WO2015123531A1 - Procédés et systèmes pour chauffer des systèmes à gaz adsorbés - Google Patents

Procédés et systèmes pour chauffer des systèmes à gaz adsorbés Download PDF

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Publication number
WO2015123531A1
WO2015123531A1 PCT/US2015/015836 US2015015836W WO2015123531A1 WO 2015123531 A1 WO2015123531 A1 WO 2015123531A1 US 2015015836 W US2015015836 W US 2015015836W WO 2015123531 A1 WO2015123531 A1 WO 2015123531A1
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WIPO (PCT)
Prior art keywords
container
particles
gas
vehicle
heat
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PCT/US2015/015836
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English (en)
Inventor
William Dolan
Christoph GARBOTZ
Adam Lack
Joseph Lynch
Ulrich Mueller
Michael SANTAMARIA
Mathias WEICKERT
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Basf Corporation
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Publication of WO2015123531A1 publication Critical patent/WO2015123531A1/fr

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels

Definitions

  • 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.
  • 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.
  • metal ions e.g. zinc, aluminum
  • organic compounds Each of the organic compounds can attach to at least two metal ions (at least bidentate), serving as a linker for them.
  • metal ions at least bidentate
  • 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.
  • metal organic framework can be used for many applications such as gas storage, gas/vapor separation, catalysis, luminescence and drug delivery.
  • metal organic framework can have (show) a specific surface area of up to 10,000 m 2 /g determined by Langmuir model.
  • metal organic framework for gas storage (e.g., natural gas) in gas powered vehicles.
  • gas storage e.g., natural gas
  • 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.
  • adsorbent materials e.g., metal organic framework
  • adsorption materials e.g., metal organic framework
  • adsorption materials e.g., metal organic framework
  • gas powered machines e.g., vehicles, heavy equipment
  • 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.
  • 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.
  • 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.
  • Certain other embodiments are directed to a method of preparing or method of operating the systems disclosed herein.
  • Certain other embodiments are directed to a vehicle utilizing the systems and methods disclosed herein.
  • adsorbent particles comprise metal organic framework particles or activated carbon.
  • 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 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 15,000 m 2 /g.
  • 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.
  • 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.
  • the metal organic framework particles are in a form of pellets, extrudates, beads, monoliths, or any other defined or irregular shape.
  • the adsorbent particles comprise metal organic framework particles or activated charcoal.
  • the adsorbent particles are disposed within a container having a form of a tank, cyclindrical, toroidal, or rectanguloid.
  • 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.
  • 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.
  • the container is suitable to hold the adsorbed gas under pressure or compression.
  • 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.
  • activation refers to the treatment of adsorption materials (e.g., metal organic framework particles) in a manner to increase their storage capacity.
  • adsorption materials e.g., metal organic framework particles
  • 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.
  • 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.
  • 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.
  • 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.
  • multiple monoliths can be arranged together to form a desired shape.
  • 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).
  • a fluid e.g., a gas
  • 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.
  • 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.
  • 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).
  • Figure 1 depicts a regenerative brake system of the present disclosure with an external heater according to an embodiment of the disclosure
  • Figure 2 depicts a regenerative brake system of the present disclosure with an internal heater according to an embodiment of the disclosure
  • Figure 3 is a block diagram illustrating a method for heating adsorbent particles according to an embodiment of the disclosure
  • Figure 4 depicts a system including three adsorbed gas containers according to an embodiment of the disclosure.
  • 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.
  • 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.
  • the application of heat to absorption particles may also be used to activate the particles by promoting the desorption of contaminants from the particles.
  • the particles after heating, 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.
  • 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.
  • 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.
  • 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.
  • the electric current (or a portion thereof) is directly provided by the regenerative brakes to heat the adsorption particles, thus bypassing a battery.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • the contaminants e.g., water, non-aqueous solvents, sulfur compounds or higher hydrocarbons
  • the activation comprises the removal of water molecules from the surface area of the particles.
  • 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.
  • 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).
  • 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.
  • the brake system 106 may be replaced with a regenerative shock system.
  • 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).
  • 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.
  • the brake system 206 may be replaced with a regenerative shock system.
  • 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).
  • FIG. 3 is a block diagram illustrating a method for heating adsorbent particles according to an embodiment of the disclosure.
  • 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.
  • heating the adsorbent particles results in desorption of gas from the particles.
  • heating the adsorbent particles results in activation of the particles.
  • the vehicle is a compressed gas vehicle
  • the adsorbent particles are in a container suitable for adsorbed gas storage in the compressed gas vehicle.
  • the electric current is received in response to application of the regenerative brakes or a regenerative shock system.
  • the electric current causes an electric heater to produce heat, the heater being in association with the adsorbed particles.
  • the electric heater is a resistance heater.
  • the electric heater is external or internal to the container.
  • the electric heater is internal and external to the container.
  • a portion of the electric current causes the electric heater to produce heat.
  • At least a portion of the electric current is generated by a source other than a battery.
  • 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.
  • a remaining portion of electric current is diverted to the battery or other automobile electric device.
  • 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.
  • 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.
  • application of the regenerative brakes occurs upon brake pedal depression.
  • 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.
  • 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.
  • ambient temperature e.g., the temperature of the environment of the container or a vehicle that includes the container
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the method can also comprise a third plurality of adsorption particles in a third container.
  • 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.
  • 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.
  • 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.
  • a current is generated that powers a resistant heater in association with the container or adsorption particles.
  • 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.
  • 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.
  • the system and methods can utilize gas fill lines in fluid connection with the adsorbed gas container(s).
  • 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.
  • 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.
  • 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.
  • FIG. 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.
  • the method 500 is performed by the system 400.
  • 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.
  • an internal combustion engine e.g., engine 404
  • 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.
  • 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.
  • 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.
  • additional containers e.g., the adsorbed gas container 403 may be utilized.
  • one or more of the heaters 401A-403A may receive current from a regenerative braking system or a regenerative shock system as described herein.
  • 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.
  • 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.
  • 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 helium
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the adsorbent material e.g., particles
  • the adsorbent material 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.
  • 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-
  • the adsorbent material includes a zeolite.
  • a chemical formula of the zeolite is of a form of M x lake[(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.
  • 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.
  • Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge, and combinations of two or more thereof.
  • Y is selected from the group consisting of Si, Ti, Zr, and combinations of two or more thereof.
  • Y is Si and/or Sn.
  • Y is Si.
  • X is selected from the group consisting of Al, B, In, Ga, and combinations of two or more thereof.
  • X is selected from the group consisting of Al, B, In, and combinations of two or more thereof.
  • X is Al and/or B.
  • X is Al.
  • 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.
  • the metal organic framework particles include a metal selected from the group consisting of Al, Mg, Zn, Cu, Zr, and a combination thereof.
  • 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.
  • 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.
  • 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.
  • radical R is not present.
  • 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.
  • 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.
  • 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.
  • certain embodiments may include, inter alia, methane, adamantane, acetylene, ethylene or butadiene.
  • 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.
  • 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.
  • the at least bidentate organic compound may be derived from a dicarboxylic, tricarboxylic or tetracarboxylic acid or a sulfur analogue thereof.
  • 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.
  • the at least bidentate organic compound can include further substituents such as -OH, -NH 2 , -OCH 3 , - CH 3 , -NH(CH 3 ), -N(CH 3 ) 2 , -CN and halides.
  • 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.
  • dicarboxylic acids 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-dicar
  • 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.
  • 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.
  • 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.
  • the linker may be a moiety selected from any of the moieties illustrated in Table 1.
  • 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.
  • 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.
  • 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.
  • disclosure herein with respect to adsorbent particles is also contemplated to be applicable to monoliths of the material where applicable.
  • Activation can occur before or after the particles are filled into a container suitable for adsorbed gas storage.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • contaminants e.g., water, non-aqueous solvents, sulfur compounds and higher
  • 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.
  • 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.
  • 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.
  • any amount of adsorbent material may be activated according to the methods described herein, or a combination thereof.
  • 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.
  • 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.
  • 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.
  • the activation can occur by placing the container in an oven.
  • a heat source internal to the vehicle or machinery can be used.
  • the heat source in a vehicle may be derived from the battery, engine, air conditioning unit, brake system, or a combination thereof.
  • the container at least partially filled with particles can be activated with an external heat source.
  • a microwave energy source may be utilized to provide microwave energy to heat and activate the particles.
  • 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.
  • a vacuum source internal or external to the vehicle or machinery can be used for activation.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the inert gas flow is initiated and terminated at the same location on the container.
  • the inert gas flow may include the utilization of a single tube for introducing and removing the inert gas from the container.
  • 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.
  • 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.
  • 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.
  • zeolites e.g., molecular sieve zeolites
  • polymers resins and clays.
  • 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.
  • 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.
  • 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.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)

