WO2015123531A1 - Methods and systems for heating adsorbed gas systems - Google Patents

Abstract

Disclosed in certain embodiments are systems and methods for heating adsorbent particles and regulating amounts of adsorbed gas in adsorbed gas containers. Certain embodiments are directed to a method of heating adsorbent particles comprising subjecting adsorbent particles to heat produced by an electric current received from a regenerative brake system of a vehicle, the adsorbent particles having gas adsorbed thereon.

Description

METHODS AND SYSTEMS FOR HEATING ADSORBED GAS SYSTEMS

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority of United States Provisional Patent

Application No. 61/939,891, filed February 14, 2014, and United States Provisional Patent Application No. 61/939,896, filed February 14, 2014, both 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, that containing empty pores and channels, the size of which is 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, catalysis, luminescence and drug delivery. By way of example, metal organic framework can have (show) a specific surface area of up to 10,000 m²/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, 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 of maximizing the efficiency and utilization of gas adsorbed onto 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) and to minimize the time necessary to adsorb gas onto the materials during fill. 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 methods of subjecting adsorbent materials (e.g., metal organic framework) comprising adsorbed gas with heat.

[0008] 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.

[0009] It is an object of certain embodiments to provide containment systems suitable for adsorbed gas storage.

[0010] It is an object of certain embodiments to provide systems and methods to adsorb gas onto adsorption materials (e.g., metal organic framework).

[0011] It is an object of certain embodiments to provide systems and methods of adsorbing gas into a fuel system comprising multiple containers with adsorption materials (e.g., metal organic framework).

[0012] It is an object of certain embodiments to provide systems and methods to minimize the time needed to fill a gas into a container with adsorption materials (metal organic framework).

[0013] It is an object of certain embodiments to provide gas powered machines (e.g., vehicles, heavy equipment) that utilize the systems and methods disclosed herein.

[0014] The above objects and others may be met by the present disclosure, in which certain embodiments are directed to a method of heating adsorbent particles comprising subjecting adsorbent particles to heat produced by an electric current received from a regenerative brake system of a vehicle, the adsorbent particles having gas adsorbed thereon.

[0015] Certain embodiments are directed to a compressed gas vehicle comprising a regenerative brake system that produces an electric current to produce heat; and adsorbent particles in association with the heat.

[0016] Certain other embodiments are directed to a compressed gas vehicle comprising a regenerative shock system that produces an electric current to produce heat; and adsorbent particles in association with the heat. [0017] The above objects and others may be met by the present disclosure, in which certain embodiments are directed to a method for regulating the amount of gas in a series of adsorbed gas containers comprising applying heat to promote the desorption of gas from a first plurality of adsorption particles in a first container fluidly connected to an internal combustion engine or fuel cell; and adsorbing a gas onto a second plurality of adsorption particles in a second container concurrently while the first adsorption particles or first container are above ambient temperature, the second container fluidly connected to the internal combustion engine or fuel cell.

[0018] Certain other embodiments are directed to a method of preparing or method of operating the systems disclosed herein.

[0019] Certain other embodiments are directed to a vehicle utilizing the systems and methods disclosed herein.

[0020] 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 m²/g, at least about 700 m²/g, at least about 1 ,000 m²/g, at least about 1,200 m²/g, at least about 1,500 m²/g, at least about 1,700 m²/g, at least about 2,000 m²/g, at least about 5,000 m²/g, or at least about 15,000 m²/g.

[0021] 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.

[0022] In certain embodiments, the metal organic framework particles are in a form of pellets, extrudates, beads, monoliths, or any other defined or irregular shape.

[0023] In certain embodiments, the adsorbent particles comprise metal organic framework particles or activated charcoal.

[0024] In certain embodiments, the adsorbent particles are disposed within a container having a form of a tank, cyclindrical, toroidal, or rectanguloid.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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).

[0033] 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.

[0034] 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.

