SYSTEMS

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority of United States Provisional Patent Application No. 61/939,884, filed February 14, 2014, United States Provisional Patent Application No. 61/939,889, filed February 14, 2014, and United States Provisional Patent Application No. 61/939,895, filed February 14, 2014, all of which are hereby incorporated by reference herein in their entireties.

BACKGROUND OF THE DISCLOSURE

[0002] Adsorbent materials can be used for the storage of gas. A particular adsorbent, metal organic framework, is a highly crystalline structure with nanometer-sized pores that allow for the storage of natural gas and other gases such as hydrocarbon gas, hydrogen and carbon dioxide. Metal organic framework can also be used in other applications such as gas purification, gas separation and in catalysis.

[0003] These materials are typically in particle form and essentially consist of two types of building units: metal ions (e.g. zinc, aluminum) and organic compounds. Each of the organic compounds can attach to at least two metal ions (at least bidentate), serving as a linker for them. In this way a three dimensional, regular framework is spread apart containing empty pores and channels, the sizes of which are defined by the size of the organic linker.

[0004] The high surface area provided by metal organic framework can be used for many applications such as gas storage, gas/vapor separation, heat exchange, catalysis, luminescence and drug delivery. By way of example, metal organic framework can have (show) a specific surface area of up to 10,000 m ² /g determined by Langmuir model.

[0005] A particular application of metal organic framework is for gas storage (e.g., natural gas) in gas powered vehicles. The larger specific surface area and high porosity on the nanometer scale enable metal organic framework to hold relatively large amounts of gases. Used as storage materials in natural gas tanks/containers, metal organic framework offers a docking area for gas molecules, which can be stored in higher densities as a result. The larger gas quantity in the tank can increase the range of a vehicle. The metal organic framework can also increase the usable time of stationary gas powered applications such as generators and machinery.

[0006] There exists a need in the art for systems and methods to improve efficiency and capacity and extend the usable life of adsorbent materials (e.g., metal organic framework). There also exists a need in the art for systems and methods of maximizing the efficiency and utilization of gas adsorbed onto adsorbent materials (e.g., metal organic framework) during periods of depressurization or during timed of increased requirements of power. There also exists a need in the art for systems and methods of maximizing the efficiency and utilization of gas adsorbed onto adsorbent materials (e.g., metal organic framework) and to minimize the aging of adsorbent particles such that they maintain their storage capacity over time. There also exists a need in the art for vehicles that are at least partially powered by such systems.

OBJECTS AND SUMMARY OF THE DISCLOSURE

[0007] It is an object of certain embodiments to provide systems and methods of determining the change in capacity over time of adsorbent materials (e.g., metal organic framework).

[0008] It is an object of certain embodiments to provide systems and methods of determining when service is due to increase the capacity of adsorbent materials (e.g., metal organic framework).

[0009] It is an object of certain embodiments to provide systems and methods of providing service to increase the capacity of adsorbent materials (e.g., metal organic framework).

[0010] It is an object of certain embodiments to provide an adsorbed gas containment system that that has increased efficiencies and utilization of the adsorbed gas.

[0011] It is an object of certain embodiments to provide containment systems suitable for adsorbed gas storage.

[0012] It is an object of certain embodiments to provide gas powered machines (e.g., vehicles, heavy equipment) that utilize the containment systems disclosed herein.

[0013] It is an object of certain embodiments to provide systems and methods of providing a compressed gas to an internal combustion engine or fuel cell.

[0014] It is an object of certain embodiments to provide systems and methods of providing increased utilization of a compressed gas to an internal combustion engine or fuel cell at times of depressurization.

[0015] It is an object of certain embodiments to provide systems and methods of providing increased utilization of a compressed gas to an internal combustion engine or fuel cell at times of increased power requirements. [0016] The above objects and others may be met by the present disclosure, in which certain embodiments are directed to an adsorbed gas containment system comprising an adsorbed gas container at least partially filled with adsorbent particles; and an analytical system to measure the containment system capacity, the analytical system having communication capability.

[0017] Certain embodiments are directed to a compressed gas vehicle comprising an adsorbed gas containment system comprising an adsorbed gas container at least partially filled with adsorbent particles; and an analytical system to measure a capacity of the adsorbed gas containment system, the analytical system having communication capability.

[0018] Certain other embodiments are directed to a method of manufacturing a vehicle comprising integrating a containment system of any of the preceding claims into the vehicle.

[0019] Certain other embodiments are directed to a method of manufacturing a vehicle comprising detachably integrating a containment system of any of the preceding claims into the vehicle.

[0020] Certain other embodiments are directed to a method of servicing an adsorbed gas containment system comprising activating the adsorbent particles at a predetermined time interval.

[0021] Certain other embodiments are directed to a method of servicing an adsorbed gas containment system comprising activating the adsorbent particles at a time when the analytical system indicates that the containment system capacity is equal to or below a predetermined level.

[0022] The above objects and others may be met by the present disclosure, in which certain embodiments are directed to a method of adsorbing a gas onto adsorption particles comprising adsorbing gas onto adsorption particles at a sufficiently reduced rate such that the capacity of the particles is higher after multiple cycles as compared to the capacity after multiple cycles at a higher rate. In one embodiment, the capacity is maintained at least about 75% over a period of 25 cycles. In one embodiment, the adsorption particles are in a container suitable for adsorbed gas storage.

[0023] Another embodiment is directed to a method of desorbing a gas from adsorption particles comprising desorbing gas from adsorption particles at a sufficiently reduced rate such that the capacity of the particles is higher after multiple cycles as compared to the capacity after multiple cycles at a higher rate. In one embodiment, the capacity is maintained at least about 75% over a period of 25 cycles.

[0024] Another embodiment is directed to a method comprising adsorbing gas onto adsorption particles in plug flow fashion.

[0025] The objects and others may be met by the present disclosure, in which certain embodiments are directed to an adsorbed gas fuel system comprising an internal combustion engine or fuel cell; a first adsorbed gas container fluidly connected to the internal combustion engine or fuel cell, the adsorbed gas container containing adsorbent particles; a compressor fluidly connected to the internal combustion engine or fuel cell and the first adsorbed gas container, the compressor adapted to remove gas from the first adsorbed gas container; and a second adsorbed gas container fluidly connected to the internal combustion engine or fuel cell and fluidly connected (or optionally fluidly connected) to the first adsorbed gas container, the second adsorbed gas container containing adsorbent particles.

[0026] Certain embodiments are directed to an adsorbed gas fuel system comprising an internal combustion engine or fuel cell; a first adsorbed gas container fluidly connected to the internal combustion engine or fuel cell, the adsorbed gas container containing adsorbent particles; and a second adsorbed gas container fluidly connected to the internal combustion engine or fuel cell and fluidly connected (or optionally fluidly connected) to the first adsorbed gas container, the second adsorbed gas container containing adsorbent particles, wherein the second adsorbed gas container is adapted to supply a gas to the internal combustion engine or fuel cell when the pressure of the first adsorbed gas container is at or below a predetermined level of reduced pressure or when the fuel requirements of the engine or fuel cell are at or above a predetermined level.

[0027] Certain other embodiments are directed to a method of preparing or method of operating the systems disclosed herein.

[0028] Certain other embodiments are directed to a vehicle utilizing the systems and methods disclosed herein.

[0029] In certain embodiments, adsorbent particles comprise metal organic framework particles or activated carbon. In certain embodiments, the metal organic framework particles have a surface area of at least about 500 m ² /g, at least about 700 m ² /g, at least about 1 ,000 m ² /g, at least about

2 2 2 2

1,200 m /g, at least about 1,500 m /g, at least about 1,700 m /g, at least about 2,000 m /g, at least about 5,000 m ² /g, or at least about 15,000 m ² /g.

[0030] In certain embodiments, the metal organic framework particles comprise a metal selected from the group consisting of Li, Mg, Ca, Sc, Y, Zr, V, Mn, Fe, Co, Ni, Cu, Zn, B, Al, Ti, and a combination thereof. In certain embodiments, the metal organic framework particles comprise a moiety selected from the group consisting of a phenyl moiety, an imidazole moiety, a pyridine moiety, a pyrazole moiety, an oxole moiety, and a combination thereof.