Abstract

Certains modes de réalisation de l'invention concernent des systèmes et des procédés pour chauffer des particules adsorbantes et réguler des quantités de gaz adsorbés dans des contenants de gaz adsorbés. Certains modes de réalisation se rapportent à un procédé permettant de chauffer des particules adsorbantes, consistant à soumettre les particules adsorbantes à la chaleur produite par un courant électrique reçu en provenance d'un système de freinage par récupération d'un véhicule, les particules adsorbantes ayant sur celles-ci du gaz adsorbé.
PCT/US2015/015836 2014-02-14 2015-02-13 Procédés et systèmes pour chauffer des systèmes à gaz adsorbés WO2015123531A1 (fr)

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US201461939896P 2014-02-14 2014-02-14
US201461939891P 2014-02-14 2014-02-14
US61/939,896 2014-02-14
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US10202323B2 (en) 2015-07-15 2019-02-12 Basf Se Process for preparing an arylpropene
US10556801B2 (en) 2015-02-12 2020-02-11 Basf Se Process for the preparation of a dealuminated zeolitic material having the BEA framework structure
US10737239B2 (en) 2015-11-27 2020-08-11 Basf Se Ultrafast high space-time-yield synthesis of metal-organic frameworks
US10737944B2 (en) 2015-12-08 2020-08-11 Basf Se Tin-containing zeolitic material having a BEA framework structure
US10766781B2 (en) 2015-12-08 2020-09-08 Basf Se Tin-containing zeolitic material having a BEA framework structure

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