[0035] 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

[0036] 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:

[0037] Figure 1 depicts a regenerative brake system of the present disclosure with an external heater according to an embodiment of the disclosure;

[0038] Figure 2 depicts a regenerative brake system of the present disclosure with an internal heater according to an embodiment of the disclosure;

[0039] Figure 3 is a block diagram illustrating a method for heating adsorbent particles according to an embodiment of the disclosure;

[0040] Figure 4 depicts a system including three adsorbed gas containers according to an embodiment of the disclosure; and

[0041] Figure 5 is a block diagram illustrating a method for regulating an amount of gas in a series of adsorbed gas containers according to an embodiment of the disclosure.

DETAILED DESCRIPTION [0042] 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.

DESORPTION SYSTEMS

[0043] Some of the embodiments of the present disclosure are directed to systems and methods to promote the desorption of gas from adsorbent particles by subjecting the particles to heat generated by an electric current obtained from a regenerative brake system of a vehicle.

[0044] By virtue of the applied heat, desorption of gas particles is promoted, thus increasing the efficiency of compressed gas powered vehicles. The increased efficiency is the result, in part, of the utilization of gas that otherwise may not have been available due to the depressurization of the system.

[0045] The application of heat to absorption particles may also be used to activate the particles by promoting the desorption of contaminants from the particles. In one embodiment after heating, the particles have a moisture or solvent content of less than about 5%, less than about 4%, less than about 3%, less than about 2%, less than about 1%, less than about 0.5% or less than about 0.1 % by weight or the available capacity 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.

[0046] In one embodiment, the electric current is obtained from the application of the regenerative brakes, e.g., by brake pedal depression. The electric current in certain embodiments, generates an electric heater (e.g., a resistance heater) to produce heat. The heater can be in association with the adsorbed particles, i.e., in a proximity such that the heat provided by the heater results in an increased temperature of the particles.

[0047] In one embodiment, the particles are contained in a container suitable for adsorbed gas storage in a compressed gas vehicle and the heater is, e.g., external to the container, internal to the container, or both internal and external to the heater.

[0048] In certain embodiments, only a portion of the electric current generated by the regenerative brakes is utilized to heat the particles. The other portion may be diverted to other components of the vehicle such as to a battery or directly (bypassing the battery) to other electric components on a vehicle. In certain embodiments, the electric current (or a portion thereof) is directly provided by the regenerative brakes to heat the adsorption particles, thus bypassing a battery.

[0049] In certain embodiments, the portion of the electric current that generates the electric heater is determined by comparing a reference temperature of the adsorbent particles with an actual temperature of the adsorbent particles. In one embodiment there is a control algorithm that resides, e.g., on the engine computer or an external controller, the algorithm determining the delivered current to achieve a target temperature or change in temperature.

[0050] In embodiments of the disclosure, the adsorbent particles are subjected to heat such that there is a temperature increase, e.g., of at least about 5°C, at least about 5°C, at least about 5°C, at least about 5°C, at least about 10°C, at least about 25°C, at least about 50°C at least about 75°C, at least about 100°C, at least about 200°C, or at least about 300°C.

[0051] In certain embodiments, the adsorbent particles are subjected to a temperature between about 10°C and about 600°C, to a temperature between about 20°C and about 500°C, to a temperature between about 40°C and about 400°C, to a temperature between about 60°C and about 250°C, to a temperature between about 100°C and about 200°C, to a temperature between about 60°C and about 200°C, to a temperature between about 60°C and about 180°C, to a temperature between about 60°C and about 170°C, to a temperature between about 60°C and about 160°C, to a temperature between about 150°C and about 200°C or to a temperature between about 150°C and about 180°C.

[0052] The disclosed fuel systems (also referred to herein as "adsorbed gas systems", "adsorbed gas fuel systems", and "adsorbed gas containment systems") comprise activated adsorption particles (e.g., metal organic framework particles) by virtue of the heat provided by the regenerative brakes. The particles may also be subjected to conditions selected from the group comprising heat from another source, vacuum, an inert gas flow and a combination thereof, for a sufficient time to activate the particles.