[0031] In certain embodiments, the metal organic framework particles are in a form of pellets, extrudates, beads, monoliths, or any other defined or irregular shape.

[0032] In certain embodiments, the adsorbent particles comprise metal organic framework particles or activated charcoal. [0033] In certain embodiments, the adsorbent particles are disposed within a container having a form of a tank, cyclindrical, toroidal, or rectanguloid.

[0034] As used herein, the term "natural gas" refers to a mixture of hydrocarbon gases that occurs naturally beneath the Earth's surface, often with or near petroleum deposits. Natural gas typically comprises methane but also may have varying amounts of ethane, propane, butane, and nitrogen.

[0035] The terms "adsorbed gas container" or "container suitable for adsorbed gas storage" refer to a container that maintains its integrity when filled or partially filled with an adsorption material that can store a gas. In certain embodiments, the container is suitable to hold the adsorbed gas under pressure or compression.

[0036] The terms "vehicle" or "automobile" refer to any motorized machine (e.g., a wheeled motorized machine) for (i) transporting of passengers or cargo or (ii) performing tasks such as construction or excavation. Vehicles can have, e.g., at least 2 wheels (e.g., a motorcycle or motorized scooter), at least 3 wheels (e.g., an all-terrain vehicle), at least 4 wheels (e.g., a passenger automobile), at least 6 wheels, at least 8 wheels, at least 10 wheels, at least 12 wheels, at least 14 wheels, at least 16 wheels or at least 18 wheels. The vehicle can be, e.g., a bus, refuse vehicle, freight truck, construction vehicle, heavy equipment, military vehicle or tractor. The vehicle can also be a train, aircraft, watercraft, submarine or spacecraft.

[0037] The term "activation" refers to the treatment of adsorption materials (e.g., metal organic framework particles) in a manner to increase their storage capacity. Typically, the treatment results in removal of contaminants (e.g., water, non-aqueous solvent, sulfur compounds and higher hydrocarbons) from adsorption sites in order to increase the capacity of the materials for their intended purpose.

[0038] The term "adsorbent material" refers to a material (e.g., adsorbent particles) that can adhere gas molecules within its structure for subsequent use in an application. Specific materials include but are not limited to metal organic framework, activated alumina, silica gel, activated carbon, molecular sieve carbon, zeolites (e.g., molecular sieve zeolites), polymers, resins and clays.

[0039] The term "particles" when referring to adsorbent materials such as metal organic framework refers to multiparticulates of the material having any suitable size such as .0001 mm to about 50 mm or 1 mm to 20 mm. The morphology of the particles may be crystalline, semi- crystalline, or amorphous. The term also encompasses powders and particles down to 1 nm. The size ranges disclosed herein can be mean or median size.

[0040] The term "monolith" when referring to absorbent materials refers to a single block of the material. The single block can be in the form of, e.g., a brick, a disk or a rod and can contain channels for increased gas flow/distribution. In certain embodiments, multiple monoliths can be arranged together to form a desired shape.

[0041] The term "fluidly connected" refers to two or more components that are arranged in such a manner that a fluid (e.g., a gas) can travel from one component to another component either directly or indirectly (e.g., through other components or a series of connectors).

[0042] The term "freely settled density" or "bulk density" is determined by measuring the volume of a known mass of particles. The measurement can be determined using the procedures described in Method I or Method II of the United States Pharmacopeia 26, section <616>, hereby incorporated by reference.

[0043] The term "tapped density" is determined by measuring the volume of a known mass of particles after agitating the materials or container or using any of the filling techniques disclosed herein. The measurement can be determined by modifying procedures described in Method I or Method II of the United States Pharmacopeia 26, section <616>, hereby incorporated by reference. The procedures therein can be modified to provide a "tapped density" after any physical manipulation of the container and /or particles, e.g., after vibrating the container or using the filling techniques as disclosed herein. The measurement can also be determined using modification of DIN 787-11 (ASTM B527).

BRIEF DESCRIPTION OF THE DRAWINGS

[0044] The present disclosure is illustrated by way of example, and not by way of limitation, in the figures of the accompanying drawings in which like references indicate similar elements, in which:

[0045] Figure 1 depicts an adsorbed gas containment system according to an embodiment of the disclosure;

[0046] Figure 2A illustrates a process flow for a capacity test performed during vehicle operation according to an embodiment of the disclosure;

[0047] Figure 2B illustrates a process flow for a capacity test performed during vehicle fueling according to an embodiment of the disclosure;

[0048] Figure 3 is a block diagram illustrating a method of servicing an adsorbed gas containment system according to an embodiment of the disclosure;

[0049] Figure 4A depicts a multiple container system in a first state according to an embodiment of the disclosure; [0050] Figure 4B depicts a multiple container system in a second state according to an embodiment of the disclosure;

[0051] Figure 4C depicts a multiple container system in a third state according to an embodiment of the disclosure;

[0052] Figure 5 is a block diagram illustrating a method of adsorbing/desorbing gas onto adsorbent particles according to an embodiment of the disclosure;

[0053] Figure 6A is a plot showing aging of a zinc-based metal organic framework under a first controlled pressurization rate according to an embodiment of the disclosure; and

[0054] Figure 6B is a comparative plot showing aging of a zinc-based metal organic framework under a second controlled pressurization rate according to an embodiment of the disclosure.

DETAILED DESCRIPTION

[0055] The present invention has been described with reference to specific exemplary embodiments thereof. It will, however, be evident that various modifications and changes may be made thereto without departing from the broader scope of the embodiments of the invention as set for in the appended claims. The specification and drawings are, accordingly, to be regarded in an illustrative rather than a restrictive sense.

DETERMINING ADSORBENT PARTICLE CAPACITY

[0056] Over time, adsorbent particles may lose capacity after multiple pressurization and depressurization cycles. Due to this loss of capacity, a machine that is powered by these systems (e.g., a vehicle) will show a decrease in run time per fill-up which results in overall inefficiencies of the system. For vehicles, this may lead to decreased range for subsequent fill-ups.

[0057] By virtue of the present disclosure, there is provided a system and method to determine the change in capacity of an adsorbent containment system over time. There are also provided methods to service the systems, e.g., upon indication by a system component that service is due, or by servicing at predetermined intervals.

[0058] On one embodiment, the disclosure is directed to an adsorbed gas containment system comprising an adsorbed gas container at least partially filled with adsorbent particles; and an analytical system to measure the containment system capacity, the analytical system having communication capability, e.g., with a display. The display can be a simple indicator (e.g., a flashing or constant light) or provide text as to the system capacity. The text can be a code, a numerical value or a simple message in the appropriate language.

[0059] Depicted in Figure 1 is an illustrative embodiment of an adsorbed gas containment system 100 which comprises a container 101 having adsorbent particles 102 disposed therein. An analytical system 103 is connected to the container in order to measure the capacity of the container. The analytical system has communication capability with an on- board or off-board display 104. In order to increase the capacity of the adsorbent particles, the containment system is equipped with a gas line 105 to introduce an activation gas and a second line 106 to have the activation gas vent from the system. The containment system also has a fuel gas line 107 to fluidly connect to a vehicle engine 108. In some embodiments, one or more sensors 109 may be used to measure gas temperature, gas pressure, or other suitable parameters. The one or more sensors 109 may be operatively coupled to the analytical system 103.

[0060] The display 104 can be integrated on a vehicle that comprises the adsorbed gas containment system 100. Alternatively, the analytical system 103 is capable of having

communication with a display external to a vehicle that incorporates the absorbed gas containment system 100. For example, a vehicle can be taken to a service station and communicatively coupled to a diagnostic system.

[0061] The analytical system 103 can also provide communication with using any other methods to provide information, e.g., via a printer or audio device.

[0062] In certain embodiments, the analytical system 103 indicates that the containment system capacity is equal to or below a predetermined level indicative of the need for activation of the adsorbent particles.

[0063] The analytical system 103 may measure the containment system capacity during fill or during operation of a vehicle.

[0064] During fill, the analytical system 103 may utilize an algorithm that measures system capacity by factoring the system pressure before fill and the system pressure after fill. The algorithm may further factor the known capacity of the system and the amount of gas delivered during fill. The algorithm may further factor the containment system temperature. The analytical system may execute the algorithm using a processing device, and the algorithm may be stored in a memory that is communicatively coupled to the processing device.

