of adsorbent dopants (both type and concentration), and post-synthetic compositing of two or more different MOFs with each other, or compositing of two or more MOFs and / or covalent organic frameworks (COFs) with each other.

[0211] Energy savings may be gained from the inclusion of the adsorbent to reach any given temperature or pressure gas storage container condition.

[0212] The gas stored within the gas storage system may be substantially stored adsorbed to a surface area of the adsorbent material, not as a gas or liquid, resulting in an inherently safe system. “Substantially” in the context may be at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95% of the gas stored within the system is adsorbed to a surface area of the adsorbent material, not as a gas or liquid.

[0213] In the unlikely event of rupture of the gas storage container, the gas is released slowly from the adsorbent and reduces the likelihood of a gas explosion (where the gas is flammable or explosive, for example hydrogen), demonstrating inherent safety.

[0214] The gas storage system may have substantially zero boil-off at any given temperature or pressure gas storage container condition.

[0215] The adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material, comprises Metal-Organic-Framework (MOF) materials, Covalent-Organic-Framework (COF) materials, MOF-composite materials, MOF-hybrid materials, and / or MOF-hybrid-composite materials.

[0216] The adsorbent material may be highly porous having >700 m2 / g, >1000 m2 / g, 1300 m2 / g, >1600 m2 / g, >1800 m2 / g, >2000 m2 / g, >2200 m2 / g, >2400 m2 / g, >2600 m2 / g, >2800 m2 / g, >3000 m2 / g, >4000 m2 / g, > 8000 m2 / g of surface area to absorb gas. 51

[0217] The adsorbent material may be able adsorb the gas at > 37.5 to>77.5 g(hydrogen) / L at 85 - 25 K respectively and 30 bar pressure charge conditions (for hydrogen), or >140 g(methane / biomethane / natural gas / biogas) / L to 240 g(methane / biomethane / natural gas / biogas) / L at 298 K and 50 bar pressure, or around greater than >155 g(methane / biomethane / natural gas / biogas) / L at 298 K and 50 bar pressure (for methane / biomethane / natural gas / biogas). This may increase the efficiency and / or reduce the cost of the storage system.

[0218] The adsorbent material may be replaceable, without changes to the gas storage container certification. This may be facilitated through the utilisation of mechanically robust and chemically robust MOF selection. Suitable MOFs may have proven cyclability even with exposure to impurities. For example, cycling data with water and other gaseous impurities within a hydrogen gas is shown for [(Fem2FeH(p3-O))2(ABTC)3] and Cu3BTC2. Both materials show the trapping of hydrogen without penalty to the gravimetric uptake as the water and other gas impurities do not adsorb to the material at the high Heat of Adsorption sites for target gases, such as hydrogen. The data also shows that impurities trapped in the pores can be removed with simply low-level vacuum for between 1 and 6 hours as shown in FIG. 50, where deliverable capacity of hydrogen does not change even as the mass of the sample increases with moisture sorption, and where pristine performance is restored with a simple vacuum of 10-3 mbar pressure.

[0219] The adsorbent material can be reused in a gas storage container and / or gas storage system without reprocessing or recycling the adsorbent material.

[0220] The gas may be released by a user on changes in temperature or pressure or both.

[0221] The gas storage system may be utilized in gas storage containers greater than 0.1 litres.

[0222] The gas storage system may operate at pressures above 1 bar and up to 950 bar. The gas storage system may operate at pressures from 2 to 3 bar for super scale storage, at 10 bar for international shipping, 30-60 bar for ISO containers, and up to 400 bar for ambient temperature high-pressure storage for automotive.

[0223] The system may be operated at different temperatures greater than 4 K and up to 500 K, if pressures do not rise above the certified maximum pressure rating of the inner shell, with the upper bound of temperature bound by the allowable working temperatures of the balance of plant components on the gas storage container.

[0224] The adsorbent material filling the void in the gas storage container acts as an adsorbent for the gas being stored, and increases the dormancy / dwell time / hold time days up to 20 days, up to 30 days, up to 40 days, up to 50 days, up to 60 days up to 130 days, up to 160 days, without the need for an active powered cooling system to keep the system at the correct temperature.

[0225] The gas storage container, when operating a cryogenic temperatures in use, remains safe without human intervention for up to 20 days, up to 30 days, up to 40 days, up to 50 days, up to 60 days up to 130 days, up to 160 days, at a time which means up to 20 days, up to 30 days, up to 40 days, up to 50 days, up to 60 days, up to 130 days up to 160 days. The gas storage container when operating at ambient temperature remains safe without human intervention for an unlimited amount of time.

[0226] The gas storage container, when operating a cryogenic temperatures in use operates autonomously without human intervention for up to 20 days, up to 30 days, up to 40 days, up to 50 days, up to 60 days up to 130 days, up to 160 days, at a time which means up to 20 days, up to 30 days, up to 40 days, up to 50 days, up to 60 days, up to 130 days up to 160 days. The gas storage container when operating at ambient temperature remains safe without human intervention for an unlimited amount of time.

[0227] The metal organic framework (MOF) material may be optimized for temperatures and pressures, above 1 - 950 bar and temperatures to 4-500 degrees K.

[0228] The gas storage container may be conformable into a variety of shapes.

[0229] The gas storage container may be an ISO-certified compliant storage system for intermodal shipping containers between 8ft and up to 45ft long.

[0230] The gas storage system may be at least 30 Litres and up to 60,000 Litres. The system may be utilised for one-to-many, many-to-one, and many-to-many bulk gas distribution, to facilitate efficient bulk gas transport, and this can be digitalised and digitally visualised in real time to provide information to algorithms and third-party software.

[0231] The figures are now referenced in more detail. It is understood that examples of the disclosures herein are provided. The figures are not intended to be limiting.

[0232] In the accompanying drawings there is disclosed in FIG. 1 a gas storage system (100) example of a cryo-compressed double-walled vacuum insulated gas storage container (11) full of adsorbent material (7). The gas storage container (10) comprises an outer shell (1) surrounding an inner shell (2), a void volume of the space under vacuum (3) between the inner and outer shell, and / or insulation (4) there between. The outer shell (1) made of either metal (e.g. steel, aluminium) or a carbon fibre composite material and the inner shell (2) comprising either a 316 stainless steel or other metal alloys that do not suffer corrosion or embrittlement over time metal (Type-I) or metal wrapped with carbon-fibre composite (Type-II or Type-III), or polymer wrapped with carbon-fibre composite (Type-IV) or carbon-fibre composite material (Type-V). The entire gas storage container being filled with adsorbent materials as described herein, for example, a Metal-Organic-Framework (MOF) nanoporous material , or a MOF-hybrid nanoporous material or MOF-composite nanoporous material or a MOF-hybrid-composite nanoporous material, which is highly adsorbent, the adsorbent material being adapted in use to adsorb and release gas.

[0233] There is shown an insulation layer (4) which either wraps the inner shell (2) or fills the void volume of the space under vacuum (3) between the outer shell (1) and inner shell (2), or both. There is also shown piping (5) for filling and / or withdrawal of cryo-conditioned gases or the like via the boss-head and valve fittings (6) or the like. The adsorbent (7) may have various macromorphologies, which fill the void volume of the space under vacuum (3) between the outer shell (1) and inner shell (2) of the gas storage container. The coatings (8) can optionally be applied to improve longevity of the inner shell (2).

[0234] FIG. 2 shows an example gas storage system (100) wherein the ambient temperature operation single-walled pressurised gas storage container (12) is full of adsorbent material (7). The ambient temperature operation single-walled storage container shell (21) of a single-walled gas storage container comprises of either a 316 stainless steel or other metal alloys that does not suffer corrosion or embrittlement over time metal (Type-I) or metal wrapped with carbon-fibre composite (Type-II or Type-III), or polymer wrapped with carbon-fibre composite (Type-IV) or carbon-fibre composite material (Type-V).

[0235] A coating (22) can optionally be applied to improve longevity of the ambient temperature operation single walled inner shell pressure storage container or the ambient temperature operation single walled pressurised gas storage container (12). A boss-head and valve fittings (23) or the like is installed to assist with gas filling / withdrawal. The adsorbent may have various macromorphologies, which fills the void of the ambient temperature operation-single walled gas storage container (12).

[0236] Referring now to FIG. 3 and FIG. 4, shown is an example of a gas storage container (10) suitable for use as a gas storage system (100). The exemplary gas storage container (10) is a 1000 Litre double-walled (1,2) cryogenic gas storage container (11) suitable for filling with adsorbent (7) for storing and / or transporting gas, for example hydrogen, methane, helium, oxygen, nitrogen, argon, carbon dioxide, or any other desired gas or gas mixtures in conjunction with selection of a suitable adsorbent according to the principles of general application set out herein. The gas storage container (10) has a vertical orientation with dimensions of approximately 1300x1200x2300 mm (LxWxH), and is designed to operate from 18 K to 400 K, and from 24 bar maximum allowable working pressure down to full vacuum (<0.001 mbar). The total weight of the cryogenic gas storage container (11), including adsorbent material (7), peripheral piping (5) and instrumentation is less than 1460 kg. The void volume of the space under vacuum (3) between the outer shell (1) and the inner shell (2) has a vacuum hardness of 10-6 mbar absolute pressure with the inner shell (2) wrapped using multilayer insulation (4) to minimize heat leak into the inner shell (2). The vacuum hardness may be selected according to the required dormancy of the gas storage container, within practical bounds of what is manufacturable. For example, a higher vacuum of 10-7 mbar pressure is desirable but may be difficult to achieve. Lower vacuums of 10-5 mbar pressure would be lower cost to achieve but may start to sacrifice dormancy performance. The gas storage container (10) outlet is from the bottom of the gas storage container through an in-storage container filter and out through a super insulated vacuum line to minimize heat losses, for example, using multi-layered insulation (MLI). The gas storage container (10) is also fitted with a flanged port for passage of adsorbent material (7) and may also be used for instrumentation, safety vents etc.

[0237] FIG. 5 shows a possible Process and Instrumentation Diagram for a cryogenic gas storage container (11), which is an exemplar gas storage container (10) in a vertical orientation, suitable for use in a gas storage system (100).

[0238] Referring now to FIG. 6, shown is a process and instrumentation diagram for an exemplar gas storage container (10), in horizontal orientation, for a cryogenic gas storage container (11) in the form of a 20ft ISO 20,000 Litre ISO gas storage container suitable for use in a gas storage system (100). The FIG. 6 gas storage container (10) has a horizontal orientation with a 20,000 Litre volume, and like the example of FIG. 3, FIG. 4 and FIG. 5 is double-walled and designed to operate at a range of temperatures including cryogenic temperatures between 18 K and 400 K, and 0 bar to 50barg and under full vacuum (of vacuum hardness 10-3 mbar), making it suitable for cryogenic storage of gases such as hydrogen.

[0239] The exemplary gas storage container (10) is shown to be equipped with a pressure transducer and indicator as well as multiple temperature sensors to monitor temperature and pressure inside the gas storage container in the gas space and adsorbent bed. The gas storage container (10) has three primary relief valves where each one is capable of full relieving capacity required, thus providing redundancy. The relief valves can also be isolated with venting provision on each one to facilitate maintenance. The gas storage container (10) is also provided with a provision to be vented through a separate isolation valve if required. Connections C1 and C2, and the associated piping to the gas storage container are super insulated vacuum type to minimise the heat leak into the cryogenic gas as it is cooled through recirculation through an external cryocooler. Any gas inlet into the gas storage container is routed through connection C1 which distributes the gas at one horizontal end of the gas storage container. Any gas exiting the gas storage container during charging / discharging recirculation is routed through connection C2. In-line filters are provided outside the gas storage container (10) on connection C2 with redundancy to take one in maintenance if required. Both these inlets and the outlet connections are provided with double isolation valves for redundancy and relief valves between the isolation points. One of these isolation valves on each connection are automated to achieve remote isolation. The connections C1 and C2 are also provided with provisions to be equalised, purged and vented as required. The MOF adsorbent material (7) can be charged or discharged from the gas storage container through a low heat-leak flange connection M1. The connection C3 acts as a gas discharging point equipped with an inline filter with redundancy and double isolation valves with one of them automated. The outer shell (1) is provided with a provision to vacuum purge the interspace void volume (3) between the inner shell (2) and the outer shell (1). The outer shell (1) is also equipped with a blow-off disc to provide a safety relief for the void volume of the space under vacuum (3) between the outer shell (1) and inner shell (2). The vacuum hardness in the vacuum interspace can be monitored with a pressure transducer provided on the outer shell (1) of the cryogenic gas storage container (11) with an isolation valve.

[0240] It is to be understood that the gas storage container (10) of FIG. 1, FIG. 2, FIG. 3, FIG. 4, FIG. 5 and FIG. 6 are provided as examples only, and that the gas storage system disclosed herein may be used with gas storage container of various shape and 56 configuration using the general principles set out herein, including but not limited to large gas storage containers for industrial gas storage, static gas capture applications, gas capture applications on bulk gas carriers such as ancillary boil-off gas prevention on liquefied gas carriers, boil-off gas prevention for other applications, small gas cylinders, fuel tanks for vehicles, or any other application of gas storage of any size, such as but not limited to smaller gas storage container of less than 30L, or a larger gas storage container of up to 300 Litres, or up to 500 Litres, or up to 1000 Litres, or up to 950 Litres, or up to 2500 Litres, or up to 4,000 Litres, or up to 7000 Litres, or up to 9,000 Litres, or larger gas storage container of 17,500 Litres or 20,000 Litres as typical for 20ft ISO gas storage container, larger 30,000 Litres or 33,000 Litres gas storage container as typical for 30ft ISO gas storage container, larger 40,000 Litres or up to 44,000 Litres gas storage container as typical for 40ft ISO gas storage container, giga-scalable Type-C tanks used as gas storage containers of up to 12,300,000 Litres, or up to 266,000,000 Litres, for example.

[0241] Referring now to FIG. 7 and FIG. 8, shown are gas storage systems (100) having example charging subsystems (200) that may be used to charge gas to the gas storage container (10) containing adsorbent (7) for gas storage. By way of example, cryogenic storage of gases such as hydrogen at low temperatures, and the FIG. 7 charging subsystem (200) advantageously makes use of the gas to be stored itself as a heat transfer fluid. This is achieved by a charging loop (201) whereby cold gas is added to the gas storage container (10) a portion of which is adsorbing to the adsorbent (7) thus releasing heat from the exothermic adsorption process. This heat released from Heat of Adsorption is then transferred to the remaining portion of hydrogen which is not adsorbed and within the void space between adsorbent particles, as well as sensible heat from the gas storage container (10) and the adsorbent (7) as gas travels through the gas storage container (10). This remaining portion of not-yet-adsorbed gas then exits the gas storage container, carrying away heat, and returns to the charging loop (201) to be cooled back down to the charging temperature and circulated back into the gas storage container (10) to equilibrate the system to the target charging temperature. This loop may be repeated until the target temperature is achieved as shown in FIG. 23 (A) for a 20,000 Litre gas storage container.

[0242] The charging loop connects with an inlet (203) of the gas storage container (10) and an outlet (204) of the gas storage container to thus form the loop (201) allowing recirculation of gas. The charging loop (201) may include a charging closed-loop heat 57 exchanger (202) upstream of the inlet to cool gas before introduction into the gas storage container (10). The circulation may also include a charging pressurising device (206), such as a blower or compressor to circulate gas through the charging loop (201). The charging subsystem (200) continues to operate until the gas storage system achieves the storage temperature and pressure.

[0243] FIG. 7 and FIG. 8 show the feed gas from the gas supply line (205) being added to the charging loop (201) upstream of the charging closed-loop heat exchanger (202). The feed gas may be cooled with a separate heat exchanger.