[0053] In certain embodiments, the activation comprises the removal of water molecules from the adsorption sites. In other embodiments, the activation comprises 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 comprises 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. [0054] In a particular embodiment, the activation comprises 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 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 capacity 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).

[0055] Figure 1 depicts an embodiment of the disclosure which is a vehicle 100 having an engine 101, a transmission 102, and wheels 103. The vehicle further comprises an adsorbed gas container 104 (e.g., which contains adsorbent particles), and an external heater 105 that is supplied a current from a regenerative brake system 106. In some embodiments, the brake system 106 may be replaced with a regenerative shock system. In some embodiments, the vehicle 100 may include both the brake system 106 and a regenerative shock system (e.g., which also supplies current to the external heater 105).

[0056] Figure 2 depicts an embodiment of the disclosure which is a vehicle 200 having an engine 201, a transmission 202, and wheels 203. The vehicle further comprises an adsorbed gas container 204 and an internal heater 205 disposed therein that is supplied a current from a regenerative brake system 206. In some embodiments, the brake system 206 may be replaced with a regenerative shock system. In some embodiments, the vehicle 200 may include both the brake system 206 and a regenerative shock system (e.g., which also supplies current to the internal heater 205).

[0057] Figure 3 is a block diagram illustrating a method for heating adsorbent particles according to an embodiment of the disclosure. At block 310, adsorbent particles are heated by subjecting the adsorbent particles to heat produced by an electric current received from a regenerative brake system or a regenerative shock system of a vehicle.

[0058] In some embodiments, heating the adsorbent particles results in desorption of gas from the particles.

[0059] In some embodiments, heating the adsorbent particles results in activation of the particles.

[0060] In some embodiments, the vehicle is a compressed gas vehicle, and the adsorbent particles are in a container suitable for adsorbed gas storage in the compressed gas vehicle.

[0061] In some embodiments, the electric current is received in response to application of the regenerative brakes or a regenerative shock system. [0062] In some embodiments, the electric current causes an electric heater to produce heat, the heater being in association with the adsorbed particles.

[0063] In some embodiments, the electric heater is a resistance heater.

[0064] In some embodiments, the electric heater is external or internal to the container.

[0065] In some embodiments, the electric heater is internal and external to the container.

[0066] In some embodiments, a portion of the electric current causes the electric heater to produce heat.

[0067] In some embodiments, at least a portion of the electric current is generated by a source other than a battery. In some embodiments, the portion of the electric current is determined by comparing a reference temperature of the adsorbent particles with an actual temperature of the adsorbent particles. In some embodiments, a remaining portion of electric current is diverted to the battery or other automobile electric device.

[0068] In some embodiments, the method 300 further includes determining, using a control algorithm executed by a processing device, a magnitude of the current to achieve a target temperature or change in temperature. In some embodiments, the processing device is a processing device of an engine computer/controller or an external computer/controller, and wherein the control algorithm is stored in a memory of the engine computer or external controller, the memory being communicatively coupled to the processing device.

[0069] In some embodiments, application of the regenerative brakes occurs upon brake pedal depression.

REGULATING GAS IN A SERIES OF CONTAINERS

[0070] Additional embodiments of the present disclosure are directed to systems and methods to improve the efficiencies of filling a gas into a container with adsorption materials therein.

[0071] In order to maximize the utilization of gas adsorbed onto materials such as metal organic framework, it is often beneficial to heat the container or particles in order to promote the desorption of gas, thus maximizing the utilization of the gas (e.g., to power an engine).

[0072] However, promoting desorption with heat, may result in an empty or low pressurized container that is above ambient temperature (e.g., the temperature of the environment of the container or a vehicle that includes the container) that needs refilling in order to maintain an acceptable range of activity. When a container or adsorption particles are above ambient temperature, absorption of a gas therein is difficult requiring the necessity to wait until the container or particles cool before starting the adsorption process associated with filling the container. However, this is not an acceptable procedure as one may have to wait a considerable amount of time for the container or particles to cool prior to refilling.