[0065] During operation, the analytical system 103 may contain an algorithm that measures system capacity by factoring the mass of gas delivered to the engine and the system pressure change. The algorithm may further factor the containment system temperature. The algorithm may also measure system capacity by factoring the total gas mass in the container and the fuel mass flow rate. The fuel mass flow rate may be obtained by a diagnostic system such as a vehicle computer. In one embodiment, the analytical system 103 indicates a loss of capacity when the calculated mass of delivered fuel is more than the integrated mass, e.g., as provided by a vehicle computer. The calculated mass of delivered fuel can be measured by the mass of fuel in the container at start of integration minus the mass of fuel in the container at the end of integration. Figures 2A and 2B illustrate process flow 200 and process flow 250, respectively. Process flows 200 and 250 correspond, respectively, to illustrative capacity tests performed during vehicle operation and vehicle fueling.

[0066] When the containment system is serviced, the adsorbent particles are activated, e.g., to remove water and/or contaminants. A mechanism, e.g., a sensor, can indicate the amount of moisture in the system during activation of the particles. In one embodiment, the sensor indicates that the moisture level is equal to or below a predetermined level indicative that activation of the adsorbent particles is complete.

[0067] The containment system may comprise a one or more gas line in fluid communication with the container through an orifice such as a regulation device. The gas line can be configured to introduce an activation gas into the container. The containment system may also comprise a second gas line in fluid communication with the container through a second orifice, wherein the gas line is configured to release an activation gas from the container. Alternatively, the containment system can be configured to introduce and release the activation gas from the same line.

[0068] The service of the adsorbent material to increase capacity may comprise activating the adsorbent particles at a predetermined time interval or at a time when the analytical system 103 indicates that the containment system capacity is equal to or below a predetermined level.

[0069] In one embodiment, the service of the adsorbent material can be performed at an adsorbed gas fill station. For example, a vehicle or multiple vehicles may be filled simultaneously (e.g., overnight) from a single or multiple sources. The fill stations can have activation or reactivation capability designed into the hardware so that the activation or reactivation can be performed instead of, or prior to a fill. Incorporating this feature into a filling station alleviates the need for a separate activation or reactivation station. The present disclosure encompasses all methods and systems directed to this embodiment.

[0070] Figure 3 is a block diagram illustrating a method 300 of servicing an adsorbed gas containment system (e.g., the adsorbed gas containment system 100) according to an embodiment of the disclosure. At block 310, an analytical system of a vehicle (e.g., the analytical system 103) determines a time (either during operation of the vehicle or during fueling/re-fueling of the vehicle) at which a capacity of the adsorbed gas containment system of the vehicle is at or below a predetermined level. At block 320, the adsorbed gas containment system activates adsorbent particles at the determined time by subjecting the adsorbent particles to one or more conditions. In some embodiments, the conditions include one or more of above ambient temperature, vacuum, an inert gas flow, or a combination thereof.

MULTI-CONTAINER SYSTEMS

[0071] The present disclosure is further directed to systems and methods to provide gas to an internal combustion engine or a fuel cell by utilizing multiple adsorbed gas containers. The systems and methods can be used, e.g., during periods of depressurization or at times of increased energy requirements.

[0072] By virtue of the disclosure, increased efficiency and performance of compressed gas powered vehicles may obtained.

[0073] In certain embodiments, the present disclosure is directed to an adsorbed gas fuel system comprising an internal combustion engine or fuel cell; a first adsorbed gas container fluidly connected to the internal combustion engine, the adsorbed gas container containing adsorbent particles; a compressor fluidly connected to the internal combustion engine and the first adsorbed gas container, the compressor adapted to remove gas from the first adsorbed gas container; and a second adsorbed gas container fluidly connected to the internal combustion engine and fluidly connected (or optionally fluidly connected) to the first adsorbed gas container, the second adsorbed gas container containing adsorbent particles.

[0074] In one embodiment, the second adsorbed gas container is adapted to supply a gas to the internal combustion engine or fuel cell when the pressure of the first adsorbed gas container is at or below a predetermined level of reduced pressure.

[0075] In other embodiment, the second adsorbed gas container is adapted to supply a gas to the internal combustion engine when the fuel requirements of the engine are at or above a

predetermined level.

[0076] In certain embodiments, some or all of the containers are fluidly connected to the engine while bypassing the other containers (in parallel). In other embodiments, some or all of subsequent containers are fluidly connected to other containers (in series) in a manner to provide increased gas flow to the engine at times of low pressure.

[0077] In other embodiments, some or all of containers are each individually connected to the engine in both series and parallel. In such embodiments, valves can be opened or closed in order to have (i) a container bypass another container to provide gas to an engine (ii) provide fuel to the engine through another container without bypassing another container or (iii) providing a portion of fuel to an engine in series (through another container) and in parallel (bypassing another container).

[0078] In embodiments with containers connected in series, gas from one container sweeps through the adsorbent material of another container. This may result in the desorption of contaminant materials (e.g., moisture or hydrocarbons) from the absorbent material being subject to the gas flow from the other container.

[0079] In one embodiment, the adsorbed gas fuel system as disclosed herein comprises a third adsorbed gas container fluidly connected to the internal combustion engine or fuel cell and fluidly connected (or optionally fluidly connected) to the first and/or second adsorbed gas containers, the third adsorbed gas container containing adsorbent particles. The third adsorbed gas container can be adapted to supply a gas to the internal combustion engine or fuel cell when the pressure of the first or second adsorbed gas container is at or below a predetermined level of reduced pressure. In another embodiment, the third adsorbed gas container may be adapted to supply a gas to the internal combustion engine or fuel cell when the fuel requirements of the engine or fuel cell are at or above a predetermined level.

[0080] In one embodiment, the second adsorbed gas container is adapted to supply a gas to the internal combustion engine or fuel cell when the pressure of the first adsorbed gas container is, e.g., at or below 90% of filling capacity, at or below 80% of filling capacity, at or below 70% of filling capacity, at or below 60% of filling capacity, at or below 50% of filling capacity, at or below 40% of filling capacity, at or below 30% of filling capacity, at or below 20% of filling capacity, at or below 10% of filling capacity or at or below 5% of filling capacity.

[0081] In other embodiments, the third adsorbed gas container is adapted to supply a gas to the internal combustion engine when the pressure of the first adsorbed gas container is at or below 90% of filling capacity, at or below 80% of filling capacity, at or below 70% of filling capacity, at or below 60% of filling capacity, at or below 50% of filling capacity, at or below 40% of filling capacity, at or below 30% of filling capacity, at or below 20% of filling capacity, at or below 10% of filling capacity or at or below 5% of filling capacity.

[0082] In an embodiment of the disclosure, the first gas container is adapted to supply gas to the internal combustion engine or fuel cell simultaneously with the second gas container. In other embodiments, the first gas container is adapted to not supply gas to the internal combustion engine simultaneously with the second gas container.

[0083] In another embodiment of the disclosure, the third gas container is adapted to supply gas to the internal combustion engine or fuel cell simultaneously with the first or second gas container. In other embodiments, the third gas container is adapted to not supply gas to the internal combustion engine or fuel cell simultaneously with the first or second gas container.

[0084] Alternatively, in embodiments with a compressor, the compressor is adapted to aid the first gas container to supply gas to the internal combustion engine or fuel cell. The compressor can also aid one or more additional containers to supply gas to the internal combustion engine or fuel cell. There can also be multiple compressors, each dedicated to one container, each dedicated to multiple containers, or multiple compressors dedicated to a single container.

[0085] In one embodiment, the system further comprises a second compressor fluidly connected to the internal combustion engine or fuel cell and the second adsorbed gas container. Alternatively, the system may comprise a second compressor fluidly connected to the internal combustion engine or fuel cell and the second adsorbed gas container and a third compressor fluidly connected to the internal combustion engine or fuel cell and the second adsorbed gas container.

[0086] In one embodiment, the system further comprises a control system to modulate the supply pressure (P _e ) to the internal combustion engine or fuel cell. There can also be in certain embodiments a fuel injector in fluid connection between the engine or fuel cell and the first and second adsorbed gas containers.

[0087] In embodiments with a compressor, the compressor may be adapted to remove gas from the first adsorbed gas container when the container pressure is about 150 psi or less when the engine is running, about 125 psi or less when the engine is running, about 100 psi or less when the engine is running, about 75 psi or less when the engine is running, about 50 psi or less when the engine is running, or about 25 psi or less when the engine is running.