[0244] The charging subsystem (200) thus utilizes the Heat of Adsorption for the stored gas during charging by having a portion pass through the gas storage container (10), with only a portion adsorbing to the adsorbent material (7) on each pass through the charging loop (201). Thus, a portion of gas moves through the interstitial spaces between adsorbent materials as a heat transfer fluid, exiting the gas storage container (10) carrying with it the waste heat from exothermic adsorption. The charging subsystem (200) thereby allows the system (100) to reach the final temperature pressure equilibrium at improved speed and energy efficiency.

[0245] Using the stored gas as a heat transfer fluid and as the adsorbed gas, simultaneously, with non-adsorbed gas carrying heat released from adsorption back to the charging closed-loop heat exchanger (202) to be recycled, re-cooled and returned to the gas storage container (10), enables elimination of gas blow-off in the process so that the system can operate as a closed-loop system to increase energy efficiency, and eliminate gaseous molecule losses. In contrast with existing systems, where gases are presently loaded into liquefied gas storage containers whereby boil-off gas is blown through and allowed to release to the atmosphere, a major source of thermal energy inefficiency, gas molecule losses, and source of safety hazard for flammable gases.

[0246] FIG. 8 exemplifies a charging subsystem (200) adapted to a cryogenic gas storage system (11) and thus use a cryocooler as a charging closed-loop heat exchanger (202) and a cryoblower as a charging pressurizing device (206). These components may be co-located in a housing (207) under vacuum conditions to minimize heat loss. Said housing (207) may also include instrumentation to track system performance during the charging process and is represented as the dotted line box in FIG. 8.

[0247] Advantageous use of the charging subsystem (200) is not limited to cryogenically stored gases such as hydrogen. Gas storage systems (10) with adsorbent material (7) filled gas storage container operating at ambient temperatures, for example storing biogases such as biomethane, can similarly have the heat generated by adsorption removed using the charging subsystem (200) to enable rapid charging of biomethane into compressed biomethane gas storage containers operating at ambient temperatures (12), and removal of heat from exothermic adsorption in a similar loop (201). However, in such situations alternative charging closed-loop heat exchangers (202) to a cryocooler may be selected. For example, a heat exchanger making use of ambient air may be sufficient for gases stored at ambient temperature conditions. The person skilled in the art is able to select an appropriate heat exchanger for any gas storage temperature according to normal principles. The heat exchanger may involve natural convection to provide cooling to the circulating gas. The heat exchanger may involve forced convection to provide cooling to the circulating gas. The heat exchanger may simply comprise a section of the charging loop being exposed to ambient temperature and pressure. The heat exchanger may comprise a section of the charging loop being exposed to ambient temperature and pressure, wherein said section is configured with fins or some other structure to increase heat transfer area. The heat exchanger may be a refrigeration device. The heat exchanger may involve a secondary fluid to remove heat from the circulating gas in a shell and tube or plate style heat exchanger, or any other suitable method to remove heat to the circulating gas.

[0248] Gas which loads into the adsorbent material (7), including a nanoporous, microporous, or mesoporous adsorbent material (7)-filled gas storage container (10), loads into the pores of the adsorbent material (7) at sites with the highest Heat of Adsorption first, followed by further adsorption and loading at sites with lower Heat of Adsorption. As nanoporous, microporous or mesoporous adsorbent material (7)-filled gas storage container (10) is loaded, the free space volume of the adsorbent (7)-filled gas storage container has no sites for adsorption, so will be filled with gas at a lower volumetric density than gas adsorbed within the pores of the material.

[0249] As the adsorbent materials (7) are relatively insulating in their thermal conductivity, a secondary thermal transfer fluid passed through internal tubes in a gas storage container (10) would be less efficient in providing the thermal conditioning required to cool the system in the case of cryogenic gas storage containers (11), as the conduction would be ineffective to cool the adsorbent materials (7). By using the gas to be stored, as its own heat transfer fluid, this enables utilisation of convection supported 59 energy efficient heat transfer from the gas at cryogenic temperatures to recondition the cryogenic gas storage container (11) to the target temperature and pressure.

[0250] Referring now to FIG. 55, shown is a flowchart of a method for charging gas to a gas storage container comprising one or more adsorbent material (1000). The method comprises circulating gas through the storage container (1001), cooling unadsorbed gas from the gas storage container prior to recirculating (1002), and repeating steps (1001) and (1002) until the target temperature and / or pressure is achieved (1003) as discussed above in relation to FIG. 7 and FIG. 8 as well as elsewhere throughout the present disclosure.

[0251] Referring now to FIG. 9, FIG. 10, FIG. 11 and FIG. 12, shown are example gas storage systems (100) having a decanting subsystem (300) that may be used to discharge gas stored in the gas storage container (10). Like the charging subsystem (200), the decanting subsystem advantageously makes use of the gas stored in the gas storage container (10) itself as a heat transfer fluid to provide energy to desorb gas from the adsorbent material (7). This is achieved using a decanting loop (301) whereby heated gas is added to the gas storage container (1) to provide the requisite Heat of Desorption to release the adsorbed gas from the adsorbent material (7) which then exits the gas storage container (10) through the decanting loop (301) to be heated and recirculated back through the gas storage container (10). As the circulation of gas is established in the circulation loop (301), the gas storage container (10) pressure will begin to increase due to the release of gas from the adsorbent (7). Once the target pressure is obtained, it can be maintained by decanting excess gas. Once the target temperature is achieved, circulation of gas can be stopped, and further decanting of gas can be achieved by lowering the gas storage container (10) pressure.

[0252] The decanting loop (301) comprises a decanting closed-loop heat exchanger (302) to provide heat to the circulating gas. In the example of FIG. 10 and FIG. 11, a decanting closed-loop electric heater (302) is used as the decanting closed-loop heat exchanger. In the example of FIG. 12, an intermediate glycol-water decanting closed-loop heat exchanger (302) utilizing waste heat from fuel cell is used. The person skilled in the art is able to select an appropriate heat exchanger according to normal principles. The decanting closed-loop heat exchanger (302) may involve natural convection to provide heat to the circulating gas. The decanting closed-loop heat exchanger (302) may involve forced convection to provide heat to the circulating gas. The decanting closed-loop heat exchanger (302) may simply comprise a section of the decanting loop being exposed to ambient temperature and pressure. The decanting closed-loop heat exchanger (302) may comprise a section of the decanting loop being exposed to ambient temperature and pressure, wherein said section is configured with fins or some other structure to increase heat transfer area. The decanting closed-loop heat exchanger (302) may be a heater. Said decanting closed-loop heater (302) may be an electric heater or a gas heater. The decanting closed-loop heat exchanger (302) may involve a secondary fluid to provide heat to the circulating gas in a shell and tube or plate style heat exchanger, or any other suitable method to provide heat to the circulating gas. FIG.9 shows the decanting pressurising device (306) on a portion on the loop (301) in dotted lines to thereby indicate the decanting pressurizing device (306) would not be present where a thermosiphon effect is used to induce flow within the loop (301). Alternatively, decanting pressurizing device (306) may be used to initiate flow within the loop (301) to begin the decanting process, whereafter it is not used as a thermosiphon effect continues circulation of gas within the loop (301). FIG. 9 also shows a gas discharge line (305) with a gas decanting line heating device (307), however, gas storage system may not include said gas decanting line heating device (307) depending on the gas storage system (100) design and user requirements. In alternative examples, the gas discharge line may be drawn off the loop (301) and optionally make use of the decanting closed-loop heating device (302).

[0253] The decanting loop may also comprise a decanting pressurizing device (306) to encourage flow of gas in the decanting loop (301), such as a blower or compressor in FIG. 10 and FIG. 12. Alternatively, a thermosiphon effect may induce natural convection of gas within the decanting loop as in example of FIG. 11. Use of natural convection in this manner may lower the energy requirements of decanting the gas. This may be particularly advantageous when compared to existing devices, as the energy requirements of the gas storage system (100) may be effectively front loaded to the charging process, as the gas storage system (100) provides for improved dormancy in relation to storage of cryogenically stored gasses without energy inputs as hereinbefore described, and the energy requirements of decanting can be reduced using natural convection to circulate gas through the decanting loop (301). Such an effect may be enhanced where passive heat exchange can be used to heat the gas circulating in the decanting loop (301), for example using atmospheric air. Front loading the gas storage system (100) end-to-end energy demand requirements enables spend of energy where it is typically the lowest cost - at the gas source or the at the place of gas production, thereby reducing the overall cost of storing and transporting the gas.

[0254] Referring now to FIG. 56, shown is a flowchart of a method for decanting gas from a gas storage container comprising one or more adsorbent material (2000). The method comprises heating desorbed gas from the gas storage container (2001), recirculated said heated gas back through the gas storage container (2002) and repeating steps (2001) and (2002) until the target pressure is achieved (2003) as discussed above in relation to FIG. 9, FIG. 10, FIG. 11 and FIG. 12 as well as elsewhere throughout the present disclosure.

[0255] Referring now to FIG. 13 and FIG. 14, shown are example gas storage systems (100) having an activation subsystem (400) that may be used to activate the adsorbent material (7) of the gas storage container (10). Activation of the adsorbent (7) is required prior to charging with gas in order to maximise gas storage capacity at any defined temperature and pressure. Activation can either be carried out in-situ with the adsorbent (7) within the gas storage container (10), or ex-situ before the adsorbent (7) is loaded into the gas storage container (10), or both ex-situ at temperatures above 120oC followed by a second in-situ activation step at about 120oC. The one-stage in-situ activation of adsorbent materials (7) with an activation temperature less than 120oC or two-stage ex-situ-in-situ activation process for adsorbent materials (7) with activation temperature greater than 120oC enables any adsorbent material (7) to be activated without compromising the safety integrity of the balance of plant of the gas storage container (10).

[0256] Activation involves a first stage where the adsorbent material (7) is heated using air, nitrogen or any other inert gas. An activation heat exchanger (402) may be used to heat the inert gas. An activation loop (401) may be provided to remove moisture from the gas after it passes the adsorbent material (7) before being recirculated back into the gas storage container (10). Moisture may be removed using a dehydrator or dryer element (403). The temperature of the first stage of activation is dependent on the adsorbent (7) being used. In cases where a high activation temperature is required, it may be impractical or otherwise unable for the first activation step to be performed insitu in the gas storage container (10), in which case, the first stage of activation can be performed ex-situ using ancillary equipment. A second stage of in-situ activation then involves vacuum purging contaminants from the adsorbent material (7). An activation vacuum pump (404) or similar may be used to induce said vacuum. The second stage in-situ activation may be performed at approximately 120°C under a flow of hot inert gas (such as nitrogen or dry air) for 24 hours to 72 hours, or between ambient temperature and 120°C under vacuum of 0.1-1 mbar of pressure for 24 hours to 72 hours, as an insitu adsorbent material activation or reactivation.

[0257] In general, this two-stage ex-situ-in-situ activation process means an adsorbent material (7) can be manufactured and activated in a first stage at the adsorbent materials (7) manufacturing site or otherwise prior to loading into the gas storage container (10).

[0258] Then, following shipment and loaded into the gas storage container (10), the gas storage container (10) is able to be used as a secondary second stage in-situ activation, in case the adsorbent material (7) was exposed to air and gases from air adsorbed into the pore space. Accordingly, the second stage does not require as high temperature as the first and can therefore be done in-situ in the gas storage container (10) without damage to the gas storage container or valves or fittings, with off-the-shelf fittings typically rated to about 135°C or to about 150oC. Where the gas storage container (10) balance of plant components are rated for higher temperatures, higher second stage insitu activation temperatures may be used to reduce the time taken for reactivation.

[0259] If there are certain impurities which get temporarily trapped in the adsorbent material (7) during operation, this second stage in-situ activation can be used as a reactivation technique to restore the adsorbent material (7) to operable condition on maintenance schedule, for example, every 1-5 years during a 20-40 year life of the gas storage container (10). Shorter maintenance schedule cycles for lower grade gas mixes are anticipated as they have higher concentrations of impurities (such as for low grade biomethane or biogas). Longer maintenance cycles are anticipated for cryogases, especially cryogenic hydrogen as these gases are likely to be of higher purity, owing to their charge temperature as impurities tend to liquefy, separate out, and are removed in the cryocooler.

[0260] The activation temperature is dependent on the adsorbent. For example, some MOFs have an activation temperature and pressure of 120°C under vacuum and other MOFs have an activation temperature of 200°C under vacuum and others still have activation temperatures in excess of 300°C under vacuum. Adsorbents with activation temperature of 120T and below, can generally be activated in-situ in the gas storage container at 120°C under hot dry nitrogen, or hot dry air. This reduces the cost of activation, especially at large scale, and is a protocol which protects conventional gas valves, fittings, seals and other enabling equipment from degrading under temperature and pressure conditions for which they are not designed, maximising safety of the overall system. For example, for Cu3BTC2., which has a literature activation of between 120-140°C under vacuum, successful in-situ gas storage container activation was achieved under a flow of 120°C of hot nitrogen for 24 hours. For materials with a higher activation temperature than 120°C, ex-situ activation can be conducted at the activation temperature, for example, and can then be vacuum bagged and sealed before being filled into the gas storage containers, at ambient temperature conditions at 20°C with any new moisture or gas impurities removable with an in-situ reactivation at 120°C for 12-24 hours. Testing has shown, such activated and vacuumed sealed adsorbents may have a shelf life in excess of 12 months. For example, as shown in the thermogravimetric analysis in FIG. 51, [(Fem2FeH(p3-O))2(ABTC)3] was activated ex-situ at 200 degree Celsius 60 minutes using a flow of hot dry nitrogen gas, as shown in FIG. 51 (A). The material was exposed to air for a period of 6000 minutes simulating storage in ambient temperature and pressure conditions, where the material adsorbs gases such as water vapour in the atmosphere as shown in FIG. 51 (B). These gases can then be completely removed during the in-situ stage-two activation process at 120 degrees Celsius with a flow of hot nitrogen gas, with the sample showing complete restoration of pore volume after 12 hours as shown in FIG. 51 (C).

[0261] Referring now to FIG. 57, shown is a flowchart of a method for activating adsorbent material for use in a gas storage system (3000). The method (3000) comprises the first activation stage (3001) and the second stage (3002) as discussed above in relation to FIG. 13 and FIG. 14, as well as elsewhere throughout the present disclosure.

[0262] The gas storage system may comprise a single gas storage container. The gas storage system may comprise a single gas storage container mounted to a structure, such as a frame or skid, along with one or more of the disclosed sub systems. For example, the gas storage system may comprise a gas storage container with the charging subsystem and / or the decanting subsystem and / or activation subsystem mounted to a common structure for co-location. Continuing the example, the gas storage system may comprise a structure to which a gas storage container in the form of an ISO gas storage container is mounted along with ancillary equipment comprising one or more of the charging subsystem, decanting subsystem or activation subsystem. The gas storage container may be transported along with one or more subsystems 64 thereby obviating the need for such subsystems to be located or separately transported to the point of their required use. Multiple gas storage containers may be mounted to a common structure along with one or more subsystems.

[0263] The gas storage system may comprise a gas storage container that is discreet from the associated subsystems. The gas storage container may be used to store and transport gas between two locations, with the charging subsystem at a first location to load the gas storage container, and the decanting subsystem at the second location to discharge the gas storage container.

[0264] The gas storage system may comprise multiple gas storage containers. The example of FIG. 15 shows a Process & Instrumentation Diagram (P&ID) of a gas storage system comprising gas storage containers (multiple 20,000 Litre 20ft ISO gas storage container) connected to a single decanting subsystem so that the storage containers may be discharged in parallel according to user requirements. The Example of FIG. 16 shows a Process & Instrumentation Diagram (P&ID) comprising multiple gas storage containers (in this case multiple 20ft ISO 20,000 Litre gas storage containers) connected to a single active decanting subsystem whereby waste heat provided by a downstream fuel-cell power unit is used by the decanting system to increase the discharge flow rate of the gas storage container to between 120 kg(hydrogen) / hour and 800 kg(hydrogen) / hour using the waste heat source to discharge multiple gas storage containers in parallel thereby increasing energy efficiency. Advantageously, the Process & Instrumentation Diagram (P&ID) also passes the cold energy recovery from cryogenic hydrogen back to the fuel-cell to improve its net output power efficiency. Ambient temperature gas storage containers may use similar multi-element gas containment configuration to enable rapid deployment of infrastructure scale gas storage for biogas / methane / natural gas / biomethane / carbon dioxide at 50 bar pressure.