[0073] This problem is met by the present disclosure by embodiments directed to a system and method of having multiple adsorption containers, such that when one container is heated to desorb the gas therein, a cooler container (e.g., at or below ambient temperature) is available to be utilized or refilled while the first container is in a cooling process.

[0074] In one embodiment, the disclosure is directed to a method of regulating the amount of gas in a series of adsorbed gas containers comprising applying heat to promote the desorption of gas from a first plurality of adsorption particles in a first container fluidly connected to an internal combustion engine or fuel cell; and adsorbing a gas onto a second plurality of adsorption particles in a second container concurrently while the first adsorption particles or first container are above ambient temperature, the second container fluidly connected to the internal combustion engine or fuel cell.

[0075] In another embodiment, the invention is directed to a method of regulating the amount of gas in a series of adsorbed gas containers comprising applying heat to promote the desorption of gas from a first plurality of adsorption particles in a first container fluidly connected to an internal combustion engine or fuel cell; and utilizing a gas from a second plurality of adsorption particles in a second container concurrently while the first adsorption particles or first container are above ambient temperature, the second container fluidly connected to the internal combustion engine or fuel cell.

[0076] This process can be utilized with multiple containers, e.g., 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more or 8 or more containers.

[0077] In one embodiment, the method further comprises applying heat to promote the desorption of gas from the second plurality of adsorption particles in the second container and then in certain embodiments, further comprises adsorbing a gas onto the first plurality of adsorption particles in the first container concurrently while the second adsorption particles or second container are above ambient temperature.

[0078] The method can also comprise a third plurality of adsorption particles in a third container. In such an embodiment, the method further comprises applying heat to promote the desorption of gas from the third plurality of adsorption particles in the third container. Such an embodiment can also comprise adsorbing a gas onto the first or second plurality of adsorption particles in the first or second container concurrently while the third adsorption particles or third container are above ambient temperature. [0079] The systems and methods may further comprise one or more compressors fluidly connected to the internal combustion engine or fuel cell and one or more of the adsorbed gas containers, the compressor adapted to remove gas from the adsorbed gas containers, e.g., at times of low pressure.

[0080] The heat can be applied to the container(s) externally, internally or a combination thereof. The heat can be derived from the engine, a battery, an external source, regenerative brakes, exhaust or any other heat source of a vehicle. In one embodiment, a current is generated that powers a resistant heater in association with the container or adsorption particles.

[0081] In one embodiment, the heat is applied to the first, second or additional adsorbed gas container when the pressure of the respective 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 another embodiment, the systems and methods allows for at least a 70%, at least an 80%, or at least a 90% utilization of the adsorbed gas capacity of a filled gas adsorption container.

[0083] The system and methods can utilize gas fill lines in fluid connection with the adsorbed gas container(s).

[0084] The system and methods 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.

[0085] In an additional embodiment, a vehicle computer can control the timing of when a container is at a suitable temperature to be refilled. The computer can have an indicator to show when a container can be filled or cannot be refilled. The computer can also prevent a gas line from being opened on a container that is not at a suitable temperature to be refilled or allow a gal line to be opened when a container is at a temperature to be refilled.

[0086] Figure 4 depicts an embodiment of the disclosure which includes a system 400 having a first adsorbed gas container 401, a second adsorbed gas container 402, and a third adsorbed gas container 403 each fluidly connected to an engine 404. The containers are equipped with radiant heaters 401A, 402A, and 403A, respectively, to promote desorption of gas. A compressor 406 is also included to promote the removal of gas from the containers at periods of low pressure. A computer 407 controls the timing of when a container is at a suitable temperature to be refilled or not to be refilled.