[0088] Alternatively, the second adsorbed gas container is adapted to supply gas to the internal combustion engine or fuel cell when the container pressure of the first adsorbed gas container is about 150 psi or less when the engine is running, about 125 psi or less when the engine is running, about 100 psi or less when the engine is running, about 75 psi or less when the engine is running, about 50 psi or less when the engine is running, about 25 psi or less when the engine is running, about 15 psi or less when the engine is running, about 10 psi or less when the engine is running or about 5 psi or less when the engine is running.

[0089] In further embodiments, a third adsorbed gas container is adapted to supply gas to the internal combustion engine or fuel cell when the container pressure of the first or second adsorbed gas container is about 150 psi or less when the engine is running, about 125 psi or less when the engine is running, about 100 psi or less when the engine is running, about 75 psi or less when the engine is running, about 50 psi or less when the engine is running, about 25 psi or less when the engine is running, about 15 psi or less when the engine is running, about 10 psi or less when the engine is running or about 5 psi or less when the engine is running.

[0090] Alternatively, the system may be adapted to maintain the pressure of compressed gas at the engine at about 10 psi or greater when the engine is running, about 25 psi or greater the engine is running, at about 50 psi or greater when the engine is running, about 75 psi or greater the engine is running, at about 100 psi or greater when the engine is running, about 150 psi or greater the engine is running, or about 200 psi or greater when the engine is running.

[0091] The system may be adapted to maintain the pressure of compressed gas at the engine at from about 10 psi to about 5,000 psi when the engine is running, from about 25 psi to about 4,000 psi when the engine is running, from about 50 psi to about 4,000 psi when the engine is running, or from about 100 psi to about 3,000 psi when the engine is running.

[0092] The disclosed fuel systems (also referred to herein as "adsorbed gas systems", "adsorbed gas fuel systems", and "adsorbed gas containment systems") may allow for at least a 70%, at least an 80%, or at least a 90% utilization of the adsorbed gas capacity of a filled first adsorbed gas container.

[0093] In one embodiment, a control system modulates the supply pressure to the internal combustion engine based on a parameter selected from the group consisting of storage system pressure (P _s ), storage system temperature (T _s ) of the first and/or second containers and P _e .

[0094] In other embodiments, the control system modulates the supply pressure to the internal combustion engine based on P _s and T _s of the first and/or second containers.

[0095] Alternatively, the control system utilizes P _e as a direct feedback signal for

controllability.

[0096] The system of the present disclosure can be used in dedicated adsorbed gas vehicles or hybrid vehicles that also utilize another fuel such as gasoline and/or electricity.

[0097] The fuel system of the disclosure may also comprise a gas fill line fluidly connected to the first adsorbed gas container, the second adsorbed gas container, and any additional containers. There can be one line for multiple containers or a dedicated line for each container.

[0098] Figures 4A-4C depict various states (Cases A-C) of a system 400 according to an embodiment of the disclosure. The system 400 includes a first adsorbed gas container 401 (or tank 401 as illustrated) and a second adsorbed gas container 402 (or tank 402 as illustrated), each fluidly connected to an engine 403. The first container 401 has a first line 404 to connect to the engine 403 in parallel depending on the opening or closing of valve 405B. A second line 406 connects the first container 401 to the second container to supply the engine 403 in series depending on the opening or closing of valves 405B-405C. Also shown are a regulator device 407 and a compressor 408. In some embodiments, more or less valves, regulators, and/or compressors may be present in system 400.

[0099] Figure 4A illustrates Case A, in which only container 402 supplies the engine 403 as valve 405 A and valve 405B are closed (e.g., with closed valves indicated by shading). Figure 4B illustrates Case B, in which container 401 and container 402 supply the engine 403 only in series as valve 405A is closed. Figure 4C illustrates Case C, in which container 401 supplies the engine 403 while bypassing container 402 as valve 405B and valve 405C are closed. Container 402 does not supply the engine 403 in Case C when valve 405B and valve 405C are closed.

[0100] Exemplary parameters for each of Cases A, B and C are set forth below in Table 1.

Table 1 : Parameters at Different States for Two-Container Fuel System

ADSORPTION AND DESORPTION EMBODIMENTS

[0101] The present disclosure which is further directed in certain embodiments to a method of adsorbing a gas onto adsorption particles comprising adsorbing gas onto adsorption particles at a sufficiently reduced rate such that the capacity of the particles is maintained at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 95% or at least about 99% over multiple cycles (e.g., a period of 25 cycles, 100 cycles, 250 cycles, 500 cycles, 750 cycles, 1,000 cycles, 1,250 cycles, 1,500 cycles, 1,750 cycles or 2,000 cycles.

[0102] In certain embodiments, the method comprises adsorbing gas onto adsorption particles at a sufficiently reduced rate such that the capacity of the particles is maintained at least about 75% over a period of 100 cycles, 250 cycles, 500 cycles, 750 cycles, 1,000 cycles, 1,250 cycles, 1,500 cycles, 1,750 cycles or 2,000 cycles.

[0103] In certain embodiments, the method comprises adsorbing gas onto adsorption particles at a sufficiently reduced rate such that the capacity of the particles is maintained at least about 85% over a period of 100 cycles, 250 cycles, 500 cycles, 750 cycles, 1,000 cycles, 1,250 cycles, 1,500 cycles, 1,750 cycles or 2,000 cycles.

[0104] In certain embodiments, the method comprises adsorbing gas onto adsorption particles at a sufficiently reduced rate such that the capacity of the particles is maintained at least about 90% over a period of 100 cycles, 250 cycles, 500 cycles, 750 cycles, 1,000 cycles, 1,250 cycles, 1,500 cycles, 1,750 cycles or 2,000 cycles.

[0105] In certain embodiments, the method comprises adsorbing gas onto adsorption particles at a sufficiently reduced rate such that the capacity of the particles is maintained at least about 92% over a period of 100 cycles, 250 cycles, 500 cycles, 750 cycles, 1,000 cycles, 1,250 cycles, 1,500 cycles, 1,750 cycles or 2,000 cycles.

[0106] In certain embodiments, the method comprises adsorbing gas onto adsorption particles at a sufficiently reduced rate such that the capacity of the particles is maintained at least about 95% over a period of 100 cycles, 250 cycles, 500 cycles, 750 cycles, 1,000 cycles, 1,250 cycles, 1,500 cycles, 1,750 cycles or 2,000 cycles.

[0107] In certain embodiments, the method comprises adsorbing gas onto adsorption particles at a sufficiently reduced rate such that the capacity of the particles is maintained at least about 97% over a period of 100 cycles, 250 cycles, 500 cycles, 750 cycles, 1,000 cycles, 1,250 cycles, 1,500 cycles, 1,750 cycles or 2,000 cycles.

[0108] In certain embodiments, the method comprises adsorbing gas onto adsorption particles at a sufficiently reduced rate such that the capacity of the particles is maintained at least about 99% over a period of 100 cycles, 250 cycles, 500 cycles, 750 cycles, 1,000 cycles, 1,250 cycles, 1,500 cycles, 1,750 cycles or 2,000 cycles.

[0109] In one embodiment, the time to fill the container is at least about 60 second, at least about 90 seconds, at least about 120 seconds, at least about 150 seconds, at least about 180 seconds, at least about 210, seconds at least about 240 seconds, at least about 270 seconds or at least about 300 seconds.

[0110] In other embodiments, the time to fill the container is from about 60 second to about 600 seconds, from about 90 seconds to about 500 seconds or from about 120 seconds to about 300 seconds.

[0111] Certain embodiments are directed to a method of desorbing a gas from adsorption particles comprising desorbing gas from adsorption particles at a sufficiently reduced rate such that the capacity of the particles is maintained at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 95% or at least about 99% over multiple cycles (e.g., a period of 25 cycles, 100 cycles, 250 cycles, 500 cycles, 750 cycles, 1,000 cycles, 1,250 cycles, 1,500 cycles, 1,750 cycles or 2,000 cycles.