[0265] For cryogenic low-pressure storage of hydrogen between 20 K to 150 K temperature and 1 bar to 150 bar pressure, the charging and decanting system leverages the increasing proportion of para spin-state hydrogen to ortho spin-state hydrogen at decreasing temperature. This is due to ortho-hydrogen being the more stable form at high temperatures, while para-hydrogen is the more stable form at low temperatures, as well as there being approximately 50:50 ratio of para to ortho at 77 K. Cold cryogenic hydrogen may be at a temperature of 77 K, 80 K, 85 K, 65 K, 60 K, 50 K, 40 K, 30 K, or 20 K. The temperature may enable energy efficient heat transfer using the “metallic” or para proportion of hydrogen in the inbound gas stream to effectively condition the gas storage container to the target temperature. The high percentage of para-hydrogen in the cryogenic hydrogen enables a high energy efficiency and few losses during charging and discharging. For example a gas storage system using [CuIICoIII(CN)6] as the adsorbent within the gas storage container will have a Heat of Adsorption for hydrogen between -2 and -6 kJ / mol as shown in FIG. 22 with Heat of Adsorption varying with loading conditions, and resultantly charge with total end-to-end losses of as low as 0.5-1.9 kWh / kg(hydrogen) for the gas storage system, which is approximately 7.8x more energy efficient than liquefaction, which typically requires about 15 kWh / kg(hydrogen) to liquefy and more energy to maintain extreme cold temperatures to manage liquefied hydrogen gas boiloff (typically between 1-6% per day). For example for a gas storage container which uses [Cu3(BTC)2] as the adsorbent material within the gas storage container, this system will have a Heat of Adsorption for hydrogen between -4 and -6 kJ / mol (shown in FIG. 21; Qst varying with loading conditions) and resultantly charge with total end-to-end losses of as low as 1.1-1.9 kWh / kg(hydrogen) for the system as shown in FIG. 21.

[0266] For hydrogen specifically, MOF selection can be used to catalyse the spin-state switch behaviour of hydrogen, catalysing the switch from ortho-hydrogen to parahydrogen, and maintaining the para-hydrogen spin-state, once switched. For example, MOFs which specific para-magnetic metal-cluster moieties such as the CuII-CuII paddlewheel within Cu3BTC2 can be utilised both in gas storage container within the storage system, and within the components of the hydrogen cryo-cooler and decant skid to catalyse the hydrogen switching behaviour to increase the proportion of parahydrogen at a given temperature, thereby increasing the energy efficiency of both the gas storage container, and the system-of-systems which includes the cryo-charging system and the decant system. Without wishing to be bound by theory, the inventor theorizes that this principle applies generally to all nanoporous, microporous or mesoporous MOF materials which comprise a paramagnetic metal-ion cluster or core within the framework. For example, Cu3BTC2 may be used within the gas storage container, and / or, within the charging cooler loop, and / or, within the decant system. The invention’s enabling charging cooler loop and decant systems may also be modified to deliver energy efficiency gains to other kinds of gas storage containers such as conventional liquefied hydrogen gas systems. For example, Cu3BTC2 may be used within a modified gas storage container and / or decant system to act as an ex-situ boil-off control and management system for bulk liquefied hydrogen gas systems to 66 eliminate the significant boil-off losses (between 1-6% per day losses) experienced by liquid hydrogen. Boil-off in liquid hydrogen is driven principally by exothermic spin state switching of para-hydrogen back to ortho-hydrogen, and thus, utilisation of a nanoporous, microporous adsorbent material such as Cu3BTC2 may be used to slow or stop this process. Boil-off may also be slowed by including a MOF such as Cu3BTC2 inside a conventional liquefied hydrogen gas system as a para-hydrogen catalyst to maintain the para-hydrogen spin-state, slowing the rate of para-to-ortho switching resulting in a reduction in exothermic heat release, to slow or eliminate hydrogen boil-off, delivering energy efficiency and gas loss-reduction economic and environmental benefits.

[0267] The gas storage container for storage and transport may implement nanoporous adsorbent materials including Metal-Organic-Framework (MOF) materials, Covalent-Organic-Framework (COF) materials, MOF-composite materials, MOF-hybrid materials, and / or MOF-hybrid-composite materials, optimized specifically for gas storage, at more moderate temperatures and lower pressures which are allowable or practicable for bulk storage and transport. The implementation of the nanoporous adsorbent increases dormancy or dwell time or holding time without active cooling intervention, improves energy efficiency of filling and emptying, improves inherent safety through the storage of gas adsorbed to the surface area of the nanoporous materials, rather than entirely in gaseous or liquid form, enabling a dramatic lowering of pressures, and improving volumetric density of gas storage on a kg / m3 basis.

[0268] Such a gas storage system uniquely brings together two technologies for the first time: advanced nanoporous sorbent (Metal-Organic-Framework (MOF) materials, Covalent-Organic-Framework (COF) materials, MOF-composite materials, MOF-hybrid materials, and / or MOF-hybrid-composite materials) and a gas storage container comprising carbon-fibre composite material which enables higher volumetric density of gas storage. This system enables an increase in gas storage densities. For example, in the case of hydrogen storage, improvements in densities up to 450% at a given temperature and pressure are demonstrated, compared with the same stored volume of hydrogen without adsorbent material. This enables higher storage volumes per container at much lower pressures.

[0269] The gas storage system has a simplified balance of plant, resulting from reduced or eliminated active cooling requirements, elimination of boil-off recovery systems, and 67 reduction in pressure relief valves and other safety systems, because the adsorbent material filled-gas storage container of the gas storage system is inherently safe.

[0270] The gas storage container may have an outer shell surrounding an inner shell, both made of metallic in steel or aluminium that is filled with the nanoporous adsorbent materials (including Metal-Organic-Framework (MOF) materials, Covalent-Organic-Framework (COF) materials, MOF-composite materials, MOF-hybrid materials, and / or MOF-hybrid-composite materials). Gas may be adsorbed upon the inner surface of the nanopores of the adsorbent material.

[0271] The gas storage container may have an outer shell surrounding an inner shell, made of carbon-fibre composite wrapped in a Type-III (aluminium lined with carbon-fibre overwrap), Type-IV (plastic lined with carbon-fibre overwrap) or Type-V (liner less, pure carbon-fibre) carbon composite material, that is filled with the nanoporous adsorbent materials (including Metal-Organic-Framework (MOF) materials, Covalent-Organic-Framework (COF) materials, MOF-composite materials, MOF-hybrid materials, and / or MOF-hybrid-composite materials). Gas may be adsorbed upon the inner surface of the nanopores of the adsorbent material, and the carbon-composite gas storage container facilitates a lighter construction of storage container, enabling improved gravimetric efficiency systemwide.

[0272] The thermal mass and thermal conductivity of the adsorbent material can be tuned pre-synthetically through crystal design and engineering or post-synthetically modified through composite blending or hybridizing with other advanced materials of differing thermal conductivities, enabling tuneable and longer dormancy / dwell / hold time. This contributes to the thermal optimization of the overall gas storage system. FIG. 11 shows the results of optimisation of the MOF materials to increase gas adsorption uptake.

[0273] A further contribution to thermal optimization of the overall gas storage system is the vacuum and materials-based insulation in the gas storage container walls. FIG. 23 shows the results of thermal modelling using Computational Fluid Dynamics, on the thermal impacts of gas adsorption for hydrogen, and how the gas storage container equilibrates during the charge cycle, with FIG. 23 (A) showing an operating mode where pressure is allowed to slowly reach target pressure over 360 minutes, and overall equilibrium is reached in 480 minutes, and FIG. 23 (B) showing a faster fill where pressure is reached in about 20 minutes, and overall equilibrium is reached in a faster 360 minutes. FIG. 8 shows the Process & Instrumentation Diagram (P&ID) required to 68 charge gas into the gas container to drive adsorption and prevent premature equilibrium establishing by recirculating the gas until the gas storage container has been fully charged. FIG. 25, FIG. 26, and FIG. 27 show Computational Fluid Dynamics of the decant system in different operational modes. FIG. 10, FIG. 11, and FIG. 12 shows the Process & Instrumentation Diagram (P&ID) required to decant gas to drive desorption and prevent a new equilibrium establishing recirculating the gas until the gas storage container has been fully emptied.

[0274] The gas storage container may be optimized for gas uptake and end-to-end energy efficiency, within a temperature and pressure envelope, for the specific gas to be stored and transported. The gas storage container may be passive (e.g. no active cooling applied) and has zero boiloff during normal operation. The gas storage container may be energy efficient, as minimal energy is required for initial compression or liquefaction, and no energy is required to maintain the temperature and pressure during storage and transport.

[0275] For example, the gas storage container may be optimized for both hydrogen bulk transport and for ISO dimensions and mass envelope, has 50 bar of pressure, operates at -196 degrees Celsius, and stores greater than 50 kg / m3, with zero boil-off, and only 1.9 kWh / kgh2 energy losses, and zero parasitic energy losses during transport.

[0276] For example, the gas storage container, which may be the same gas storage container as in paragraph

[0275] , may be optimized for both hydrogen bulk transport and for ISO dimensions and mass envelope, can operate at 30 bar of pressure, and at -233 degrees Celsius, and stores greater than 60 kg / m3, with zero boil-off, and 3.5-7 kWh / kgh2 energy losses, and zero parasitic energy losses during transport.

[0277] The gas storage system provides flexible use, enabling interoperation with other existing and / or emerging gas production, cooling and / or compression technologies, while also maximizing safety and / or minimizing energy losses during transport.

[0278] When the gas storage container shell may be made from Type-III, Type-IV or Type-V carbon fibre composites, the overall mass of the storage system may be greatly reduced.

[0279] When the gas storage container shell (the inner shell for double walled gas storage containers) is made from carbon fibre composites in a Type-IV (plastic lined) or Type-V (liner less) configuration, where there may be no metallic liner interfacing with the gas being stored, the plastic liner or carbon-fibre composite materials of the gas storage container walls do not suffer corrosion or embrittlement over time, so the life 69 span of gas storage system is expected to be much longer, and the gas storage system achieves greater inherent safety due to elimination of embrittlement or corrosion risk in the gas storage container wall.

[0280] When the gas storage container shell (the inner shell for double walled gas storage containers) is made from metallic materials (Type-I pressure gas storage container) or metallic with composite partial overwrap (Type-II pressure gas storage container), interfacing with the gas being stored, the metallic materials may be made from 316 stainless steel or other metal alloys that do not suffer corrosion or embrittlement over time, so the life span of systems is expected to be much longer, and the system achieves greater inherent safety due to reduction of embrittlement or corrosion risk in the storage container wall.

[0281] When the gas storage system is a double walled gas storage system, the outer shell may be made from metallic materials or carbon-fibre composite materials. Where the outer shell is made from carbon-fibre composite materials the overall mass of the gas storage system may be greatly reduced.

[0282] Different types of inner pressure shells / storage containers (Types-I, II, III, IV, or V) can be combined with different types of outer storage containers (made of either metallic or carbon-fibre composite materials), in various combinations, depending on systemwide performance and user requirements.

[0283] The gas storage system may enable flexible supply and distribution models including many-to-many distribution networks. For example, in the case of hydrogen, where small to large producers can distribute to many small to large users, without the need to aggregate the gas in a centralised distribution centre or hub. One-to-many distribution networks are also possible where one medium to large producer of hydrogen can distribute to the full range of hydrogen end-users. Many-to-one distribution is also possible where many small to medium and some large producers of hydrogen can distribute to a single or few major users of hydrogen cost effectively, and with similar costs. The gas storage system enables transport and international export of gases such as hydrogen without the need of a dedicated purpose-built ship, or truck or train.

[0284] This flexibility of supply chain optionality provided by the adsorbent material, including a nanoporous, microporous, or mesoporous adsorbent material-filled storage container is unique and important to the storage and transport of gases. For example, in the case of hydrogen, novel production methods including Waste-to-Hydrogen pyrolysis and electrolytic hydrogen production are possible at small scale, low-cost interoperable solutions to store and transport the hydrogen from production to end use sites, are required. The gas storage system will enable small producers to compete with very large-scale producers and increase the uptake of gases such as hydrogen gas as a zero-carbon energy carrier and source.

[0285] Digital algorithms and software can be built as a virtual layer on the nanoporous, microporous or mesoporous adsorbent enabled gas storage container, leveraging its desirable “packaged” nature, and leveraging the long dormancy afforded by the incorporation of these materials in the gas storage container. In one embodiment, where the gas storage system is used for gases such as hydrogen, supply chain network software can enable efficient storage and distribution from both small and large producers to a range of small to large energy users. This supply chain software combined with engineering design of the Adsorbent-Material-filled gas storage container of The Gas Storage System (herein referred to as a AMTGSS. The AMTGSS being capable of utilizing a wide range of adsorbents) facilitating zero-boil-off, long dormancy / dwell / hold time, high density, and high energy efficiency, will enable the container to be financialized as a standard energy vector asset and traded in real time within many-to-many, one-to-many and many-to-one supply ecosystems, with onboard telemetry enabling faster transactions, and multivariate real time cost optimization. The elimination of boiloff losses is key to the value of any software which leverages real time data flows from the AMTGSS, as monetising the value of the gas relies on a guaranteeing that every gas molecule loaded into the AMTGSS can be delivered to the end customer, with measurable quantised precision (measuring both volume and quality of gas stored and transported). Third party software can be written for the container box, or to be installed on the container box, to enable tracking of hydrogen and automation in the calculation of carbon abatement and other energy transition incentives. This innovation solves major challenges in industry regarding how to trade different grades of gases (such as hydrogen or CO2) via pipeline, where a high grade of gas may be spoilt by injection of lower grades gas downstream. Furthermore, presently precise unquantifiable boil-off from existing cryo-gas packaged systems inhibits the building of packaged gas supply chain software as there is no way of knowing precisely how much was loaded and unloaded.

[0286] Although specific embodiments of the invention are illustrated and described herein, it will be appreciated by those of ordinary skill in the art that a variety of 71 alternative and / or equivalent implementations exist for a wide range of gases including hydrogen, carbon dioxide, methane, argon, oxygen, nitrogen and various gas mixtures. It should be appreciated that the exemplary embodiments or exemplary embodiments are examples only and are not intended to limit the scope, applicability, or configuration in any way. Rather, the foregoing summary and detailed description will provide those skilled in the art with a convenient road map for implementing at least one exemplary embodiment, it being understood that various changes embodiment may be made in the function and arrangement of elements described in an exemplary embodiment without departing from the scope as set forth in the appended claims and their legal equivalents. Generally, this application is intended to cover any adaptations or variations of the specific embodiments discussed herein.

[0287] It will also be appreciated that in this document the terms “comprise”, “comprising”, “include”, “including”, “contain”, “containing”, “have”, “having”, and any variations thereof, are intended to be understood in an inclusive (i.e. non-exclusive) sense, such that the process, method, device, apparatus or system described herein is not limited to those features or parts or elements or steps recited but may include other elements, features, parts or steps not expressly listed or inherent to such process, method, article, or apparatus. Furthermore, the terms “a” and “an” used herein are intended to be understood as meaning one or more unless explicitly stated otherwise. Moreover, the terms “first”, “second”, etc. are used merely as labels, and are not intended to impose numerical requirements on or to establish a certain ranking of importance of their objects.

[0288] Further attributes and features of the invention can be understood by reference to the following numbered items. Reference to disclosure in any of the preceding aspects is applicable to any of the following numbered items and to any combination of any number of the following items, as recognized by appropriate antecedent disclosure in any combination that can be made.