[0087] Figure 5 is a block diagram illustrating a method 500 for regulating an amount of gas in a series of adsorbed gas containers according to an embodiment of the disclosure. In some embodiments, the method 500 is performed by the system 400. At block 510, heat is applied (e.g., using radiant heater 401A under the control of the computer 407) to a first plurality of adsorption particles disposed within a first container (e.g., the first adsorbed gas container 401) to promote desorption of gas from the first plurality of adsorption particles, the first container being fluidly connected to an internal combustion engine (e.g., engine 404) or fuel cell. At block 520, gas is adsorbed onto a second plurality of adsorption particles (e.g., during a fill process) in a second container (e.g., the adsorbed gas container 402) concurrently while the first adsorption particles or first container are above ambient temperature, the second container being fluidly connected to the internal combustion engine or fuel cell. At block 530, heat is applied to the second plurality of particles to promote desorption of gas from the second plurality of adsorption particles in the second container. At block 540, gas is adsorbed onto the first plurality of adsorption particles in the first container concurrently while the second adsorption particles or second container are above ambient temperature. In some embodiments, additional containers (e.g., the adsorbed gas container 403) may be utilized. In some embodiments, one or more of the heaters 401A-403A may receive current from a regenerative braking system or a regenerative shock system as described herein.

[0088] In some embodiments, the heat is applied to the first container when a pressure of the first container is at or below a predetermined level of reduced pressure. In some embodiments, the heat is applied to the second container when a pressure of the second container is at or below a predetermined level of reduced pressure.

GENERAL FUEL SYSTEM EMBODIMENTS

[0089] The systems and methods described herein 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 of and can contain 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 a combination thereof or any other gas that can be adsorbed in a container for a variety of uses.

[0090] The fuel systems described 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 generators and construction equipment). In certain embodiments, the fuel system 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. [0091] 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.

[0092] 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.

[0093] 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.

[0094] 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 m²/g, at least about 700 m²/g, at least about 1,000 m²/g, at least about 1,200 m²/g, at least about 1,500 m²/g, at least about 1,700 m²/g, at least about 2,000 m²/g, at least about 5,000 m²/g or at least about 10,000 m²/g.

[0095] 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-

[0096] 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„[(A10₂)_x(Si0₂)_y]-mH₂0, 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.

[0097] In other embodiments the adsorbent material is a zeolitic material in which the framework structure is composed of YO₂ and X₂O₃, 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.

[0098] 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.

[0099] 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.

[0100] 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, NH₂, NH(-R-H), N(R- H)₂, CH₂OH, CH₂SH, CH₂NH₂, CH₂NH(-R-H), CH₂N(-R-H)₂, -C0₂H, COSH, -CS₂H, -N0₂, - B(OH)₂, -SO₃H, -Si(OH)₃, -Ge(OH)₃, -Sn(OH)₃, -Si(SH)₄, -Ge(SH)₄, -Sn(SH)₃, -P0₃H₂, -As0₃H, - As0₄H, -P(SH)₃, -As(SH)₃, -CH(RSH)₂, -C(RSH)₃, -CH(RNH₂)₂, -C(RNH₂)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(NH₂)₂, CH(NH(R-H))₂, CH(N(R-H)₂)₂, C(NH(R-H))₃, C(N(R-H)₂)₃, -C(NH₂)₃, -CH(OH)₂, -C(OH)₃, - CH(CN)₂, -C(CN)₃.

[0101] 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. [0102] 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.

[0103] 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.

[0104] 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 Ce 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.

[0105] 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.

[0106] 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, -NH₂, -OCH₃, - CH₃, -NH(CH₃), -N(CH₃)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.

[0107] 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-dicarboxylic 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-l,l-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.

[0108] 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.

[0109] 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 1.

Table 1 : Linker Moieties

[0110] 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.

[0111] 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.

[0112] 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.

[0113] Also, disclosure herein with respect to adsorbent particles is also contemplated to be applicable to monoliths of the material where applicable.

ACTIVATION OF PARTICLES [0114] 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.

[0115] 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.

[0116] 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.

[0117] 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.

[0118] 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.

[0119] 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.

[0120] 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.

[0121] 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.

[0122] 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.

[0123] 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., C₄_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.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] 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.

[0128] 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.

[0129] 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. [0130] 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.

[0131] 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".