[0112] In certain embodiments, the method comprises desorbing gas from adsorption particles at a sufficiently reduced rate such that the capacity of the particles is maintained at least about 75% over a period of 100 cycles, 250 cycles, 500 cycles, 750 cycles, 1,000 cycles, 1,250 cycles, 1,500 cycles, 1,750 cycles or 2,000 cycles.

[0113] In certain embodiments, the method comprises desorbing gas from adsorption particles at a sufficiently reduced rate such that the capacity of the particles is maintained at least about 85% over a period of 100 cycles, 250 cycles, 500 cycles, 750 cycles, 1,000 cycles, 1,250 cycles, 1,500 cycles, 1,750 cycles or 2,000 cycles.

[0114] In certain embodiments, the method comprises desorbing gas from adsorption particles at a sufficiently reduced rate such that the capacity of the particles is maintained at least about 90% over a period of 100 cycles, 250 cycles, 500 cycles, 750 cycles, 1,000 cycles, 1,250 cycles, 1,500 cycles, 1,750 cycles or 2,000 cycles.

[0115] In certain embodiments, the method comprises desorbing gas from adsorption particles at a sufficiently reduced rate such that the capacity of the particles is maintained at least about 92% over a period of 100 cycles, 250 cycles, 500 cycles, 750 cycles, 1,000 cycles, 1,250 cycles, 1,500 cycles, 1,750 cycles or 2,000 cycles.

[0116] In certain embodiments, the method comprises desorbing gas from adsorption particles at a sufficiently reduced rate such that the capacity of the particles is maintained at least about 95% over a period of 100 cycles, 250 cycles, 500 cycles, 750 cycles, 1,000 cycles, 1,250 cycles, 1,500 cycles, 1,750 cycles or 2,000 cycles.

[0117] In certain embodiments, the method comprises desorbing gas from adsorption particles at a sufficiently reduced rate such that the capacity of the particles is maintained at least about 97% over a period of 100 cycles, 250 cycles, 500 cycles, 750 cycles, 1,000 cycles, 1,250 cycles, 1,500 cycles, 1,750 cycles or 2,000 cycles.

[0118] In certain embodiments, the method comprises desorbing gas from adsorption particles at a sufficiently reduced rate such that the capacity of the particles is maintained at least about 99% over a period of 100 cycles, 250 cycles, 500 cycles, 750 cycles, 1,000 cycles, 1,250 cycles, 1,500 cycles, 1,750 cycles or 2,000 cycles.

[0119] In one embodiment, the time to discharge the container is at least 180 seconds, at least 300 seconds, at least 450 seconds, at least 600 seconds, at least 60 minutes, at least 90 minutes, at least 180 minutes, at least 200 minutes, at least 300 minutes, at least 400 minutes, at least 500 minutes or at least 600 minutes.

[0120] In other embodiments, the time to discharge the container is from about 180 seconds to about 600 minutes, from about 600 seconds to about 500 minutes or about 90 minutes to about 400 minutes.

[0121] In one embodiment, the gas can be introduced into the container radially or axially. In another embodiment, the gas can be introduced into the container in plug flow fashion.

[0122] In the container, the points of fill and discharge can be in proximate locations on the container. The container can also comprise a gas line in fluid communication with the container through an orifice (e.g., a regulator device).

[0123] The adsorbed gas system utilized in the present disclosure can have a maximum fill pressure, e.g., of from about 100 psi to about 4,000 psi, from about 125 psi to about 2,000 psi, from about 150 psi to about 1,500 psi, from about 200 psi to 800 psi, from about 1,000 psi to about 2,000 psi or from about 150 psi to about 500 psi.

[0124] The adsorbed gas system utilized in the present disclosure can have a minimum fill pressure, e.g., of from about 5 psi to about 250 psi, from about 10 psi to about 150 psi, from about 15 psi to about 100 psi or from about 15 psi to about 60 psi.

[0125] In an additional embodiment, a vehicle computer can control the timing of gas entering into the container with adsorption materials and can track the loss of or maintenance of capacity over multiple cycles.

[0126] Figure 5 is a block diagram illustrating a method 500 of adsorbing/desorbing gas onto adsorbent particles according to an embodiment of the disclosure. At block 510, gas is adsorbed onto or desorbed from adsorbent particles at a sufficiently reduced rate such that a capacity of the particles is maintained at least about 75% over a period of 25 cycles, the adsorbent particles being disposed within a container suitable for adsorbed gas storage. [0127] Figure 6A is a plot 600 showing aging of a zinc-based metal organic framework, which indicates minimal aging impact with a 3 minute controlled rate of pressurization and corrected to 73°F (room temperature). In contrast, Figure 6B is a plot 650 showing aging of the same system with a 30-50 second controlled rate of pressurization, showing a delta loss of 0.75 liters/cycle (overall 17% decline).

GENERAL SYSTEM EMBODIMENTS

[0128] The disclosed methods and systems may comprise containers such as cylinders, tanks or any other container that is suitable for storing adsorbed gas. The container can be suitable for adsorption, containment, and/or transportation of natural gas, hydrocarbon gas (e.g., methane, ethane, butane, propane, pentane, hexane, isomers thereof and a combination thereof), air, oxygen, nitrogen, synthetic gas, hydrogen, carbon monoxide, carbon dioxide, helium, or any other gas, or combinations thereof that can be adsorbed in a container for a variety of uses. In certain embodiments, the container may be electrically grounded during filling for safety concerns. In certain embodiments, the container is adapted to contain a quantity of compressed gas to provide a range of operation for a vehicle of about 5 miles or more, of about 10 miles or more, of about 25 miles or more, of about 50 miles or more, of about 100 miles or more, or about 200 miles or more.

[0129] The containers disclosed herein can be suitable for use in a compressed gas vehicle (such as a road vehicle or an off-road vehicle) or in heavy equipment (such as construction equipment). The containers can also be used in stationary systems such as generators.

[0130] The vehicle can have, e.g., at least 2 wheels (e.g., a motorcycle or motorized scooter), at least 3 wheels (e.g., an all-terrain vehicle), at least 4 wheels (e.g., a passenger automobile), at least 6 wheels, at least 8 wheels, at least 10 wheels, at least 12 wheels, at least 14 wheels, at least 16 wheels or at least 18 wheels. The vehicle can be, e.g., a bus, refuse vehicle, freight truck, construction vehicle, or tractor.

[0131] The adsorption container of any embodiments described herein can have a capacity, e.g., of at least about 1 liter, at least about 5 liters, at least about 10 liters, at least about 50 liters, at least about 75 liters, at least about 100 liters, at least about 200 liters, or at least about 400 liters. In certain embodiments, a vehicle fuel system can include multiple containers (e.g., tanks), e.g., at least 2 containers, at least 4 containers, at least 6 containers or at least 8 containers. In certain embodiment, the fuel system can contain 2 containers, 3 containers, 4 containers, 5 containers, 6 containers, 7 containers, 8 containers, 9 containers, 10 containers, or more containers. [0132] When filled into the container, a ratio of a tapped density of the particles to a freely settled density of the particles can be greater than 1, e.g., at least about 1.1, at least about 1.2, at least about 1.5, at least about 1.7, at least about 2.0 or at least about 2.5.

[0133] The adsorbent material (e.g., particles) that may be utilized in the disclosed systems and methods can be metal organic framework, e.g., having a surface area of at least about 500 m ² /g, at least about 700 m ² /g, at least about 1,000 m ² /g, at least about 1,200 m ² /g, at least about 1,500 m ² /g, at least about 1,700 m ² /g, at least about 2,000 m ² /g, at least about 5,000 m ² /g or at least about 10,000 m ² /g.

[0134] The surface area of the material may be determined by the BET (Brunauer-Emmett- Teller) method according to DIN ISO 9277:2003-05 (which is a revised version of DIN 66131). The specific surface area is determined by a multipoint BET measurement in the relative pressure range from 0.05 - 0.3 p/po-

[0135] In certain embodiments the adsorbent material includes a zeolite. In certain

embodiments a chemical formula of the zeolite is of a form of M _x „[(A10 ₂ ) _x (Si0 ₂ ) _y ]-mH ₂ 0, where x, y, m, and n are integers greater than or equal to 0, and M is a metal selected from the group consisting of Na and K.