[0289] For the avoidance of doubt, (1) when the phrase, for example, “of ITEM 17 or ITEM 18” is recited, it means that it applies equally and individually to each of the recited items; and (2) when the phase, for example, “any one of ITEM 3 to ITEM 6” is recited, it means that it applies equally and individually to each of the ITEM numbers bounding the range as well as the ITEM numbers included in the range, i.e. each of ITEM 3, ITEM 4, ITEM 5, and ITEM 6.

[0290] The following numbered items are provided: ITEM 1. A gas storage system including a storage container comprising an outer shell surrounding an inner shell, a vacuum and / or insulation there between, the outer shell made of either metal or a carbon fibre composite material and the inner shell comprising either metal alloy that inhibit corrosion or embrittlement over time metal (Type-I) or metal wrapped with carbon-fibre composite (Type-II or Type-III), or polymer wrapped with carbon-fibre composite (Type-IV) or carbon-fibre composite material (Type-V), the storage container being filled with a Metal-Organic-Framework (MOF) nanoporous material, or a MOF-hybrid nanoporous material or MOF-composite nanoporous material or a MOF-hybrid-composite nanoporous material which is highly adsorbent, the adsorbent material being adapted in use to adsorb and release gas upon operation of the system by a user. ITEM 2. The gas storage system of ITEM 1, wherein different types of materials of the inner shell (Types-I, II, III, IV, or V) can be combined with different types of materials of the outer shell (made of either metallic or carbon-fibre composite materials), in various combinations, to form a part of the system. ITEM 3. A gas storage system including a storage container comprising a single wall, made of 316 stainless steel or other metal alloys that inhibit corrosion or embrittlement over time (Type-I), or metal wrapped with carbon-fibre composite (Type-II or Type-III), or polymer wrapped with carbon-fibre composite (Type-IV), or carbon-fibre composite material (Type-V), the storage container being filled with a Metal-Organic-Framework (MOF) nanoporous material, or a MOF-hybrid nanoporous material or MOF-composite nanoporous material or a MOF-hybrid-composite nanoporous materials which is highly adsorbent, the adsorbent material being adapted in use to adsorb and release gas upon operation of the system by a user. ITEM 4. A storage container having the gas storage system of any one of ITEM 1 to ITEM 3, the storage container being ISO certified for intermodal (road, rail and marine) transport. ITEM 5. The gas storage system of anyone of ITEM 1 to ITEM 3, wherein the gas is hydrogen, carbon dioxide, methane, natural gas, biogas, biomethane, ammonia, oxygen, helium, neon, argon, nitrogen, medical gases, refrigerant gases, hospitality and food / beverage gas mixtures, welding gas mixtures, laser gas mixtures, acetylene, and / or other gases including gas mixtures. ITEM 6. The gas storage system of ITEM 1 or ITEM 2, wherein physical properties of the storage container such as, but not limited to, thermal and pressure conditions, rates of adsorption / desorption, mechanical strength, thermal conductivity, coefficients of thermal material or super material expansion, are tuneable through post-synthetic modification of adsorbent dopants (both type and concentration), and post-synthetic compositing of two or more different MOFs with each other, or compositing of two or more MOFs and / or covalent organic frameworks (COFs) with each other. ITEM 7. The gas storage system of ITEM 1, wherein energy savings are gained from inclusion of the adsorbent to reach any given temperature or pressure storage container condition. ITEM 8. The gas storage system of ITEM 1, wherein the gas stored within the system is substantially stored adsorbed to a surface area of the adsorbent material, not as a gas or liquid, resulting in an inherently safe system. ITEM 9. The gas storage system of ITEM 1, wherein, in the unlikely event of rupture of the storage container, the gas is released slowly from the adsorbent and reduces the likelihood of a gas explosion (where the gas is flammable or explosive, for example hydrogen), demonstrating inherent safety. ITEM 10. The gas storage system of ITEM 1, wherein the system has substantially zero boil-off at any given temperature or pressure storage container condition. ITEM 11. The gas storage system of ITEM 1, wherein the adsorbent material includes Metal-Organic-Framework (MOF) materials, Covalent-Organic-Framework (COF) materials, MOF-to-MOF composite materials, MOF-to-COF composite materials, and MOF or MOF-composite with advanced carbon allotropic -dopants (MOF-Hybrid or MOF-Hybrid-Composite Materials). ITEM 12. The gas storage system of ITEM 1, wherein the adsorbent material is highly porous having >700 m2 / g, >1000 m2 / g, >1300 m2 / g, >1600, >1800, >2000, >2200, >2400 m2 / g, >2600 m2 / g, >2800 m2 / g, >3000 m2 / g, 4000 m2 / g, >8000 m2 / g of surface area to adsorb gas. ITEM 13. The storage container of ITEM 4, wherein the adsorbent material is replaceable, without changes to storage container certification. ITEM 14. The storage container of ITEM 13, wherein the adsorbent material can be reused in a different storage container system without reprocessing or recycling the adsorbent material. ITEM 15. The gas storage system of ITEM 1, wherein the adsorbent material incorporated into the storage container can have different macromorphologies, either as powder, or pressed pellets, or densified monolithic pellets, or densified megalithic pellets or densified megalithic blocks, whereby pellets and blocks can form a rigid body within the storage container and achieve packing fractions of >93%, >91%, >87%, >85%, >80%, or >75% or >65% or >50%, or whereby megalithic blocks are hard enough and large enough to be machined to form precise 3D tessellating segments which fill the void of the storage container to achieve packing densities of >99%, or >98%, or >97, or >95%, or >90% packing fraction, or whereby megalithic blocks can be made hard enough and large enough to form a single shape precisely the dimension of the storage container void space, such that the adsorbent material can act as a mandrel during the manufacture of Type-V carbon-composite pressure storage containers, enabling both improved packing fraction of adsorbent to >99%, or >98%, or >97, or >95%, or >90% of void volume, as well as simplifying systemwide manufacturing processes. ITEM 16. The gas storage system of ITEM 1, wherein the gas is released by a user on changes in temperature or pressure or both. ITEM 17. The gas storage system of ITEM 1, wherein the system can be utilized in storage containers greater than 0.1 litres. ITEM 18. The gas storage system of ITEM 1, wherein the system operates at pressures above 1 bar and up to 950 bar In a preferred form, 2-3 bar for super scale storage, at 10-30 bar for international shipping, 30-60 bar for ISO containers and gas containers certifiable to other international standards, and up to 400 bar for ambient high pressure storage for automotive. ITEM 19. The gas storage system of ITEM 1, wherein the system may be operated at different temperatures greater than 4 Kelvin and up to 500 Kelvin, as long as pressures do not rise above the certified maximum pressure rating of the inner shell. ITEM 20. The gas storage system of ITEM 1, wherein the adsorbent filling the void in the container, acts as an adsorbent for the gas being stored, and increases the dormancy / dwell time / hold time days up to 20 days, up to 30 days, up to 40 days, up to 50 days, up to 60 days, up to 130 days, up to 160 days, without the need for an active powered cooling system to keep the system at the correct temperature. ITEM 21. The storage system of ITEM 1, wherein the container in use operates autonomously without human intervention for up to 20 days, up to 30 days, up to 40 days, up to 50 days, up to 60 days up to 130 days, up to 160 days at a time which means up to 20 days, up to 30 days, up to 40 days, up to 50 days, up to 60 days up to 130 days up to 160 days. ITEM 22. The gas storage system of ITEM 1, wherein the metal organic framework (MOF) polymers are optimized for temperatures and pressures, above 1 -950 bar and temperatures to 4-500 degrees K. ITEM 23. The gas storage system of ITEM 1, wherein the container is conformable into a variety of shapes. ITEM 24. The gas storage system of ITEM 1, wherein the container can be an ISOcertified or to other international standard, compliant storage system for intermodal shipping container between 8ft and up to 45ft long. ITEM 25. The gas storage system of ITEM 1, wherein the system of at least 400 Litres and up to 60,000 Litres can be utilised for one-to-many, many-to-one, and many-to-many bulk gas distribution, to facilitate efficient bulk gas transport, and that this can be digitalised and digitally visualised in real time to provide information to algorithms and third party software. ITEM 26. The gas storage system of ITEM 1, wherein a digital algorithms can designed for gas storage bulk transport and distribution, which draws on information generated by technologies to provide pricing (historical, current and predictive), location, logistics, gas carried, provenance, certification of origin, temperature, pressure, telemetric, GIS, safety, video, infrared and smell detection security information, which can be retained, and transmitted for centralised or decentralised monitoring and management, trading of contained gases, financialization of storage systems as flexible and agile assets, calculation of government and non-government incentives, hydrogen carbon and other tax incentives or carbon and other emissions offset credits. ITEM 27. A gas storage system of ITEM 1 where impurities in the stored gas do not impact total deliverable capacity when cycled. ITEM 28. A gas storage system comprising a storage container, wherein the gas storage container comprises one or more adsorbent materials. ITEM 29. The gas storage system of ITEM 28, wherein the one or more adsorbent materials comprises one or more nanoporous, microporous, or mesoporous adsorbent materials. ITEM 30. The gas storage system of ITEM 28 or ITEM 29, wherein the one or more adsorbent materials comprises one or more Metal-Organic-Framework (MOF) materials, Covalent-Organic-Framework (COF) materials, MOF-composite materials, MOF-hybrid materials, and / or MOF-hybrid-composite materials. ITEM 31. The gas storage system of ITEM 28 or ITEM 29, wherein the one or more adsorbent materials comprises one or more Metal-Organic-Framework (MOF) materials. ITEM 32. The gas storage system of ITEM 31, wherein the one or more adsorbent materials comprises one or more Metal-Organic-Framework (MOF) materials. ITEM 33. The gas storage system of ITEM 30, wherein the MOF-hybrid material and / or MOF-hybrid-composite material comprises one or more advanced carbon allotropic dopants, graphene, graphene oxides, carbon nanotubes, and fullerenes. ITEM 34. The gas storage system of ITEM 33, wherein the MOF-hybrid material and / or MOF-hybrid-composite material consists of advanced carbon allotropic dopants. ITEM 35. The gas storage system of any one of ITEM 28 to ITEM 34, wherein the adsorbent material has surface area of at least about 700 m2 / g to adsorb gas. ITEM 36. The gas storage system of ITEM 35, wherein the surface area of the adsorbent material is at least about 700 m2 / g to about 7900 m2 / g to absorb gas. ITEM 37. The gas storage system of any one of ITEM 28 to ITEM 36, wherein the adsorbent material has a heat of adsorption of less than 0 kJ / mol. ITEM 38. The gas storage system of any one of ITEM 28 to ITEM 37, wherein the adsorbent material has a heat of desorption of greater than 0 kJ / mol. ITEM 39. The gas storage system of ITEM 38, wherein the heat of desorption is from about 0 kJ / mol to about -51 kJ / mol. ITEM 40. The gas storage system of ITEM 38 or ITEM 39, wherein the heat of desorption is less than about -10 kJ / mol. ITEM 41. The gas storage system of any one of ITEM 38 to ITEM 40, wherein the heat of desorption is from about rom about -5 kJ / mol to about -7 kJ / mol. ITEM 42. The gas storage system of any one of ITEM 28 to ITEM 41, wherein the adsorbent material is a mechanically robust material, (mechanically robust meaning an adsorbent material which can withstand up to 70 N compressive force). ITEM 43. The gas storage system of ITEM 42, wherein the adsorbent material substantially maintains pore structure in comparison to the adsorbent material when initially filled into the gas storage container. ITEM 44. The gas storage system of any one of ITEM 28 to ITEM 43, wherein the adsorbent material is a chemically robust material (chemically robust meaning a material which can be cycled in the presence of gas impurities without loss of adsorbent performance for a target gas, as shown in FIG. 50). ITEM 45. The gas storage system of ITEM 44, wherein the surface area, pore volume, and / or active sites of adsorption of the adsorbent material is substantially maintained in comparison to the adsorbent material when initially filled into the gas storage container. ITEM 46. The gas storage system of any one of ITEM 28 to ITEM 45, wherein the adsorbent material has a packing fraction of at least about 0.58. ITEM 47. The gas storage system of ITEM 46, wherein the packing fraction is from about 0.58 to about 0.9. ITEM 48. The gas storage system of ITEM 46, wherein the packing fraction is from about 0.7 to about 0.8. ITEM 49. The gas storage system of ITEM 46, wherein the packing fraction is from about 0.75 to about 0.88 achieved via a - 0.1, 0.15 ratio of adsorbent pellets / macromorphs. ITEM 50. The gas storage system of ITEM 28 to ITEM 49, wherein the size ratio of coarse particles is about 0.154. ITEM 51. The gas storage system of ITEM 28 to ITEM 49, wherein the size ratio of coarse particles may be less than 0.15. ITEM 52. The gas storage system of ITEM 28 to ITEM 49, wherein the size ratio of coarse particles may be about 0.05 to about 0.5, or from about 0.08 to about 0.3, or from about 0.1 to about 0.2. ITEM 53. The gas storage system of any one of ITEM 28 to ITEM 52, wherein the gas storage container comprises a single wall, double wall, or triple wall. ITEM 54. The gas storage system of any one of ITEM 28 to ITEM 53, wherein the gas storage container comprises an outer shell surrounding an inner shell. ITEM 55. The gas storage system of ITEM 54, wherein the outer shell is formed from metal. ITEM 56. The gas storage system of ITEM 54, wherein the outer shell is formed from carbon fibre composite. ITEM 57. The gas storage system of any one of ITEM 54 to ITEM 56, wherein the inner shell is formed from 316 stainless steel, or aluminium, titanium alloy, or other metal alloy that inhibits corrosion or embrittlement. ITEM 58. The gas storage system of ITEM 54, wherein the inner shell is formed from Type I material. ITEM 59. The gas storage system of ITEM 55, wherein the inner shell is formed from aluminium. ITEM 60. The gas storage system of ITEM 55, wherein the inner shell is formed from 316 stainless steel. ITEM 61. The gas storage system of ITEM 55, wherein the inner shell is formed from 304 stainless steel. ITEM 62. The gas storage system of any one of ITEM 54 to ITEM 56, wherein the inner shell is formed from Type II or Type III material. ITEM 63. The gas storage system of ITEM 54 to ITEM 56, wherein the inner shell is formed from metal wrapped with carbon-fibre composite. ITEM 64. The gas storage system of any one of ITEM 54 to ITEM 56, wherein the inner shell is formed from Type-IV material. ITEM 65. The gas storage system of any one of ITEM 54 to ITEM 56, wherein the inner shell is formed from polymer wrapped with carbon fibre composite. ITEM 66. The gas storage system of any one of ITEM 54 to ITEM 56, wherein the inner shell is formed from Type V material. ITEM 67. The gas storage system of any one of ITEM 54 to ITEM 56, wherein the inner shell is formed from carbon-fibre material. ITEM 68. The gas storage system of any one of ITEM 54 to ITEM 67. Wherein the space between the inner shell and outer shell are insulated and / or under vacuum. ITEM 69. The gas storage system of any one of ITEM 28 to ITEM 68, wherein the gas storage container is certified or certifiable to ISO or other international certified for intermodal transport and international transport. ITEM 70. The gas storage container of ITEM 69, wherein the gas storage container is an 8ft to a 45ft gas storage container. ITEM 71. The gas storage container of any one of ITEM 28 to ITEM 70, wherein the gas storage system stores gas for greater than 3 days. ITEM 72. The gas storage system of ITEM 71, wherein the gas storage system stores gas for up to 30 days. ITEM 73. The gas storage system of ITEM 71, wherein the gas storage system stores gas for up to 90 days. ITEM 74. The gas storage system of ITEM 71, wherein the gas storage system stores gas for up to 100 days. ITEM 75. The gas storage system of ITEM 71, wherein the gas storage system stores gas for up to 130 days. ITEM 76. The gas storage system of ITEM 71, wherein the gas storage system stores gas for up to 160 days. ITEM 77. The gas storage system of any one of ITEM 28 to ITEM 76, wherein the gas adsorbed is hydrogen, biomethane, biogas, methane, natural gas, natural hydrogen, stimulated hydrogen, carbon dioxide, helium, neon, ammonia, oxygen, argon, nitrogen, medical gases, refrigerant gases, hospitality and food / beverage gas mixtures, welding gas mixtures, laser gas mixtures, acetylene, and / or other gases including gas mixtures. ITEM 78. The gas storage system of any one of ITEM 28 to ITEM 76, wherein the gas adsorbed is hydrogen, biomethane, biogas, methane, natural gas, natural hydrogen, stimulated hydrogen, carbon dioxide, helium, neon, ammonia, oxygen, argon, or nitrogen. ITEM 79. The gas storage system of any one of ITEM 28 to ITEM 76, wherein the gas adsorbed is hydrogen, biomethane, biogas, methane, natural gas, or carbon dioxide. ITEM 80. The gas storage system of any one of ITEM 28 to ITEM 76, wherein the gas adsorbed is hydrogen. ITEM 81. The gas storage system of any one of ITEM 28 to ITEM 76, wherein the gas adsorbed is methane, CO2 / biomethane / biogas / natural gas. ITEM 82. The gas storage system of any one of ITEM 28 to ITEM 76, wherein the gas adsorbed is carbon dioxide. ITEM 83. The gas storage system of any one of ITEM 28 to ITEM 76, wherein the gas adsorbed is a biogas. ITEM 84. The gas storage system of any one of ITEM 28 to ITEM 83, wherein the gas storage system operates at a pressure above 1 bar. ITEM 85. The gas storage system of any one of ITEM 28 to ITEM 83, wherein the gas storage system operates at a pressure up to 400 bar. ITEM 86. The gas storage system of any one of ITEM 28 to ITEM 85, further comprising a charging subsystem comprising: a charging heat exchanger, wherein the charging heat exchanger is in a charging recirculation loop with the gas storage container, said charging recirculation loop comprising a charging output line from the gas storage container to the charging heat exchanger, and a charging input line from the heat exchanger. ITEM 87. The gas storage system of any one of ITEM 28 to ITEM 86, wherein the unique para-spin catalysing behaviour of adsorbent materials with paramagnetic metal clusters within their structure, are used to increase the energy efficiency of charging the gas storage system. ITEM 88. The gas storage system of any one of ITEM 28 to ITEM 87, wherein the unique para-spin catalysing behaviour of adsorbent materials with paramagnetic metal clusters within their structure, are used to increase dormancy. ITEM 89. The gas storage system of any one of ITEM 28 to ITEM 88, wherein the unique para-spin catalysing behaviour of adsorbent materials with paramagnetic metal clusters within their structure, are used to maximise total hydrogen systemwide uptake. ITEM 90. The gas storage system of any one of ITEM 28 to ITEM 89, wherein the unique para-spin catalysing behaviour of adsorbent materials with paramagnetic metal clusters within their structure, are used to reduce or eliminate boil-off in conventional liquefied hydrogen gas storage systems. ITEM 91. The gas storage system of any one of ITEM 28 to ITEM 90, wherein the charging subsystem further comprises a gas supply line upstream of the heat exchanger. ITEM 92. The gas storage system of any one of ITEM 28 to ITEM 91, wherein the charging heat exchanger is a cryocooler. ITEM 93. The gas storage system of any one of ITEM 28 to ITEM 92, wherein the charging subsystem is connected to the storage container for co-location with the gas storage container during transport. ITEM 94. The gas storage system of any one of ITEM 28 to ITEM 93, wherein the charging subsystem is separably connectable to the gas storage container at a charging location. ITEM 95. The gas storage system of any one of ITEM 28 to ITEM 94, wherein the charging heat exchanger uses the stored gas itself as a heat transfer fluid. ITEM 96. The gas storage system of any one of ITEM 28 to ITEM 95, further comprising a decanting system comprising: a decanting heat exchanger, wherein the decanting heat exchanger is in a decanting recirculation loop with the gas storage container, said decanting recirculation loop comprising a decanting output line from the gas storage container to the decanting heat exchanger, and a decanting input line from the decanting heat exchanger. ITEM 97. The gas storage system of ITEM 96, wherein recirculation of gas through the decanting recirculation loop operates by thermosyphon. ITEM 98. The gas storage system of ITEM 96, wherein recirculation of gas through the decanting recirculation loop operates by forced convention. ITEM 99. The gas storage system of any one of ITEM 96 to ITEM 98, wherein the charging heat exchanger uses ambient air as a heat transfer fluid. ITEM 100. The gas storage system of any one of ITEM 96 to ITEM 99, wherein the decanting heat exchanger uses the stored gas itself as a heat transfer fluid. ITEM 101. The gas storage system of any one of ITEM 96 to ITEM 100, wherein the charging heat exchanger uses waste heat. ITEM 102. The gas storage system of any one of ITEM 96 to ITEM 101, wherein the charging subsystem is connected to the gas storage container for co-location with the storage container during transport. ITEM 103. The gas storage system of any one of ITEM 96 to ITEM 102, wherein the charging subsystem is separably connectable to the gas storage container at a charging location. ITEM 104. The gas storage system of any one of ITEM 28 to ITEM 103, further comprising an activation subsystem: comprising an activation input line having an activation heating element configured to deliver an inert gas to the adsorbent material at a sufficient temperature to raise the temperature of the absorbent material to an activation temperature. ITEM 105. The gas storage system of ITEM 104, wherein the activation temperature is above 100°C. ITEM 106. The gas storage system of ITEM 104 or ITEM 105, wherein the activation subsystem further comprises an activation output line having a dryer element configured to remove moisture from the inert gas after being delivered to the absorbent material, said activation output line connecting with the activation input line to return dried inert gas upstream of the activation heater element. ITEM 107. The gas storage system of any one of ITEM 104 to ITEM 106, wherein the adsorbent material can be reactivated in-situ at temperatures up to 120°C under a flow of hot dry nitrogen or hot dry air. ITEM 108. The gas storage system of any one of ITEM 104 to ITEM 107, wherein the adsorbent material can be reactivated in-situ at temperatures up to 150°C under a flow of hot dry nitrogen or hot dry air. ITEM 109. The gas storage system of any one of ITEM 104 to ITEM 108, wherein the adsorbent material can trap impurity gases without affecting the deliverable uptake performance for the target gas, and be reactivated in-situ at temperatures up to 120°C under a flow of hot dry nitrogen or hot dry air. ITEM 110. The gas storage system of any one of ITEM 104 to ITEM 109, wherein the adsorbent material can be recovered from the gas storage system, and redeployed and reused in a new gas storage or gas capture system. ITEM 111. The gas storage system of ITEM 110, wherein the adsorbent material can be reactivated in-situ at temperatures up to 150°C under a flow of hot dry nitrogen or hot dry air. ITEM 112. The gas storage system of any one of ITEM 28 to ITEM 111, wherein a digital algorithms can be designed for gas storage bulk transport and distribution, and for on-vehicle or on-marine-vessel or on-aircraft gas storage 83 fuel tanks, which draws on gas storage and transfer information generated by technologies to provide pricing (historical, current and predictive), location, logistics, gas carried, provenance, certification of origin, guarantees, temperature, pressure, precise payload value, telemetric, GIS, safety, video, infrared and smell detection security information, and real time safety information, which can be retained, and transmitted for centralised or decentralised monitoring and management, trading of contained gases, financialization of gas storage or gas capture systems as flexible, fixed or agile assets, calculation of government and non-government incentives, hydrogen and carbon dioxide and biogas and other gas tax incentives or carbon dioxide and other gaseous emissions offset credits, and support trading of fuel or carbon-dioxide. ITEM 113. The gas storage system of any one of ITEM 28 to ITEM 112, wherein third-party software or hardware or both may be installed to deliver additional value-added information generated by the gas storage system not identified in ITEM 93, to support decarbonisation and gas storage and gas transport. ITEM 114. The gas storage system of any one of ITEM 28 to ITEM 34, wherein the adsorbent material is selective for one gas. ITEM 115. The gas storage system of any one of ITEM 28 to ITEM 34, wherein the adsorbent material is selective for two gases. ITEM 116. The gas storage system of any one of ITEM 28 to ITEM 34, wherein the adsorbent material is selective for three gases. EXAMPLES