Claims

CLAIMS What is claimed is:

1. A method of heating adsorbent particles comprising:

heating adsorbent particles by subjecting the adsorbent particles to heat produced by an electric current received from a regenerative brake system of a vehicle, the adsorbent particles having gas adsorbed thereon.

2. The method of claim 1, wherein heating the adsorbent particles results in desorption of gas from the particles.

3. The method of claim 1, wherein heating the adsorbent particles results in activation of the particles.

4. The method of claim 1, wherein the vehicle is a compressed gas vehicle, and the adsorbent particles are in a container suitable for adsorbed gas storage in the compressed gas vehicle.

5. The method of claim 1, wherein the electric current is received in response to application of the regenerative brakes.

6. The method of claim 4, wherein the electric current causes an electric heater to produce heat, the heater being in association with the adsorbed particles.

7. The method of claim 6, wherein the electric heater is a resistance heater.

8. The method of claim 6, wherein the electric heater is external or internal to the container.

9. The method of claim 6, wherein the electric heater is internal and external to the container.

10. The method of claim 6, wherein a portion of the electric current causes the electric heater to produce heat.

11. The method of claim 1, wherein at least a portion of the electric current is generated by a source other than a battery.

12. The method of claim 11, wherein the portion of the electric current is determined by comparing a reference temperature of the adsorbent particles with an actual temperature of the adsorbent particles.

13. The method of claim 12, wherein a remaining portion of electric current is diverted to the battery or other automobile electric device.

14. The method of claim 1, determining, using a control algorithm executed by a processing device, a magnitude of the current to achieve a target temperature or change in temperature.

15. The method of claim 14, wherein the processing device is a processing device of an engine computer or an external controller, and wherein the control algorithm is stored in a memory of the engine computer or external controller, the memory being communicatively coupled to the processing device.

16. The method of claim 1, wherein application of the regenerative brakes occurs upon brake pedal depression.

17. A method of heating adsorbent particles comprising:

heating adsorbent particles by subjecting the adsorbent particles to heat produced by an electric current obtained from a regenerative shock system of an automobile, the adsorbent particles having gas adsorbed thereon.

18. The method of claim 17, wherein the heating results in desorption of gas from the particles.

19. The method of claim 17, wherein the heating results in activation of the particles.

20. A compressed gas vehicle comprising:

a regenerative brake system adapted to generate an electric current to produce heat; and adsorbent particles arranged to be subjected to the heat.

21. The compressed gas vehicle of claim 20, wherein the adsorbent particles being subjected to the heat results in desorption of gas from the adsorbent particles.

22. The compressed gas vehicle of claim 20, wherein the adsorbent particles being subjected to the heat results in activation of the adsorbent particles.

23. The compressed gas vehicle of claim 20, wherein the electric current is received in response to application of the regenerative brakes.

24. The compressed gas vehicle of claim 20, wherein the adsorbent particles are in a container suitable for adsorbed gas storage.

25. The compressed gas vehicle of claim 24, wherein the electric current causes an electric heater to produce heat, the electric heater being in association with the adsorbed particles.

26. The compressed gas vehicle of claim 25, wherein the electric heater is a resistance heater.

27. The compressed gas vehicle of claim 25, wherein the electric heater is external to the container.

28. The compressed gas vehicle of claim 25, wherein the electric heater is internal to the container.

29. The compressed gas vehicle of claim 25, wherein the electric heater is internal and external to the container.

30. The compressed gas vehicle of claim 25, wherein a portion of the electric current causes the electric heater to produce heat.

31. The compressed gas vehicle of claim 30, wherein at least a portion of the electric current is to be generated by a source other than a battery.

32. The compressed gas vehicle of claim 31, wherein the portion of the electric current is to be determined by comparing a reference temperature of the adsorbent particles with an actual temperature of the adsorbent particles.

33. The compressed gas vehicle of claim 32, wherein a remaining portion of electric current is to be diverted to the battery or other automobile electric device.