[0136] In other embodiments the adsorbent material is a zeolitic material in which the framework structure is composed of YO ₂ and X ₂ O ₃ , in which Y is a tetravalent element and X is a trivalent element. In one embodiment Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge, and combinations of two or more thereof. In one embodiment Y is selected from the group consisting of Si, Ti, Zr, and combinations of two or more thereof. In one embodiment Y is Si and/or Sn. In one embodiment Y is Si. In one embodiment X is selected from the group consisting of Al, B, In, Ga, and combinations of two or more thereof. In one embodiment X is selected from the group consisting of Al, B, In, and combinations of two or more thereof. In one embodiment X is Al and/or B. In one embodiment X is Al.

[0137] In certain embodiments, the metal organic framework particles may include a metal selected from the group consisting of Li, Mg, Ca, Sc, Y, Zr, V, Mn, Fe, Co, Ni, Cu, Zn, B, Al, Ti and a combination thereof. In certain embodiments, the metal organic framework particles include a metal selected from the group consisting of Al, Mg, Zn, Cu, Zr, and a combination thereof.

[0138] In certain embodiments, the bidentate organic linker has at least two atoms which are selected independently from the group consisting of oxygen, sulfur and nitrogen via which an organic compound can coordinate to the metal. These atoms can be part of the skeleton of the organic compound or be functional groups. In certain embodiments the metal organic framework particles include a moiety selected from the group consisting of a phenyl moiety, an imidazole moiety, an alkane moiety, an alkyne moiety, a pyridine moiety, a pyrazole moiety, an oxole moiety, and a combination thereof. In certain embodiments the metal organic framework particles include at least one moiety selected from the group consisting of fumaric acid, formic acid, 2- methylimidazole, and trimesic acid.

[0139] As functional groups through which the abovementioned coordinate bonds can be formed, mention may be made by way of example of, in particular: OH, SH, NH ₂ , NH(-R-H), N(R- H) ₂ , CH ₂ OH, CH ₂ SH, CH ₂ NH ₂ , CH ₂ NH(-R-H), CH ₂ N(-R-H) ₂ , -C0 ₂ H, COSH, -CS ₂ H, -N0 ₂ , - B(OH) ₂ , -SO ₃ H, -Si(OH) ₃ , -Ge(OH) ₃ , -Sn(OH) ₃ , -Si(SH) ₄ , -Ge(SH) ₄ , -Sn(SH) ₃ , -P0 ₃ H ₂ , -As0 ₃ H, - As0 ₄ H, -P(SH) ₃ , -As(SH) ₃ , -CH(RSH) ₂ , -C(RSH) ₃ , -CH(RNH ₂ ) ₂ , -C(RNH ₂ ) ₃ , -CH(ROH) ₂ , - C(ROH) ₃ -CH(RCN) ₂ , -C(RCN) ₃ , where R may be, for example, an alkylene group having 1 , 2, 3, 4 or 5 carbon atoms, for example a methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, tert-butylene or n-pentylene group, or an aryl group having 1 or 2 aromatic rings, for example 2 C rings, which may, if appropriate, be fused and may, independently of one another, be appropriately substituted by, in each case, at least one substituent and/or may, independently of one another, include, in each case, at least one heteroatom, for example N, O and/or S. In likewise embodiments, mention may be made of functional groups in which the abovementioned radical R is not present. In this regard, mention may be made of, inter alia, -CH(SH) ₂ , -C(SH) ₃ , -CH(NH ₂ ) ₂ , CH(NH(R-H)) ₂ , CH(N(R-H) ₂ ) ₂ , C(NH(R-H)) ₃ , C(N(R-H) ₂ ) ₃ , -C(NH ₂ ) ₃ , -CH(OH) ₂ , -C(OH) ₃ , - CH(CN) ₂ , -C(CN) ₃ .

[0140] The at least two functional groups can in principle be bound to any suitable organic compound as long as it is ensured that the organic compound including these functional groups is capable of forming the coordinate bond and of producing the framework.

[0141] The organic compounds which include the at least two functional groups are derived from a saturated or unsaturated aliphatic compound or an aromatic compound or a both aliphatic and aromatic compound.

[0142] The aliphatic compound or the aliphatic part of the both aliphatic and aromatic compound can be linear and/or branched and/or cyclic, with a plurality of rings per compound also being possible. The aliphatic compound or the aliphatic part of the both aliphatic and aromatic compound may include from 1 to 18, 1 to 14, 1 to 13, 1 to 12, 1 to 11, or 1 to 10 carbon atoms, for example 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. For example, certain embodiments may include, inter alia, methane, adamantane, acetylene, ethylene or butadiene.

[0143] The aromatic compound or the aromatic part of the both aromatic and aliphatic compound can have one or more rings, for example two, three, four or five rings, with the rings being able to be present separately from one another and/or at least two rings being able to be present in fused form. The aromatic compound or the aromatic part of the both aliphatic and aromatic compound particularly may have one, two, or three rings. Furthermore, each ring of the compound can include, independently of one another, at least one heteroatom such as N, O, S, B, P, and/or Si. The aromatic compound or the aromatic part of the both aromatic and aliphatic compound may include one or two C rings; in the case of two rings, they can be present either separately from one another or in fused form. Aromatic compounds of which particular mention may be made are benzene, naphthalene and/or biphenyl and/or bipyridyl and/or pyridyl.

[0144] The at least bidentate organic compound may be derived from a dicarboxylic, tricarboxylic or tetracarboxylic acid or a sulfur analogue thereof. Sulfur analogues are the functional groups -C(=0)SH and its tautomer and C(=S)SH, which can be used in place of one or more carboxylic acid groups.

[0145] For the purposes of the present disclosure, the term "derived" means that the at least bidentate organic compound can be present in partly deprotonated or completely deprotonated form in a metal organic framework subunit or metal organic framework-based material. Furthermore, the at least bidentate organic compound can include further substituents such as -OH, -NH ₂ , -OCH , - CH , -NH(CH ), -N(CH ) ₂ , -CN and halides. In certain embodiments, the at least bidentate organic compound may be an aliphatic or aromatic acyclic or cyclic hydrocarbon which has from 1 to 18 carbon atoms and, in addition, has exclusively at least two carboxy groups as functional groups.

[0146] For the purposes of the present disclosure, mention may be made by way of example of dicarboxylic acids, as may be used to realize any of the embodiments disclosed herein, such as oxalic acid, succinic acid, tartaric acid, 1,4-butanedicarboxylic acid, 1,4-butenedicarboxylic acid, 4- oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1 ,8- heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,3- pyridinedicarboxylic acid, pyridine-2, 3 -dicarboxylic acid, l,3-butadiene-l,4-dicarboxylic acid, 1 ,4- benzenedicarboxylic acid, p-benzenedicarboxylic acid, imidazole-2,4-dicarboxyolic acid, 2- methylquinoline-3,4-dicarboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3- dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4'-diaminophenylmethane-3,3'- dicarboxylic acid, quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid, diimidedicarboxylic acid, pyridine-2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran- 4,4-dicarboxylic acid, perylene-3,9-dicarboxylic acid, perylenedicarboxylic acid, Pluriol E 200- dicarboxylic acid, 3,6-dioxaoctanedicarboxylic acid, 3,5-cyclohexadiene-l ,2-dicarboxylic acid, octadicarboxylic acid, pentane-3,3-dicarboxylic acid, 4,4' -diamino-l , l '-biphenyl-3, 3 '-dicarboxylic acid, 4,4' -diaminobiphenyl-3,3' -dicarboxylic acid, benzidine-3,3'-dicarboxylic acid, 1,4- bis(phenylamino)benzene-2,5-dicarboxylic acid, Ι,Γ-binaphthyldicarboxylic acid, 7-chloro-8- methylquinoline-2,3-dicarboxylic acid, l-anilinoanthraquinone-2,4' -dicarboxylic acid,