[0291] The following examples are not intended to limit the invention. EXAMPLE 1

[0292] In this first example, a series of key parameters is shown to enable a person skilled in the art to translate fundamental properties of an nanoporous, microporous or mesoporous physisorption adsorbent material, based on established physical characterisation techniques, to accurately predict and design engineer scalable systemwide gas storage containers.

[0293] The important characterisation parameters which must be known include Brunauer-Emmett-Teller (BET) surface area (using either or a combination of nitrogen, 84 carbon dioxide, helium as a BET surface area probing gas), and then, following this, collecting the gas sorption isotherms specific to the target gas.

[0294] Strong candidates for adsorbent materials will typically adsorb the target gas to their highest energy physisorption sites first, and then once these are saturated with form a monolayers and then bilayers of gas within the pore. Because there are two processes for physisorption which typically operate in strong candidates a DualLangmuir model was used to accurately characterised the uptake behaviour. If the fit to the model is good, the resulting outcome, the Heat of Adsorption at different target gas loadings, is determined to be accurate. This fundamental property is a key scalable design engineering parameter, from which both the gas storage container, as well as all enabling charging and decanting systems can be designed. This property is unique to both the adsorbent material and the target gas in question.

[0295] For example, a Dual-Langmuir model was used to characterize the overall uptake behaviour of hydrogen gas by two MOFs - [CU3BTC2] and CuII3[CoIII(CN6)]2.

[0296] The Dual-Langmuir model was used as the subject MOFs have at least two classes of adsorption sites for Hydrogen: high energy sites which are related to open metal sites and lower energy sites or pores. A single Langmuir model usually misses the sharp increase at low pressures and fails to get the correct high-pressure plateau. However Dual-Langmuir approach resolves this by combining two site types with different saturation capacities and adsorption affinities providing a more realistic description of the overall uptake behaviour.

[0297] In the two adsorbent material cases selected, [Cu3BTC2 ] has the axial positions on the [Cu2+-Cu2+] tetracarboxylato paddlewheel as its highest energy sites, whereas in CuII3[CoIII(CN6)]2 there are bare Cu2+ located in vacancies throughout the material.

[0298] In this example, hydrogen was used as the target gas. Hydrogen, uniquely, has two spin-states for electrons in its molecular orbitals, ortho and para. At ambient temperatures, it is 75% ortho-hydrogen. At cryogenic temperatures below 200 K, hydrogen has an increase in para spin-state, increasing to approximately 50% at about 77 K, and to approximately 99% para-hydrogen at about 20K.

[0299] Six isotherms measured at six different temperatures and fitted using DualLangmuir model. Fitting six isotherms simultaneously allowed the model to reproduce both the sharp low-pressure region dominated by strong adsorption sites and the saturation behaviour at high pressures governed by weaker sites which a single Langmuir cannot describe effectively. The temperatures selected cover a wide temperature range to ensure mapping across hydrogen’s different spin states characters. While a Dual-Langmuir fit may be approximately achievable with just two or three isotherms, the method described here asserts that six isotherms, spread across a wide temperature range, are required to achieve an accurate Heat of Adsorption result.

[0300] In the Dual-Langmuir model, the absolute uptake is calculated as: q(T,P)=Zi=i  Vsati r+b^p                Equation 1 1+^1(^ ) where qsat1 and qsat2 are the saturation capacities of sites 1 and 2; and, b1 (T) and b2(T') are their temperature dependent affinity constants.

[0301] The temperature effect of on the affinity of each site may be described using Van’t Hoff’s relation which links bi(T) to adsorption enthalpy (heat): bi(T) = bo,i exp exp [- (^)] Equation 2 where b0,i is a preexponential factor; AH i is the enthalpy (heat) of adsorption; R is the universal gas constant; and T is temperature.

[0302] The exponential term indicates how the affinity of the adsorption sites decreases with increasing temperature.

[0303] The simultaneous fit of six isotherms was done while keeping qsat,1 and qsat,2 constant for all temperatures and obtaining / 1 / / 1, AH2, b0,1 and b02 from temperature dependence of b^T) Dual-Langmuir model combined with the van’t Hoff relation provides physically meaningful Heat of Adsorption output comparable to those obtained from virial analysis method, alone.

[0304] FIG. 17 and FIG. 18 show the Dual-Langmuir model fitted to the experimentally measured isotherms for [Cu3BTC2 ] and CuII3[CoIII(CN6)] , at 77 K, 123 K, 153 K, 193 K, 233 K, and 298 K, respectively. The figures show a close fit to the experimental isotherm data across a wide temperature range, meaning that the resulting output Head of Adsorption values are accurate.

[0305] While six isotherms were used in this example, more or less isotherms can be used, although accuracy is improved with additional isotherms.

[0306] For any specific adsorbent material, qsat,1 (mmol / g), qsat,2(mmol / g), b0,1, b0,2, △Hi(kJ / mol) and AH2(kJ / mol) in equations 1 and 2 are constants and can be derived from the isotherm fitted model to determine gas uptake. EXAMPLE 2

[0307] As the isosteric Head of Adsorption changes as the target gas is loaded into the pore (with high energy sites sorbed first, and lower energy sites after this), verifying the above Dual-Langmuir method using a different approach which centres adsorption as a function of loading, i.e. the below described Virial method) enables the person skilled in the art to validate their initial results, and generate new information on total heat released. This is critical to correctly size components within the charging and decanting system, including sizing of the blower / cryoblower, and sizing of the appropriate heat exchanger, and calculation of total cooling that may be required for cryogenic systems, or calculation of total blower flow rates for ambient temperature gas storage systems.

[0308] A Virial method to obtain isosteric heat of adsorption as a function of loading for [Cu3BTC2 ] and CuII3[CoIII(CN6)] using the same experimental adsorption isotherms as Example 1. This approach is based on fitting experimental adsorption isotherms measured at multiple temperatures to a virial expansion of the adsorbate-adsorbent equilibrium relationship. The virial equation expresses the logarithm of equilibrium pressure as a polynomial function of the adsorbed amount which is written as; In In (p) =ln In (n) + (1) £™0  a^1 + ^7=0  bjnj         Equation 3 where n is the adsorbed amount; T is the temperature; and, ai and bj are virial coefficients obtained by simultaneous fitting across multiple isotherms.

[0309] According to the Clausius-Clapeyron relation, the slope of ln P versus 1 / T at constant n corresponds to the isosteric Heat of Adsorption, Qst: „             InlnP^                                          .-     ..  _ . Qst = -R(-^i-)n                         Equation 4 d (f)

[0310] Substituting the virial expression into this relation and differentiating with respect to 1 / T gives; Qst = -_R£™0  atnl                                Equation 5

[0311] Equation 5 shows Qst varies with n. The Virial ai terms account for the temperature dependent enthalpy effects. During adsorption initially the strongest binding sites are occupied then it will lead to a gradual decrease in adsorption energy as loading increases.

[0312] FIG. 19 and FIG. 20 show the Virial model fitted to the measured isotherms for [Cu3BTC2 ] and CuII3[CoIII(CN6)], respectively.

[0313] The results from Examples 1 and 2 were used to inform equilibrium mass and energy balance calculations to determine the cooling energy required while charging hydrogen into a gas storage container containing an adsorbent, dormancy and heat required to discharge hydrogen. The results from Examples 1 and 2 also inform the sizing of key components within enabling charging and decanting systems, in particular, the size, pressure rating, temperature rating, flow rates of blowers / cryoblowers, and the size, pressure rating, temperature rating, flow rate capacities of a relevant heat exchanger. EXAMPLE 3

[0314] In the following example, the equilibrium of gas stored (mass balance of gas stored) at any given temperature and pressure inside the tank (or gas storage container) can be estimated using the Example 1 Dual Langmuir and Example 2 Virial model parameter outputs for a specific adsorbent material and a specific gas.

[0315] In this example, [Cu3BTC2 ] and CuII3[CoIII(CN6)] are further studied in relation to hydrogen gas, using the outputs generated in Example 1 and 2.