34. The compressed gas vehicle of claim 20, further comprising:

an engine computer or external controller, wherein the engine or external computer comprising a processing device and a memory communicatively coupled to the processing device.

35. The compressed gas vehicle of claim 34, wherein a control algorithm is stored in the memory, and wherein the control algorithm, when executed by the processing device, causes the processing device to:

determining a magnitude of the current to achieve a target temperature or change in temperature.

36. The compressed gas vehicle of claim 20, wherein application of the regenerative brakes occurs upon brake pedal depression.

37. A compressed gas vehicle comprising:

a regenerative shock system that generates an electric current to produce heat; and adsorbent particles arranged to be subjected to the heat.

38. The compressed gas vehicle of claim 37, wherein subjecting the adsorbent particles to heat results in desorption of gas from the particles.

39. The compressed gas vehicle of claim 37, wherein subjecting the adsorbent particles to heat results in activation of the particles.

40. A method of cooling adsorbent particles comprising subjecting adsorbent particles to cooling generated by an electric current received in response to application of a regenerative brake system of a vehicle, the adsorbent particles having gas adsorbed thereon.

41. A method of regulating an amount of gas in a series of adsorbed gas containers, the method comprising:

applying heat to a first plurality of adsorption particles disposed within a first container to promote desorption of gas from the first plurality of adsorption particles, the first container being fluidly connected to an internal combustion engine or fuel cell; and

causing a gas to be adsorbed onto a second plurality of adsorption particles in a second container concurrently while the first adsorption particles or first container are above ambient temperature, the second container being fluidly connected to the internal combustion engine or fuel cell.

42. The method of claim 41, further comprising applying heat to the second plurality of particles to promote desorption of gas from the second plurality of adsorption particles in the second container.

43. The method of claim 41, further comprising causing gas to be adsorbed onto the first plurality of adsorption particles in the first container concurrently while the second adsorption particles or second container are above ambient temperature.

44. The method of claim 41, further comprising a third plurality of adsorption particles in a third container.

45. The method of claim 44, further comprising applying heat to the third plurality of adsorption particles to promote desorption of gas from the third plurality of adsorption particles in the third container.

46. The method of claim 44, further comprising causing gas to be adsorbed onto the first or second plurality of adsorption particles in the first or second container concurrently while the third adsorption particles or third container are above ambient temperature.

47. The method of claim 41, further comprising a compressor fluidly connected to the internal combustion engine or fuel cell and the first container, the compressor adapted to remove gas from the first container.

48. The method of claim 41, further comprising a compressor fluidly connected to the internal combustion engine or fuel cell and the second container, the compressor adapted to remove gas from the second container.

49. The method of claim 44, further comprising a compressor fluidly connected to the internal combustion engine or fuel cell and the third container, the compressor adapted to remove gas from the third container.

50. The method of claim 41, wherein heat is applied external to the first container, internal to the first container or a combination thereof.

51. The method of claim 42, wherein heat is applied external to the second container, internal to the second container or a combination thereof.

52. The method of claim 45, wherein heat is applied external to the third container, internal to the third container or a combination thereof.

53. The method of claim 41, wherein the second adsorption particles or second container are at or below ambient temperature when adsorbing a gas.

54. The method of claim 43, wherein the first adsorption particles or first container are at or below ambient temperature when adsorbing a gas.

55. The method of claim 41, wherein the heat is applied to the first container when a pressure of the first container is at or below a predetermined level of reduced pressure.

56. The method of claim 42, wherein the heat is applied to the second container when a pressure of the second container is at or below a predetermined level of reduced pressure.

57. The method of claim 41, wherein the heat is applied to the first or second container when a pressure of the first or second 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.

58. The method of claim 41, which allows for at least a 70%, at least an 80%, or at least a 90% utilization of an adsorbed gas capacity of a filled first container.

59. The method of claim 41, wherein gas is introduced into the second container through a gas fill line fluidly connected to the second container.

60. The method of claim 43, wherein gas is introduced into the first container through a gas fill line fluidly connected to the first container.