polytetrahydrofuran-250-dicarboxylic acid, 1 ,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3,8-dicarboxylic acid, l-(4-carboxy)phenyl-3-(4-chloro)phenylpyrazoline- 4,5-dicarboxylic acid, l,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, phenylindane- dicarboxylic acid, l,3-dibenzyl-2-oxoimidazolidine-4,5-dicarboxylic acid, 1,4- cyclohexanedicarboxylic acid, naphthalene- 1,8 -dicarboxylic acid, 2-benzoylbenzene-l,3- dicarboxylic acid, l,3-dibenzyl-2-oxoimidazolidine-4,5-cis-dicarboxylic acid, 2,2'-biquinoline-4,4'- dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, hydroxybenzophenonedicarboxylic acid, Pluriol E 300-dicarboxylic acid, Pluriol E 400- dicarboxylic acid, Pluriol E 600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3- pyrazinedicarboxylic acid, 5,6-dimethyl-2,3-pyrazinedicarboxylic acid, (bis(4-aminophenyl) ether)diimidedicarboxylic acid, 4,4'-diaminodiphenylmethanediimidedicarboxylic acid, (bis(4- aminophenyl) sulfone)diimidedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6- naphthalenedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 8-methoxy-2,3-naphthalenedicarboxylic acid, 8-nitro-2,3- naphthalenecarboxylic acid, 8-sulfo-2,3-naphthalenedicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2',3'-diphenyl-p-terphenyl-4,4"-dicarboxylic acid, (diphenyl ether)-4,4' -dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4(lH)-oxothiochromene-2,8-dicarboxylic acid, 5-tert-butyl-l,3- benzenedicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 4- cyclohexene-l,2-dicarboxylic acid, hexatriacontanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptadicarboxylic acid, 5-hydroxy-l,3-benzenedicarboxylic acid, 2,5-dihydroxy-l,4- dicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, l-nonene-6,9- dicarboxylic acid, eicosenedicarboxylic acid, 4,4' -dihydroxydiphenylmethane-3,3' -dicarboxylic acid, l-amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2,3-dicar boxylic acid, 2,5- pyridinedicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,9-dichlorofluorubin-4,l l- dicarboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone- 2 ',5 '-dicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 1- methylpyrrole-3,4-dicarboxylic acid, l-benzyl-lH-pyrrole-3,4-dicarboxylic acid, anthraquinone- 1,5-dicarboxylic acid, 3,5-pyrazoledicarboxylic acid, 2-nitrobenzene-l,4-dicarboxylic acid, heptane- 1,7-dicarboxylic acid, cyclobutane- 1,1 -dicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 5,6-dehydronorbornane-2,3-dicarboxylic acid, 5-ethyl-2,3-pyridinedicarboxylic acid or camphordicarboxylic acid, tricarboxylic acids such as 2-hydroxy-l,2,3-propanetricarboxylic acid, 7- chloro-2,3,8-quinolinetricarboxylic acid, 1,2,3-, 1,2,4-benzenetricarboxylic acid, 1,2,4- butanetricarboxylic acid, 2-phosphono-l,2,4-butanetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, l-hydroxy-l,2,3-propanetricarboxylic acid, 4,5-dihydro-4,5-dioxo-lH-pyrrolo[2,3- F]quinoline-2,7,9-tricarboxylic acid, 5-acetyl-3-amino-6-methylbenzene-l,2,4-tricarboxylic acid, 3- amino-5-benzoyl-6-methylbenzene-l,2,4-tricarboxylic acid, 1,2,3-propanetricarboxylic acid or aurintricarboxylic acid, or tetracarboxylic acids such as l,l-dioxidoperylo[l, 12-BCD]thiophene- 3,4,9, 10-tetracarboxylic acid, perylenetetracarboxylic acids such as perylene-3,4,9,10- tetracarboxylic acid or (perylene l,12-sulfone)-3,4,9, 10-tetracarboxylic acid, butanetetracarboxylic acids such as 1,2,3,4-butanetetracarboxylic acid or meso-l,2,3,4-butanetetracarboxylic acid, decane- 2,4,6,8-tetracarboxylic acid, l,4,7,10, 13,16-hexaoxacyclooctadecane-2,3,l l,12-tetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,11,12-dodecanetetracarboxylic acid, 1,2,5,6- hexanetetracarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, 1,4,5, 8-naphthalenetetracarboxylic acid, 1,2,9,10-decanetetracarboxylic acid, benzophenonetetracarboxylic acid, 3,3',4,4'-benzo- phenonetetracarboxylic acid, tetrahydrofurantetracarboxylic acid or cyclopentanetetracarboxylic acids such as cyclopentane-l,2,3,4-tetracarboxylic acid.

[0147] Certain embodiments may use at least monosubstituted aromatic dicarboxylic, tricarboxylic or tetracarboxylic acids which have one, two, three, four or more rings and in which each of the rings can include at least one heteroatom, with two or more rings being able to include identical or different heteroatoms. For example, certain embodiments may use one -ring dicarboxylic acids, one -ring tricarboxylic acids, one-ring tetracarboxylic acids, two-ring dicarboxylic acids, two-ring tricarboxylic acids, two-ring tetracarboxylic acids, three-ring dicarboxylic acids, three -ring tricarboxylic acids, three-ring tetracarboxylic acids, four-ring dicarboxylic acids, four-ring tricarboxylic acids and/or four-ring tetracarboxylic acids. Suitable heteroatoms are, for example, N, O, S, B, and/or P. Suitable substituents which may be mentioned in this respect are, inter alia, -OH, a nitro group, an amino group or an alkyl or alkoxy group.

[0148] In certain embodiments, the linker may include a moiety selected from the group consisting of a phenyl moiety, an imidazole moiety, an alkane moiety, an alkyne moiety, a pyridine moiety, a pyrazole moiety, an oxole moiety and a combination thereof. In a particular embodiment, the linker may be a moiety selected from any of the moieties illustrated in Table 2.

Table 2: Linker Moieties

[0149] The metal organic framework particles can be in any form, such as, e.g., pellets, extrudates, beads, powders or any other defined or irregular shape. The particles can be any size, e.g., from about .0001 mm to about 10 mm, from about .001 mm to about 5 mm, from about .01 mm to about 3 mm, or from about .1 mm to about 1 mm.

[0150] In one embodiment, the containment system includes a container suitable for compressed/adsorbed gas storage having a capacity of at least 1 liter at least partially filled with metal organic framework particles such that a ratio of a tapped density of the particles to a freely settled density of the particles is at least 1.1. Still further embodiments are directed to vehicles including a containment system as disclosed herein. Other embodiments are directed to methods of manufacturing such vehicles by integrating a container as disclosed herein into a fuel system of a vehicle. The fuel system can be part of an assembly of a new vehicle or can be retrofitted into an existing vehicle.

[0151] In certain embodiments, the metal organic framework particles can be incorporated into a matrix material and thereafter introduced into a container. The matrix may be a plastic material in any suitable form such as a sheet which can be formed, e.g., by extrusion. The material can be optionally corrugated. The material can be rolled or otherwise manipulated and incorporated into a container. Prior to introduction into a container, the material can be bound by polymer fibers.

ACTIVATION OF PARTICLES

[0152] Certain embodiments are directed to a method of activating adsorbent particles (e.g., metal organic framework particles) including subjecting the adsorbent particles to conditions selected from the group consisting of above ambient temperature, heat, vacuum, an inert gas flow and a combination thereof, for a sufficient time to activate the particles.

[0153] In certain embodiments, the activation includes the removal of water molecules from the adsorption sites. In other embodiments, the activation includes the removal of non-aqueous solvent molecules from the adsorption sites that are residual from the manufacture of the particles. In still further embodiments, the activation includes the removal of sulfur compounds or higher hydrocarbons from the adsorption sites. In embodiments utilizing an inert gas purge in the activation process, a subsequent solvent recovery step is also contemplated. In certain

embodiments, the contaminants (e.g., water, non-aqueous solvents, sulfur compounds or higher hydrocarbons) are removed from the adsorption material at a molecular level.

[0154] In a particular embodiment, the activation includes the removal of water molecules from the surface area of the particles. After activation, the particles may have a moisture content of less than about 10%, less than about 8%, less than about 5%, less than about 3%, less than about 1%, less than about 0.8%, less than about 0.5%, less than about 0.3% or less than about 0.1% by weight of the particles. Alternatively, the available surface area of the adsorption material for adsorption of the intended gas is greater than about 80%, greater than about 85%, greater than about 90%, greater than about 95% or greater than about 98% of the accepted value (i.e., the theoretical surface area free of adsorbed contaminants). [0155] The activation can occur before or after the particles are filled into a container suitable for adsorbed gas storage. Alternatively, the particles may be removed and activated external to a container suitable. Activating particles outside of the container may be beneficial in certain circumstances as the container may have temperature limitations that may impede the activation process. The external process may also result in a shorter activation time due to the ability to apply a higher temperature to the particles outside of the tank.