[0316] The mass of adsorbed hydrogen is determined by: mH2MOF = Vtank x PBuik x q( t,P) x 2.016 X 0.001               Equation 6 where, mh2mof: Hydrogen adsorbed in the adsorbent material in the tank (kg) Vtank: Volume of the adsorbent material enabled tank (m3); and, PBulk: Bulk density of adsorbent material in the tank (kg / m3)

[0317] The bulk density of the adsorbent material PBulk in the tank is calculated as the material envelope density multiplied by the packing fraction.

[0318] The mass of free (unadsorbed) hydrogen is determined by: mH2void = Vtank x (1-PBulk x (1 / PSkeletal + Vpore)) x PH2ig                Equation 7 where, mh2void: Hydrogen in the void space of adsorbent material bed PSkeletal: Skeletal density of the specific adsorbent material (kg / m3); Vpore: Pore volume of the specific adsorbent material (m3); and, PH2ig: Ideal gas density of Hydrogen (kg / m3)

[0319] The total mass of hydrogen in kilograms is then the mass of gas adsorbed onto the surface of the material plus the “free gas” within the void space between material particles, and determined by: mtankh2 = mh2mof + mh2void                                   Equation 8 where, mtankh2: Total hydrogen in the adsorbent material enabled tank (or adsorbent material enabled gas storage container) EXAMPLE 4

[0320] Once the mass balance of gas stored in a system has been accurately, calculated, the results can be used to then accurately calculate the energy balance of the gas storage container for any change in internal temperature and internal pressure can be calculated based on the following equations. These equations can also be used to specify the appropriate size, temperature range, pressure range, and flow rate of enabling systems components to achieve gas charging, storage and decanting outcomes relevant to user needs.

[0321] Heat absorbed or released by a tank (or gas storage container) is determined by: Qtank-shell = mtank-shell x Cptank-shell X (T(i+1) - T(i))                      Equation 9

[0322] Heat absorbed or released by the MOF / adsorbent material is determined by: Qmof = mMOF x Cpmof x (T(i+i) - T(i))                           Equation 10

[0323] Heat absorbed or released by the gas / hydrogen in the adsorbed phase or gaseous phase in the storage tank, Qtankh2 = mtankh2(i) x Cvh2 x (T(i+1) - T(i)) Equation 11

[0324] Heat of adsorption or desorption of Hydrogen from the MOF / adsorbent material, Qadsorption / desorption = madsorbed / desorbed x △Hadsorption / desorption X               Equation 12 where, △Hadsorption / desorption is a polynomial function of the amount of hydrogen adsorbed or desorbed at any equilibrium condition. For hydrogen gas specifically, it is to be noted that the energy released / absorbed due ortho / para isomer conversion based on equilibrium temperature and pressure conditions is included in the △Hadsorption / desorption. △Hadsorption / desorption = — R * X^o ajQj                         Equation 13 madsorbed / desorbed = mh2mof(i+1) - mh2mof(i)                         Equation 14

[0325] It is noted that while Equations 13 and 5 are similar, Equation 13 corresponds to systemwide calculation Head of Adsorption / Desorption for a scale system, versus Equation 5 which corresponds to Head of Adsorption at the material level when and during loading with a target gas.

[0326] Enthalpy of the hydrogen / gas introduced inside the tank or gas storage container is determined by: QH2out= mH2out * CpH2 * (TH2in - Tref)                         Equation 15 where Tref = Reference temperature

[0327] Enthalpy of the Hydrogen leaving the tank or gas storage container is determined by: Z^X                                   . . Z~\          . . / T—              —!—    \                                                           I—         I ■           Z^ QH2out = -mH2out * CpH2 * (TH2out - Tref)                          Equation 16 where, mH2out = mH2in - (mtankH2(i+i) - mtankH2(i)) / t                         Equation 17

[0328] Assuming that the Hydrogen leaving the tank or gas storage container during recirculation is in equilibrium with the tank, Th2out = T(i+1), heat absorbed by the hydrogen / gas adsorbed in the storage tank or gas storage container during charging is determined by: Qchargeh2 = (mtankh2(i+1) - mtankh2(i)) * Cph2 * (T(i+1) - Th2in)           Equation 18

[0329] Heat released by the Hydrogen that is desorbed in the storage tank during discharging is determined by: Qdichargeh2 = (mtankh2(i+1) - mtankh2(i)) * Cph2 * (T(i+1) - Tdischarge)      Equation 19

[0330] Assuming that the Hydrogen leaving the tank or gas storage container during discharging is in equilibrium with the tank or gas storage container, 90 Tdischarge = T(i+1), heat leak (conductive and / or radiative) into the gas storage tank (or gas storage container_ is determined by: Qleak = constant                                     Equation 20

[0331] The overall energy balance for the MOF tank gas storage system (or adsorbent material filled gas storage container) can be expressed (for charging the system as (a) and discharging the systems (b) as: Q H2in + Q H2out + Q leak = Qtank-shell + QmOF + QtankH2 + Qadsorption + QchargeH2     Equation 21a Q H2in + Q H2out + Q leak = Qtank-shell + QmOF + QtankH2 + Qdesorption + QdischargeH2   Equation 21b

[0332] It is to be noted that the heat of expansion / compression of hydrogen / gas is not considered in the energy balance as the magnitude is estimated to be relatively very low.

[0333] The time required for the tank gas storage system (or gas storage container) to go from one equilibrium condition to another (i.e. the time tcharge to charge the system or the time tdischarge to discharge the system) can then be expressed as, tcharge = (Qtank-shell + QmOF + QtankH2 + Qadsorption+ QchargeH2) / (Q H2in + Q H2out + Q leak) Equation 22a tdischarge) = (Qtank-shell + QmOF + QtankH2 + Qdesorption+ QdischargeH2) / (Q H2in + Q H2out + Q leak) Equation 22b EXAMPLE 5

[0334] The above method described in Examples 1 to 4, provides a coherent and complete approach to accurately design a scalable gas storage system using the fundamental material properties of an adsorbent material for specific target gases. Putting these learnings into practice, the Dual-Langmuir Method (Example 1), Virial Method (Example 2), Mass Balance Method (Example 3) and Energy Balance Method (Example 4) were used to accurate calculate a charging profile of an example energy storage system in accordance with the present disclosure, using hydrogen as the target gas.

[0335] In this example, with outputs shown in FIG. 23 (A), a 20,000L gas storage container loaded with 15,000 kg of the adsorbent material [Cu3BTC2.] is initially at 120 K and 1 bar absolute pressure. The system is charged with hydrogen at 1,000 kg / hr at 80 K, and the inner shell of the gas storage container is allowed to cool while simultaneously building pressure in the inner shell of the gas storage container to reach a final temperature of 82K and 31 bar absolute.

[0336] The charging process between initial and final temperature and pressure conditions may be discretized into multiple finite small steps, with mass and energy conserved at each step as well as the time required for each step being iteratively estimated based on the above calculation methodology. The heat leak into the gas storage tank (or gas storage container) can be neglected for the example charging process as the magnitude is considered low for the time scale under consideration.

[0337] The following Dual-Langmuir parameters for [Cu3BTC2.] were determined in accordance with Example 1 and assumed constant. qsat,1         = 12.95 mmol / g qsat,2         = 15.47 mmol / g b0,1          = 0.00018 b0,2         = 0.000325 AHi         = -3.69 kJ / mol AH2        = -6.02 kJ / mol

[0338] The following polynomial function parameters for [Cu3BTC2.] were determined in accordance with Example 2: a0           = -726.995 ai           = 5.320 a2           = -0.486 a3           = 0.i09 a4           = -0.005 a5          = 0.00008

[0339] The following parameters were used for the mass and energy balance models of a hydrogen storage system using the adsorbent material [Cu3BTC2.] in accordance with Examples 3 and 4: mtank-shell     = 7200 kg Cptank-shell    = 0.305 kJ / kg / K Cpmof      = 0.5 kJ / kg / K CpH2        = i2.5 kJ / kg / K CvH2        = 6.5 kJ / kg / K pBuik         = 750 kg / m3 pskeietai               = 2600 kg / m3 Vpore        = 0.000636 m3 / kg Tref          = 80 K

[0340] Exampie 5(a): By using the modeis of Exampies 1 to 4, a charging profiie was simuiated as shown in FIG. 23 (A) for the charging process described above. The rate of hydrogen storage in the tank (or gas storage container) is higher initiaiiy and as the tank (or gas storage container) approaches the feed Hydrogen temperature of 80 K, the Hydrogen ioading rate drops. At the 1000 kg / h of feed rate considered in this exampie, it is estimated to take around 9.2 hours for the gas storage tank (gas storage container) to reach 82 K temperature, 31 bara pressure and store ~723 kg of Hydrogen. It is to be noted that the feed rate of 1000 kg / h is higher than the ioading rate or storage rate at any given time and the baiance of the Hydrogen ieaves the tank (or gas storage container) carrying the heat reieased from cooiing.

[0341] Exampie 5(b): To demonstrate the voracity of the method, a different charging profiie was triaiied, assuming the same initiai conditions (a 20,000L gas storage container ioaded with 15,000 kg of the adsorbent materiai [Cu3BTC2] is initiaiiy at 120 K and 1 bar absoiute pressure). Cryogenic hydrogen at 80 K is charged into the gas storage tank (or gas storage container) adiabaticaiiy, with no Hydrogen ieaving the tank (or gas storage container) to buiid pressure inside the tank (or gas storage container) to 31 bara. The temperature inside the tank (or gas storage container) after the tank (or gas storage container) is pressurised can be iterativeiy estimated by doing energy baiance based on the caicuiation basis. This pressure buiiding phase is assumed to take 0.5 hours. The Hydrogen is then charged into the storage tank (or gas storage container) at 1000 kg / h at 80 K and the tank (or gas storage container) is aiiowed to cooi to reach a finai temperature of 82 K at 31 bar absoiute pressure inside the tank (or gas storage container). Simiiar to Exampie 5(a), the charging process can be discretized into muitipie finite smaii steps and the mass and energy can be conserved at each step as weii as the time required for each step can be iterativeiy estimated based on the caicuiation basis. The heat ieak into the storage tank (or gas storage container) can be negiected again.

[0342] FIG. 23 (B) iiiustrates the profiie output from Exampie 5(b) inside the storage tank (or gas storage container) during the charging process as described above. During the initial phase where the storage tank (or gas storage container) is adiabatically charged with 80 K hydrogen to pressurise the tank (or gas storage container) to 31 bara, the temperature inside the tank (or gas storage container) increases from 120 K to about 152 K due to exothermic Heat of Adsorption being absorbed by the tank shell (or inner shell of the gas storage container) and the adsorbent material. For the 30 minutes considered for this phase, the hydrogen loading rate is estimated to be about 507 kg / h. Approximately 313 kg of hydrogen is stored in the tank (or gas storage container) at the equilibrium condition reached at the end of this phase. In the next phase where 80 K hydrogen is introduced into the tank (or gas storage container) at 1000 kg / h, the profile is similar to that seen before. The major difference is the cooling load in the initial phase of cooling which is higher in this example owing to the higher temperature of the tank (or gas storage container). Overall, it takes around 8.2 hours to reach the same equilibrium conditions. The slightly faster fill rate is due to the higher driving force for cooling the tank (or gas storage container) in this example as it starts from a higher temperature.

[0343] Simulation of the charging process allows for the system to be designed according to the required use case for the specific adsorbent, gas and equipment being used. In this example, it is desirable for the inner tank (or inner shell of the gas storage container) temperature to drop as gas storage increases without any temperature spike, allowing for the cooling load to be determined. EXAMPLE 6

[0344] Dormancy is a critical safety performance characteristic for cryogenic or refrigerated gas storage containers and accurately calculating the systemwide dormancy is essential for transportation of gas.

[0345] The Dual-Langmuir Method (Example 1), Virial Method (Example 2), Mass Balance Method (Example 3) and Energy Balance Method (Example 4) were used to simulate the dormancy of an example energy storage system in accordance with the present disclosure. Dormancy refers to the time taken to reach the maximum allowable working pressure for the system. As the gas-filled adsorbent materials enabled cryogenic gas storage container warms up, it desorbs, and the gas desorbing from the material can only escape into the void space. Accurately calculating the dormancy therefore allows the design engineer to select the appropriate packing fraction, the charge temperature, the charge pressure, the maximum allowable working pressure of the pressure vessel component of the gas storage system, and consequently, the total 94 mass of adsorbent material required for the gas storage system, and the resulting maximum amount of gas which can be stored and transported.

[0346] In this example, a 20,000L gas storage container loaded with 15,000kg of the adsorbent material [Cu3BTC2] is initially at 82 K and 31 bar absolute pressure like that of Example 5(a) after 9.2 hours charging.

[0347] Assuming that the tank (or gas storage container) is isolated with no hydrogen allowed to leave the tank (or gas storage container), if we consider a heat leak of 60 W in the storage tank (or gas storage container), the temperature and pressure inside the tank (or gas storage container) will gradually increase until it reaches the maximum allowable working pressure (MAWP) of the inner tank (or inner shell of the gas storage container) which is considered as 51 bara in this example. The temperature and pressure profile inside the inner tank (or inner shell of the gas storage container) as well the distribution of hydrogen in the adsorbed phase and gaseous phase can be estimated based on the calculation basis by discretizing the profile into multiple finite small steps. The constant parameters are the same as that assumed in Example 5(a) except for the heat capacity of the inner tank shell (Cptank-shell) (or inner shell of the gas storage container) which is assumed to be 0.231 kJ / kg / K.

[0348] The dormancy profile is shown in FIG. 24. It is estimated to take approximately 36 days for the inner tank (or inner shell of the gas storage container) pressure to reach 51 bara with an equilibrium temperature of 93.2 K. This increase in inner tank (or inner shell of the gas storage container) pressure is due to desorption of gas from the adsorbent as the system temperature increases and the amount of free gas in the void space inside the inner shell increases from 43.6 kg (about 6.0% free gas) to 63.2 kg (about 8.7% free gas). The total hydrogen inside the tank (or gas storage container) remains constant at approximately 723 kg during this pressure and temperature rise. EXAMPLE 7

[0349] The Dual-Langmuir, Virial, mass and energy balance models of Examples 1 to 4 were used to simulate the decanting process of an example energy storage system in accordance with the present disclosure.

[0350] In this example, a 20,000 L gas storage container loaded with 15,000 kg of the adsorbent material [Cu3BTC2] is initially at 82 K and 31 bar absolute pressure like that of Example 5(a) after 9.2 hours charging.

[0351] In order to discharge the system and release the stored Hydrogen at a constant rate of 50 kg / h, consider hydrogen is being recirculated into the gas storage tank (or gas storage container) at 273 K while being heated through an external heater. The gas storage tank (or gas storage container) is allowed to heat while simultaneously releasing the hydrogen to reach an intermediate temperature of 160 K with a pressure of 31 bar absolute still inside the tank (or gas storage container).

[0352] The remaining stored hydrogen is then released by dropping the pressure inside the tank (or gas storage container) to 1 bar absolute pressure without any external recirculation and heating to reach a final equilibrium temperature which is expected to be lower than 160 K. The point at which circulation and heating is ceased, and the pressure is dropped can be selected to cool the tank (or gas storage container) in preparation for recharging due to the endothermic desorption process.

[0353] The discharging process between initial and final, temperature and pressure conditions can be discretized into multiple finite small steps, and the mass and energy can be conserved at each step as well as the time and the recirculation rate required for each step can be iteratively estimated based on the calculation basis described above. The heat leak into the gas storage tank (or gas storage container) can be neglected for the discharging process as the magnitude is considered low for the time scale under consideration. The constant parameters are the same as that assumed in Example 5.