[0156] Certain embodiments are directed to the activation of metal organic framework particles. The particles can be subject to a suitable temperature for removal of contaminants (e.g., water, nonaqueous solvents, sulfur compounds and higher hydrocarbons) from adsorption sites. The activation may include exposure of the metal organic framework particles to a temperature, e.g., above about 40°C, above about 60°C, above about 100°C, above about 150°C, above about 250°C, or above about 350°C. In other embodiments, the temperature may be between about 40°C and about 400°C, between about 60°C and about 250°C, between about 100°C and about 200°C, between about 60°C and about 200°C, between about 60°C and about 180°C, between about 60°C and about 170°C, between about 60°C and about 160°C, between about 150°C and about 200°C or between about 150°C and about 180°C.

[0157] The activation of particles may be subject to a vacuum in order to remove contaminants (e.g., water, non-aqueous solvents, sulfur compounds and higher hydrocarbons) from adsorption sites. The vacuum may be, e.g., from about 10% to about 80% below atmospheric pressure, from about 10% to about 50% below atmospheric pressure, from about 10% to about 20% below atmospheric pressure, from about 20% to about 30% below atmospheric pressure or from about 30% to about 40% below atmospheric pressure.

[0158] The activation of the particles can also include flowing inert gas through the material to remove contaminants (e.g., water, non-aqueous solvents, sulfur compounds and higher

hydrocarbons). The inert gas flow can include nitrogen or a noble gas. The total amount of inert gas used in the purge can be any suitable amount to activate the materials. In a particular embodiment, the amount of gas is at least the volume of a container holding the particles. In other embodiments, the amount of gas is at least 2 times the container volume or at least 3 times the container volume. The inert gas can be flowed through the materials for any suitable time, such as at least about 10 minutes, at least about 30 minutes, at least about 1 hour, at least about 6 hours, at least about 8 hours, at least about 16 hours, at least about 24 hours or at least about 48 hours.

Alternatively, the time can be from about 10 minutes to about 48 hours, from about 10 minutes to about 28 hours, from about 10 minutes to about 16 hours, from about 30 minutes to about 48 hours, from about 30 minutes to about 24 hours, from about 30 minutes to about 16 hours, from about 1 hour to about 48 hours, from about 1 hour to about 24 hours, from about 1 hour to about 16 hours, from about 10 minutes to about 1 hour, from about 30 minutes to about 1 hour, from about 2 hours to about 24 hours, or from about 4 hours to about 16 hours. In some embodiments, the time can be from at least about 5 minutes.

[0159] Any amount of adsorbent material (e.g., metal organic framework particles) may be activated according to the methods described herein, or a combination thereof. In a particular embodiment, the particles may be in an amount of at least about 1 kg, at least about 500 kg, from about 20 kg to about 500 kg, from about 50 kg to about 300 kg or from about 100 kg to about 200 kg. In another embodiment, the adsorbent material may be in an amount of at least about 1 g, at least about 500 g, from about 20 g to about 500 g, from about 50 g to about 300 g, from about 100 g to about 200 g, or greater than 500 g.

[0160] The activated particles can be at least partially filled into a container suitable for compressed gas storage, e.g., having a capacity of at least about 1 liter. The filling can optionally encompass any of the filling procedures disclosed herein. The filling of activated particles may also result in the tapped density of particles disclosed herein.

[0161] After the particles are filled into a suitable adsorption container, the activation can occur by placing the container in an oven. Alternatively, if the container is mounted onto a vehicle or machinery (e.g., a generator), a heat source internal to the vehicle or machinery can be used. For example, the heat source in a vehicle may be derived from the battery, engine, air conditioning unit, brake system, or a combination thereof. In alternative embodiments, the container at least partially filled with particles can be activated with an external heat source.

[0162] In certain embodiments, a microwave energy source may be utilized to provide microwave energy to heat and activate the particles. In some embodiments, the microwave energy source may be part of the container or located externally to the container. In some embodiments, more than one microwave energy source may be used. In some embodiments, one or more microwave energy sources may be utilized along with other energy sources to activate the particles.

[0163] In other embodiments, if the container is mounted onto a vehicle or machinery, a vacuum source internal or external to the vehicle or machinery can be used for activation. For example, the energy source in a vehicle for the internal vacuum may be derived from the battery, engine, the air conditioning unit, the brake system, or a combination thereof.

[0164] In embodiments wherein the container is mounted onto a vehicle or machinery, it may be necessary at a point in time after the initial activation to re-activate the particles. For instance, after one or more cycles wherein the container is filled with a compressed gas with subsequent release (e.g., upon running the vehicle), certain contaminants may remain on the adsorption sites. These contaminants may include sulfur compounds or higher hydrocarbons (e.g., C ₄ _6 hydrocarbons). The reactivation can include subjecting the particles in the container to heat, vacuum and/or inert gas flow for a sufficient time for reactivation. In one embodiment, the reactivation can occur at a service visit or can be performed at a standard fueling station. The reactivation can also include washing and/or extraction of the particles in the container with non-aqueous solvent or water.

[0165] The time period for the activation or reactivation of the particles can be determined by measuring the flow of water or non-aqueous solvent in a vacuum. In a certain embodiment, the flow is terminated when the water or solvent content is less than about 10%, less than about 8%, less than about 5%, less than about 3%, less than about 1%, less than about 0.8%, less than about 0.5%, less than about 0.3% or less than about 0.1% by weight of the particles.

[0166] In certain embodiments, the container can include a heating element in order to provide activation of the materials after filling. The energy for the heating element can be provided internally from the vehicle (e.g., from a battery, engine, air conditioning unit, brake system, or a combination thereof) or externally from the vehicle. Whether the activation is before or after filling, the container may be dried prior to the introduction of particles into the container. The container can be dried, e.g., with air, ethanol, heat or a combination thereof.

[0167] When the particles are activated outside of the container, it may be necessary to store and/or ship the particles prior to incorporation into an adsorption container. In certain

embodiments, the activated particles are stored in a plastic receptacle with an optional barrier layer between the receptacle and the particles. The barrier layer may include, e.g., one or more plastic layers.

[0168] When the particles are activated by an inert gas flow, the flow may be initiated at an inlet of the container and may be terminated at an outlet of the container at a different location than the inlet. In alternative embodiments, the inert gas flow is initiated and terminated at the same location on the container.

[0169] The inert gas flow may include the utilization of a single tube for introducing and removing the inert gas from the container. In such an embodiment, the tube may include an outer section with at least one opening to allow the inert gas to enter the container and an inner section without openings to allow for the inert gas to be removed from the container. In other

embodiments, the flow may include the utilization of a first tube for introducing the inert gas into the container and a second tube to remove the inert gas from the container.

[0170] Disclosure herein specifically directed to metal organic framework is also contemplated to be applicable to other adsorbent materials such as activated alumina, silica gel, activated carbon, molecular sieve carbon, zeolites (e.g., molecular sieve zeolites), polymers, resins and clays. [0171] Also, disclosure herein with respect to adsorbent particles is also contemplated to be applicable to monoliths of the material where applicable.

[0172] In the foregoing description, numerous specific details are set forth, such as specific materials, dimensions, processes parameters, etc., to provide a thorough understanding of the present invention. The particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments. The words "example" or "exemplary" are used herein to mean serving as an example, instance, or illustration. Any aspect or design described herein as "example" or "exemplary" is not necessarily to be construed as preferred or advantageous over other aspects or designs. Rather, use of the words "example" or "exemplary" is intended to present concepts in a concrete fashion. As used in this application, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or". That is, unless specified otherwise, or clear from context, "X includes A or B" is intended to mean any of the natural inclusive permutations. That is, if X includes A; X includes B; or X includes both A and B, then "X includes A or B" is satisfied under any of the foregoing instances. In addition, the articles "a" and "an" as used in this application and the appended claims should generally be construed to mean "one or more" unless specified otherwise or clear from context to be directed to a singular form.

[0173] Reference throughout this specification to "an embodiment", "certain embodiments", or "one embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the appearances of the phrase "an embodiment", "certain embodiments", or "one embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment, and such references mean "at least one".