[0354] The discharging profile is shown in FIG. 25. The Hydrogen recirculation rate required is lower initially and as the tank (or gas storage container) heats up, the recirculation rate required increases due to the decreasing temperature difference between the recirculation Hydrogen temperature (273 K) and the tank (or gas storage container) temperature. The final equilibrium temperature inside the tank is estimated to be around 122 K as the pressure inside the tank (or gas storage container) is dropped from 31 bar to 1 bar absolute pressure without any external heating. At the 50 kg / h of discharge rate considered in this example, it is estimated to take around 13.3 hours to release approximately 667 kg of the total 723 kg of hydrogen stored at the initial conditions. It is noted that the hydrogen discharged from the tank (or gas storage container) is assumed to be at the same temperature as that inside the tank (or gas storage container) and further downstream heating is required to bring the temperature to ambient temperature if that is required by the end user. EXAMPLE 8

[0355] Example 7 was repeated, but altered with the temperature and pressure changing simultaneously, unlike the initially constant pressure process of Example 7.

[0356] FIG. 26 illustrates the profile inside the storage tank (or gas storage container) during the discharging process. The hydrogen recirculation rate required is around 6065 kg / h throughout the discharging process which is lower than the recirculation rate required in Example 7. However, the corresponding volumetric flow rate is higher in this Example as the density of hydrogen drops as the pressure inside the tank (or gas storage container) decreases. Compared to Example 7, the heating load inside the tank (or gas storage container) is lower as the tank (or gas storage container) is not heated to a higher temperature. However, since the total hydrogen discharged is the same, the total energy required is also expected to be the same with the higher heating energy required in the downstream heater to heat the discharged hydrogen to ambient temperature.

[0357] In this Example 8, decanting also takes approximately 13.3 hours, however the heating load and recirculation rates are kept more constant throughout the operation which may be desirable if the ultimate end-user system design requires lower heating load maximum, in this specific case, 50% smaller than in Example 7.

[0358] The above Examples 7 and 8 provide different optionality for decant system design and demonstrate robustness of method. EXAMPLE 9

[0359] Modelling of the discharge process was repeated for 1,000L gas storage container discharging 5 kg / hr of hydrogen. This example differs from Examples 7 and 8 by passively heating circulated hydrogen to induce a thermosyphon effect as described in relation to FIG. 27. The thermosyphon effect utilises the difference in temperature between ambient temperature conditions outside the tank (or gas storage container) and the cryogenic temperature and high-pressure condition inside the tank (or gas storage container), and brings these systems into temperature and pressure equilibrium, thus driving forward desorption energy efficiently.

[0360] FIG. 27 illustrates the profile inside the gas storage tank (or gas storage container) during the discharging process using passive heating. The recirculation rate required was initially around 8 kg / hr, which increases with the increase of temperature to around 16 kg / hr.

[0361] The recirculation rate that can be achieved in a passive discharging system will depend on the pressure drop across the various components in the recirculation loop. The system can be designed to achieve the pressure drop and thus the recirculation rate depending on the discharge rate required. The recirculation is ideally done at higher pressures so as the density of hydrogen is higher thereby reducing the volumetric flow rate and thus the pressure drop in the recirculation loop.

[0362] It is to be noted that there are limitations to minimising the pressure drop and thus, the maximum recirculation rate that can be achieved. EXAMPLE 10

[0363] The effect of varying hydrogen charge pressure, amount of adsorbent in a specified volume and charge temperature on the amount of hydrogen stored and the corresponding dormancy time achieved in a 20,000 L gas storage container containing [Cu3BTC2.]. The methodology was based on that of Example 6 assumes a constant heat loss of 5.5 W for the 1,000 Litre system in FIG.28(A), FIG.29(A), FIG.30(A) and a constant heat loss of 60 W for the 20,000 Litre system in FIG. 28(B), FIG. 29(B), FIG. 30(B), and a maximum allowable working pressure of 50 barg for both.

[0364] FIG. 28 shows the hydrogen stored and dormancy time until the maximum working pressure is met as a function of charge pressure for a 1000L gas storage container (FIG. 28 (A)) and a 20,000L gas storage container (FIG. 28 (B)). It is evident that altering the charge pressure results in a trade-off between the amount of hydrogen stored and dormancy. The greater the charge pressure, the shorter the dormancy. This is because the maximum allowable working pressure is held constant at 50 barg. The figures demonstrate the range available in dormancy to the system designer.

[0365] FIG. 29 shows the hydrogen stored and dormancy time until the maximum working pressure is met as a function of adsorbent bulk density (which relates to packing fraction), for a 1000L gas storage container (FIG. 29 (A)) and a 20,000L gas storage container (FIG. 29 (B)). Here we show that, counterintuitively, a packing fraction of adsorbent between 0.55 and 0.88 is desirable, as the void space, even though it is less efficient at storing gas, it plays an important role in accommodating space for the materials to desorb gas into, and space to drive effective convection for efficient and fast charging and discharge. Conversely if dormancy requirements for the end-user are minimal, then maximising the amount of adsorbent in a given volume closer to 0.88, increases the amount of hydrogen stored, at a cost of a reduction in dormancy time 98 owing to the lower void space to accommodate gaseous hydrogen. The example shows that packing fraction is a key element for system design to control both total gas stored and dormancy.

[0366] FIG. 30 shows the hydrogen stored and dormancy time until the maximum working pressure is met as a function of charge temperature, for a 1000L gas storage container (FIG. 30(A)) and a 20,000L gas storage container (FIG. 30(B)). Higher charge temperatures are not seen to have any major impact on the dormancy time of the system. However, it is noted that a constant heat leak is assumed in the system, whereas higher charge temperatures are expected to have slightly lower heat leak thereby improving dormancy time. Increasing the charge temperature lowers the amount of hydrogen stored in the gas storage container but it can offer lower operation cost as the cooling energy of the system is extracted at a relatively higher temperature. Charge temperature does however have a significant impact on total gas stored, therefore while it does not significantly affect dormancy, it is still a key element for system design. EXAMPLE 11

[0367] Gas separations can be undertaken using the method described herein, also using fundamental properties of the selected adsorbent material, determining its selectivity based on isotherms at the planned gas separation temperature and over a wide pressure range of 0 to 100 bar pressure, as shown below.

[0368] The gas separation performance based on different hydrogen / methane mixture on our CuII3[CoIII(CN6)] samples was evaluated using the Ideal Adsorbed Solution Theory . First the pure component adsorption isotherms of methane and hydrogen at 298 K were fitted to the Langmuir model as shown in FIG. 31. Then, the Langmuir parameters were used as the input for the IAST equations to estimate the hydrogen / methane mixture isotherms as the function of feed composition and pressure as shown in FIG. 32, FIG. 33, FIG. 34, FIG. 35 and FIG. 36. The Ideal Adsorbed Solution Theory (IAST) originally was developed by Myers and Prausnitz in 1965 and is still one of the most widely used thermodynamic models for predicting adsorption behaviour of multicomponent gas mixtures from single component isotherms. Because of its simplicity and reasonable accuracy for many microporous materials, IAST still remains a standard tool for mixture adsorption calculations specially when experimental mixture data are not available.

[0369] IAST assumes that at equilibrium the adsorbed phase behaves like an ideal solution similar to Raoult’s law for liquid mixtures and each component in the adsorbed phase has the same spreading pressure (n) at equilibrium. The surface potential of mixture (¢) is the same as surface potential of all pure components, as shown below: nA CPi nAP) 0 = — =       dP R T / P r                              Equation 23

[0370] FIG. 32 shows the binary IAST uptake versus pressure assuming a methane mole fraction of 0.8 in the feed at 298 K.

[0371] FIG. 33 shows the binary IAST uptake versus pressure assuming a methane mole fraction of 0.3 in the feed at 298 K.

[0372] FIG. 34, FIG. 35 and FIG. 36 show the absolute amount adsorbed as well adsorbed phase compositions of each component, at 30 bar for hydrogen and methane, at different hydrogen and methane mole fractions at 298K. This demonstrates the ability of the systems to deliver gas capture and separation based on the relative selectivity of adsorbent material to a gas within a gas mix.

[0373] The hydrogen / methane gas mixture isotherms and IAST outputs represent selectivity curves to inform design of a system for separation and storage of gases. EXAMPLE 12

[0374] Effect of volume fraction of coarse particles on the overall packing fraction for different size ratios of fine to coarse particles as shown in FIG. 37, and effect of size ratio on the overall packing fraction for a volume fraction of fine and coarse particles of 0.5 as shown in FIG. 38 for binary mixture of spherical particles based on research by A. B. Yu, R. P. Zou and N. Standish (1996) “Modifying the linear packing model for predicting the porosity of nonspherical particle mixtures”, J Industrial & Engineering Chemistry Research, 35(10).

[0375] The ‘linear-mixture packing model’ proposed by Yu et al. (1996) broadly classifies the packing mechanism of a binary spherical particle mixture based on the size ratio of the fine to coarse particles. If the size ratio is lower than 0.154, the filling mechanism is dominant where the finer particles fill the voids between the coarse particles and if the size ratio is higher than 0.154, the mixing effect starts to dominate where the fine particles influence the packing of the coarse particles.

[0376] These methods were applied to adsorbent materials to produce different packing fraction models and shown in FIG. 37 and FIG. 38. 100

[0377] As evident from FIG. 37, based on the model, the lower the size ratio, the higher the overall packing fraction that can be achieved for any volume fraction of the coarse particles and the maximum overall packing fraction for a size ratio of 0.1 is >81% for the volume fraction of coarse particles approximately >70%. These theoretical estimates are based on the overall packing fraction of the coarse or fine spherical particles to be 64% assuming a random packing of spherical particles with minimal wall effects considering the inner shell diameter of the gas storage container to be orders of magnitude higher than the individual particle diameter. The overall packing fraction can further be increased above 90% using a ternary mixture while still maintaining the size ratio between the different sizes to be less than 0.154.

[0378] Field trials of 16.3 kg of adsorbent material of [Cu3BTC2] in a 30 Litre gas storage container showed approximately single sized ellipsoidal particles achieved a packing fraction of 59%, close to the theoretical maximum for a single particle shape and size, validating the theoretical approach. EXAMPLE 13

[0379] The Dual-Langmuir, Virial, mass and energy balance models of Examples 1 to 4 were used to compare a gas storage container loaded with the adsorbent material [Cu3BTC2.] in comparison with an unloaded gas storage container under various conditions to ascertain comparable performance advantages and also to ascertain the total free gas volume within the void, a key metric to determine inherent safety.

[0380] FIG. 39 compares the hydrogen stored in an empty gas storage container versus a [Cu3BTC2.] loaded gas storage container at 80K and a packing fraction of 75% for various pressures (at 10 bar, 30 bar and 50 bar pressure). FIG. 40 repeats this study with pressure held constant at 50bar with temperature being varied (at 80 K, 100 K and 120 K). It is evident from FIG. 39 and FIG. 40 that the adsorbent loaded gas storage container stores much greater hydrogen with a much lower amount of free (unadsorbed) gas at each pressure and temperature.

[0381] The reduction of free gas in the adsorbent loaded gas storage container inherently improves the safety compared to the bare gas storage container, as less gas is available for release, at any given temperature or pressure, in the event the gas storage container is ruptured or equipment such as a valve fails. System safety is therefore always improved by a factor of at least 4x with the adsorbent material in the gas storage container. EXAMPLE 14

[0382] A field trial of a 30L gas storage container loaded with 16.3kg equivalent to a packing fraction of 59% [Cu3BTC2] and charged with hydrogen was performed by opening a valve to profile pressure, average temperature and the hydrogen release. Fully opening a valve on this gas storage container simulates the behaviour of sudden gas release, such as in the event of gas storage container rupture or valve failure. This was performed to demonstrate the safety enhancement the adsorbent material presents when incorporated in the gas storage container.

[0383] FIG. 41 shows that upon opening the valve, gas storage container pressure dropped rapidly and approximately 16% of the stored hydrogen was released. As most stored hydrogen is not a free gas but rather adsorbed, the remaining release of hydrogen occurred gradually over many hours as the temperature inside the gas storage container increased.

[0384] The higher initial release is due to lower packing fraction inside the gas storage container as well as desorption of the adsorbed Hydrogen as the pressure inside the gas storage container decreases. This supports the modelling results indicating only a small fraction of the hydrogen is free hydrogen at the corresponding equilibrium conditions. EXAMPLE 15

[0385] The Dual-Langmuir, Virial, mass and energy balance models of Examples 1 to 4 were used to consider the effects of certain parameters on the deliverable capacity of hydrogen in a gas storage container loaded with the adsorbent material [Cu3BTC2].

[0386] FIG. 42 compares the deliverable capacity for a gas storage container loaded with the MOF [Cu3BTC2] and a bare gas storage container under two scenarios. Under the first scenario, the deliverable capacity is considered at the same temperature as the storage temperature, namely 80K. In the second scenario, the discharge temperature ‘swings’ to 120K i.e. higher than the storage temperature of 80K.

[0387] The deliverable capacity of hydrogen in the bare gas storage container is the same under both scenarios. However, the deliverable capacity increases for the adsorbent material (in this case a MOF) loaded gas storage container under the second scenario as the additional ‘swing’ temperature provides energy to desorb hydrogen for delivery.

[0388] FIG. 43 shows the deliverable capacity of hydrogen increases with increasing packing fraction.

[0389] FIG. 44 shows that the discharge capacity increases with increasing ‘swing’ temperature, that is with increased difference in temperature above the storage temperature. Also evident from FIG. 42 is the increase in deliverable capacity with increased temperature swing plateaus.

[0390] FIG. 44 compares the effect of ‘swing’ temperature on the discharge capacity for the adsorbent material (in this case a MOF) loaded gas storage container and a bare gas storage container, showing no effect for the bare gas storage container.

[0391] FIG. 45 shows the effect of different packing fractions at certain ‘swing’ temperatures, confirming that capacity increases with both packing fraction and maximum temperature swing range, although with diminishing returns above 117 K as >91.6% of the hydrogen gas is desorbed above 117 K, and 94.5% of the hydrogen gas is desorbed above 127 K, and 96.2% is desorbed above 137 K, and 97.3% is desorbed above 147 K.

[0392] The example provides a method to design and characterise key safety data on available free gas volume in the void space, demonstrates the total uptake performance enhancement of the adsorbed material in the gas storage container, and provides detail on the key design parameters which deliver impact, including packing fraction, load temperature, maximum discharge temperature, charge pressure and maximum working pressure of the gas storage system. EXAMPLE 16

[0393] Thermogravitational analysis (TGA) of [Cu2BTC3] under flowing N2 was performed to simulate the in-situ activation of the material in the gas storage container to remove adventitious species such as water that may adsorb during storage and handling. The test was performed at 100°C, 120°C and 150°C as shown in FIG. 45, FIG. 46 and FIG. 47 respectively. The weight of the sample reached a lower endpoint at a quicker rate for increasing temperature. The example demonstrates that adsorbent materials with activation temperatures <150°C can be fully activated in-situ in the gas storage system. EXAMPLE 17

[0394] A field trial was performed whereby a gas storage container containing [Cu3BTC2] was charged with hydrogen to 30 bar and then discharged (i.e. to 1 bar) multiple times to study the ability of the adsorbent to be reused.

[0395] As shown in FIG. 48, as the amount of delivered hydrogen remained effectively constant across the repeated trials, while the uptake in wt(%) gradually increased at both charge (30bar) and discharge (1bar) between cycles 1 to 50 and again between cycles 51 to 100. This monotonic increase in mass was due to adsorption of impurities, primarily water, in the source hydrogen. Despite the adsorption of impurities in every cycle, no decline in hydrogen deliverable capacity was observed. This demonstrates the reusability of adsorbents designed and selected so that the impurities bind to different sites to the target gas in a manner that they are not desorbed at the decanting temperature and pressure of the target gas. EXAMPLE 18

[0396] FIG. 50 is a plot of adsorbent uptake cycles of [Cu3BTC2], 100 cycles using hydrogen gas, conducted between 1 and 30 bar pressure at 298 K, with a single evacuation reactivation cycle before the 50th cycle (conducted at 10-3 mbar). The cycling shows firstly that during cycling; the adsorbent material adsorbs impurities from the source gas without disruption to the delivered hydrogen (hydrogen adsorbed minus hydrogen desorbed).

[0397] Secondly, the example shows that performance is restored using just only evacuation at 10-3 mbar and at ambient temperature, demonstrating that once the system is sealed, in-situ re-activation with only vacuum at ambient temperature is feasible. EXAMPLE 19

[0398] FIG. 51 shows an example of a two-step activation protocol for of adsorbent materials with high activation temperatures, using [(Fem2FeH(p3-O))2(ABTC)3] as an exemplar adsorbent material with high activation temperature. The two-stage activation protocol is generalisable for all adsorbent materials with activations temperatures greater than 120oC. Adsorbent materials with activation temperature at 120oC or less, can be activated in-situ within the gas storage container, using the method described above (using hot dry nitrogen or hot dry air at 120oC for 12 hours to 72 hours). For adsorbent materials with higher activation temperature, the following two stage approach achieves the same result, without damaging gas storage container components which may typically be only rated to around 150oC as their maximum temperature. (Specialist components can be manufactured with higher temperature rating however this adds significant cost (sometime 10x increase in component cost), and the two-step activation is designed to achieve cost efficiency using off-the-shelf gas storage container balance of plant components). In this example, we use the exemplar adsorbent material [(Fem2FeH(p3-O))2(ABTC)3], which has an activation temperature of 200oC. Using the two-step activation protocol, activation is first done as an ex-situ activation (Stage 1) at 200°C under flowing Nitrogen gas in conventional oven equipment, followed by in-situ activation (inside the gas storage container enabled with adsorbent materials), with this activation conducted at 120°C under flowing nitrogen gas (Stage 2). Stage 1 activation removes synthesis solvent from the surface and the pores of the nanoporous material which are trapped in the materials during synthesis. Stage 2 activation removes any moisture or gases from air which may adsorb to the material during handling and packing. Thermogravimetric analysis (TGA) in FIG. 51(A) shows successful ex-situ activation at high temperature at 200oC. The adsorbent material was then exposed to air for 6000 minutes on the TGA instrument to simulate how a material may gain adsorbed water during handling, packing, transport or storage, recorded as 23% mass gain due to water shown in FIG. 51 (B). The example then shows that this unwanted moisture can be completely removed during a Stage 2 in-situ activation process, as shown in FIG. 51 (C), conducted at lower 120°C under a flow of hot dry nitrogen for 3000 minutes. As shown in FIG. 5, re-activation is complete after about 12 hours. Activation and re-activation of the nanoporous adsorbent material can be therefore be conducted by application of heat under flowing nitrogen gas or alternatively under active vacuum at 120°C. Conventional cryogenic and ambient temperature pressure vessel components are typically rated for a maximum 150oC maximum temperature range, so validating the ability to conduct re-activation in-situ within the gas storage system, simplifies the manufacturing and certification of the gas storage container if the above method is followed. This will significantly reduce cost of production and improve safety. EXAMPLE 20

[0399] FIG. 52 shows the gravimetric hydrogen uptake for various nanoporous, microporous or mesoporous adsorbent materials (a) [Cu2(ABTC)] (b) [Cu3BTC2] (c) 105 [(Al"I3(|J3-O))2(ABTC)3].|(NO3)2| (d) cubic CuII3[CoIII(CN6)]; all at 77 K (-196oC), and between 0 - 100 bar pressure. These isotherms are the first step in determining adsorbent material selection according to the method described above.

[0400] FIG. 53 shows the volumetric hydrogen storage of (a) [Cu3BTC2] and (b) cubic CuII3[CoIII(CN6)] (c) plain gas storage container without adsorbent; at 77 K, and between 0 - 100 bar pressure, assuming a packing fraction of 75%. FIG. 52 and FIG. 53 together demonstrate the need to consider bulk density of the material when selecting an adsorbent material for a gas container. CuII3[CoIII(CN6)] performs less well on a gravimetric basis compared with [Cu3BTC2], but more similarly on a volumetric basis owing to its large bulk material density. EXAMPLE 21

[0401] FIG. 54 shows the volumetric methane uptake for (a) [Cu3BTC2] and (b) cubic CuII3[CoIII(CN6)] (c) plain gas storage container without adsorbent; at 298 K, and between 0 - 100 bar pressure, assuming a 75% packing fraction. The example demonstrates that adsorbent materials can outperform conventional compressed natural gas (volumetric energy density of 155 g(methane) / L at 250 bar pressure), at pressures greater than 40 bar pressure for [Cu3BTC2] and 100 bar pressure for CuII3[CoIII(CN6)].

Claims

1. A gas storage system comprising:a gas storage container comprising one or more adsorbent materials.

2. The gas storage system of claim 1, wherein the adsorbent materials compriseone or more nanoporous, microporous or mesoporous absorbent material.

3. The gas storage system of claim 1 or claim 2, wherein one or more adsorbentmaterials comprises one or more Metal-Organic-Framework (MOF) materials, Covalent-Organic-Framework (COF) materials, MOF-composite materials, MOF-hybrid materials, and / or MOF-hybrid-composite materials.

4. The gas storage system of claim 3, wherein the one or more adsorbentmaterials comprise one or more MOFs.

5. The gas storage system of any one of claims 1 to 4, further comprising acharging subsystem comprising: a charging heat exchanger, wherein the charging heat exchanger is in a charging recirculation loop with the gas storage container, said charging recirculation loop comprises a charging output line from the storage container to the charging heat exchanger, and a charging input line from the heat exchanger to the gas storage container.

6. The gas storage system of claim 5, wherein the charging subsystem furthercomprises a gas supply line upstream of the heat exchanger.

7. The gas storage system of claim 5 or claim 6, wherein the charging heatexchanger is a cryocooler.

8. The gas storage system of any one of the preceding claims, further comprisinga decanting system comprising: a decanting heat exchanger, wherein the decanting heat exchanger is in a decanting recirculation loop with the gas storage container, said decanting recirculation loop comprising a decanting output line from the gas storage container to the decanting heat exchanger, and a decanting input line from the decanting heat exchanger to the gas storage container.

9. The gas storage system of claim 8, wherein recirculation of gas through thedecanting recirculation loop operates by thermosyphon.

10. The gas storage system of claim 8, wherein recirculation of gas through thedecanting recirculation loop operates by forced convection.

11. The gas storage system of any one of claims 8 to 10, wherein the decantingsubsystem heat exchanger uses ambient air as a heat transfer fluid.

12. The gas storage system of any one of claims 8 to 10, wherein the decantingsubsystem heat exchanger uses waste heat.

13. The gas storage system of any one of claims 5 to 12, wherein the charging anddecanting subsystems use unique para-spin-state catalysing effect of adsorbent materials with paramagnetic clusters within their structure to increase energy efficiency of the charger for hydrogen storage systems.

14. The gas storage system of any one of claims 5 to 13, wherein the charging anddecanting subsystems are separably connectable to the gas storage container at a charging location.

15. The gas storage system of any one of claims 5 to 10, wherein the charging anddecanting subsystems use the storage gas as its own heat transfer fluid in a closed loop.

16. The gas storage system of any one of the proceeding claims, wherein the gasstorage system can be used to energy efficiently capture boil-off from conventional liquefied hydrogen gas and conventional liquefied natural gas storage systems.

17. The gas storage system of any one of the preceding claims, further comprisingan activation subsystem: comprising an activation input line having an activation heating element configured to deliver an inert gas to the absorbent material at a sufficient temperature to raise the temperature of the absorbent material to an activation temperature.

18. The gas storage system of claim 17, wherein the activation temperature isabove 100°C, under a flow of hot dry nitrogen, or under a flow of hot dry air, or under vacuum of at least 10-2 mbar.

19. The gas storage system of claim 17 or claim 18, wherein the activationsubsystem further comprises an activation output line having a dryer element configured to remove moisture from the inert gas after being delivered to the absorbent material, said activation output line connecting with the activation input line to return dried inert gas upstream of the activation heater element.

20. The gas storage system of any one of the preceding claims, wherein the at leastone adsorbent material has a Heat of Adsorption of between -3 and -10 kJ / mol for cryogenic hydrogen gas storage systems and between -10 and -25 kJ / mol for ambient temperature gas storage systems.

21. The gas storage system of any one of the preceding claims, wherein the systemcan leverage the gas selectivity properties of the adsorbent materials to separate, capture, store and transport gases energy efficiently.

22. The gas storage system of any one of the preceding claims, wherein digitalalgorithms, third-party software or hardware or both, can be designed and integrated for gas storage bulk transport and distribution, and for on-vehicle or on-marine-vessel or on-aircraft gas storage fuel tanks, which draws on gas storage and transfer information generated by technologies to provide pricing (historical, current and predictive), location, logistics, gas carried, provenance, certification of origin, guarantees, temperature, pressure, precise payload value, telemetric, GIS, safety, video, infrared and smell detection security information, and real time safety information, which can be retained, and transmitted for centralised or decentralised monitoring and management, trading of contained gases, financialization of gas storage or gas capture systems as flexible, fixed or agile assets, calculation of government and non-government incentives, hydrogen and carbon dioxide and biogas and other gas tax incentives or carbon dioxide and other gaseous emissions offset credits, and support trading of fuel or carbon-dioxide. and deliver any other value-added information generated by the gas storage or gas capture system, to support decarbonisation and gas storage and gas transport.

23. The gas storage system of any one of the preceding claims, wherein the gasmay be selected from one or more of hydrogen, biomethane, biogas, carbon dioxide, methane, natural gas, natural hydrogen, stimulated hydrogen, ammonia, oxygen, air, helium, neon, argon, nitrogen, medical gases, refrigerant gases, hospitality and food / beverage gas mixtures, welding gas mixtures, laser gas mixtures or acetylene.

24. The gas storage system of any one of the preceding claims, whereby the gasstorage container operates autonomously, is passively cooled, maintains hold or dwell or dormancy temperature for at least 3 days and up to 60+ days at a time.

25. The gas storage system of any one of the preceding claims, whereby the gasstorage container can withstand impacts without opening and releasing the contents.

26. The gas storage system of any one of the preceding claims, whereby the gasstorage container would not exhibit boiloff during a hold or dwell or dormancy period, and would be able to maintain its temperature, passively.

27. The gas storage system of any one of the preceding claims, whereby the gasstorage container would operate at pressures less than 100 bar pressure, while maintaining high volumetric densities greater than 20 kg / m3 in the case of hydrogen storage.

28. A system for storing hydrogen gas comprising:a storage container comprising at least one adsorbent material configured to induce a switch from ortho-hydrogen spin-state to para-hydrogen spin-state, and maintain the para-hydrogen spin-state.

29. The system of claim 28, wherein the at least one adsorbent material comprisesat least one para-magnetic cluster moiety.

30. The system of claim 29, wherein the at least one para-magnetic paddlewheelmetal-ion cluster moiety comprises d-block transition metal ions forming a secondary building unit within a MOF.

31. The system of claim 29, wherein the moiety is a copper paddlewheel CuII-CuIImoiety, the copper paddlewheel moiety within [CuII3BTC2] or [CuII2(ABTC)](where BTC = benzenetricarboxylate, and ABTC = azobenzenetetracarboxylate).

32. The system of claim 29, wherein the at least one para-magnetic cluster moietyis a metal-ion-oxo trimer comprising of d-block transition metal ions, the iron-ion trimer comprising a single FeII and two FeIII within [(Fem2FeH(p3-O))2(ABTC)3] (where ABTC = azobenzenetetracarboxylate).

33. The system of claim 28 to 32, wherein the gas storage system can be used tocapture boil-off from conventional liquefied hydrogen gas.

34. The system of claim 28 to 32, wherein the gas storage system delivers end-to-end energy efficiency for cryogenic hydrogen storage.

35. The system of any one of claims 28 to 34, wherein the system operatesbetween about 20 K to about 300 K temperature.

36. The system of any one of claims 28 to 35, wherein the system operatesbetween about 1 bar to about 150 bar pressure.

37. A method for charging gas to a container comprising one or more adsorbentmaterials, comprising recirculating the gas through the container via a recirculation loop, wherein the gas is cooled in the recirculation loop.

38. The method according to claim 37, wherein the gas is cooled in the recirculationloop via ambient air.

39. The method according to claim 37, wherein the gas is cooled in the recirculationloop via a heat exchanger.

40. The method according to claim 39, wherein the heat exchanger is a cryo-cooler.

41. The method according to any one of claims 37 to 39, wherein recirculation ofgas through the container via the recirculation loop continues until a target storage pressure and / or temperature is achieved within the container.

42. A method for decanting gas from a container comprising one or more adsorbentmaterials, comprising recirculating the gas through the container via a recirculation loop, wherein the gas is heated in the recirculation loop.

43. The method according to claim 42, wherein the gas is heated in the recirculationloop via ambient air, or a source of waste heat from waste hot water or waste hot steam.

44. The method according to claim 43, whereby the waste hot water or waste hotsteam comes from a fuel cell, combustion engine, or steam turbine.

45. The method according to claim 43, whereby the waste heat comes from a fuelcell or generated as waste hot water or hot steam from an internal-combustionengine, or generated as waste hot water or hot steam from a turbine, or generated as waste hot water from a data centre, or generated as waste hot water or hot steam from industrial processes.

46. The method according to claim 45, whereby the waste heat passes through aheat exchanger to warm a secondary heat transfer fluid, such as ethylene glycol, which is then used to warm cryo-hydrogen at the appropriate rate to achieve precise flow rates required by the end user47.    The method according to claim 42, wherein the gas is heated in the recirculationloop via a heat exchanger.

48. The method according to claim 42, wherein the recirculation of gas through thecontainer via the recirculation loop continues until a target discharge pressure is achieved, wherein upon achieving the target discharge pressure, gas is discharged from the container.

49. The method according to claim 48, wherein the gas is discharged from thecontainer at a rate configured to maintain the target discharge pressure.

50. The method according to claim 48 or claim 49, wherein the target pressure isselected according to a desired discharge rate.

51. The method according to claim 48, wherein the recirculation of gas through thecontainer via the recirculation loop continues while the gas is being discharged until a target discharge pressure is achieved, whereupon recirculation of the gas is ceased while gas remaining in the container is discharged.

52. The method according to claim 51, wherein a target temperature is selectedaccording to a desired final temperature of the gas storage container induced by the gas remaining in the desorbing gas storage container.

53. A method for activating an absorbent material for use in a gas storagecontainer, comprising:a first stage whereby the adsorbent material is heated to a first activation temperature configured to evacuate solvents and other contaminants from activation sites of the adsorbent material under a flow of hot dry nitrogen, or a flow of hot dry air, and / or under a vacuum; anda second stage whereby the adsorbent to a second activation temperature under a flow of hot dry nitrogen, or a flow of hot dry air, and / or under vacuum.

54. The method according to claim 53, wherein the second activation temperatureis equal to or less than the first activation temperature.

55. The method according to claim 53, wherein the second activation temperatureis less than the first activation temperature.

56. The method according to any one of claims 53 to 55, wherein the first stage isperformed in-situ in the gas storage container.

57. The method according to any one of claims 53 to 55, wherein the first stage isperformed ex-situ from the gas storage container.

58. The method according to claim 57, wherein upon activation in the first stage, theadsorbent material is vacuum packed.

59. The method according to any one of claims 53 to 58, wherein the second stageis performed in-situ in the gas storage container.

60. The method according to any one of claims 53 to 59, wherein the secondactivation temperature is between about 100°C to about 120°C.

61. The method according to any one of claims 53 to 59, wherein the secondactivation temperature is about 120°C.

62. The method according to any one of claims 53 to 61, wherein the vacuumhardness is about 10-3 mbar.

63. The system of any one of claims 1 to 36, wherein the storage container ischarged according to the charging method of any one of claims 37 to 41.

64. The system of any one of claims 1 to 36, wherein the storage container isdecanted according to decanting method of any one of claims 42 to 52.

65. The system of any one of claims 1 to 36, wherein the adsorbent material isactivated according to the activation method of any one of claims 53 to 62.

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