WO2015048489A1 - Procédé pour améliorer des rendements de systèmes de gaz à l'aide d'un compresseur - Google Patents
Procédé pour améliorer des rendements de systèmes de gaz à l'aide d'un compresseur Download PDFInfo
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- WO2015048489A1 WO2015048489A1 PCT/US2014/057778 US2014057778W WO2015048489A1 WO 2015048489 A1 WO2015048489 A1 WO 2015048489A1 US 2014057778 W US2014057778 W US 2014057778W WO 2015048489 A1 WO2015048489 A1 WO 2015048489A1
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- fuel system
- container
- gas
- particles
- adsorbed gas
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Classifications
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- 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
- F17C11/007—Use of gas-solvents or gas-sorbents in vessels for hydrocarbon gases, such as methane or natural gas, propane, butane or mixtures thereof [LPG]
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 containing empty pores and channels, the sizes of which are defined by the size of the organic linker.
- metal organic framework can be used for many applications such as gas storage, gas/vapor separation, heat exchange, 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
- the larger specific surface area and high porosity on the nanometer scale enable metal organic framework to hold relatively large amounts of gases.
- metal organic framework 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.
- an adsorbed gas fuel system including an internal combustion engine; an adsorbed gas container fluidly connected to the fuel injector, the adsorbed gas container containing adsorption particles; a compressor fluidly connected to the internal combustion engine and the adsorbed gas container, the compressor adapted to remove gas from the adsorbed gas container; and a control system to modulate the supply pressure (P e ) to the internal combustion engine.
- FIG. 1 Other embodiments are directed to a fuel system including: an internal combustion engine; an adsorbed gas container fluidly connected to the internal combustion engine, the adsorbed gas container containing an adsorbent; a gasoline container fluidly connected to the internal combustion engine and the adsorbed gas container; and a compressor capable of extracting gasoline vapor from the gasoline container and depositing the gasoline vapor into the adsorbed gas container.
- the present disclosure is directed to a fuel system including: an internal combustion engine; a gas container optionally fluidly connected to the internal combustion engine; a gasoline container fluidly connected to the internal combustion engine and the gas container; and a compressor capable of extracting gasoline vapor from the gasoline container and depositing the gasoline vapor into the gas container.
- Additional embodiments are directed to a fuel system including: an internal combustion engine; an adsorbed gas container fluidly connected to the internal combustion engine, the adsorbed gas container containing an adsorbent; a gasoline container fluidly connected to the internal combustion engine and optionally the adsorbed gas container; an additional gas container and a compressor capable of extracting gasoline vapor from the gasoline container and depositing the gasoline vapor into the additional gas container.
- the adsorption material utilized in the systems is metal organic framework.
- 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 includes 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 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 "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 fuel system of an embodiment of the disclosure that utilizes a compressor to extract adsorbed gas from a container;
- Figure 2 depicts a control system for a fuel system of an embodiment of the disclosure that utilizes a compressor to extract adsorbed gas from a container;
- Figure 3 depicts a fuel system of an embodiment of the disclosure that utilizes a compressor to recover vapor from a gasoline container;
- Figure 4 depicts a fuel system of an alternate embodiment of the disclosure that utilizes a compressor to recover vapor from a gasoline container;
- Figure 5 is a flow diagram illustrating a method for implementing a fuel system in accordance with an embodiment of the disclosure.
- Adsorption materials are capable of storing large amount of gas for subsequent use in applications such as gas powered vehicles.
- the containers that hold the adsorbent materials are depressurized as a result of consumption of the gas contained therein, a significant amount of the gas can remain adsorbed on the materials.
- a fuel injector may require pressures, e.g., of greater than about 150 psi, or 500 psi or more
- the adsorbed gas at low pressures is not accessible to fuel the engine. This results in an inefficient utilization of fuels which is addressed by certain embodiments disclosed herein.
- an adsorbed gas fuel system including an outlet (11) that may be fluidly connected to an internal combustion engine, an adsorbed gas container (12) containing adsorption particles and being fluidly connected to the internal combustion, and a compressor (13) fluidly connected to the internal combustion engine and the adsorbed gas container (12).
- the compressor (13) may be adapted remove gas from the adsorbed gas container (12).
- a control system (14) may be communicatively coupled to the compressor (13) to modulate an engine supply pressure, P e , to the internal combustion engine.
- the controller (14) may be connected to a pressure sensor (18) adapted to measure the engine supply pressure, P e .
- the controller (14) may also be connected to a pressure sensor (17) for measuring a storage system pressure, P s , and connected to a temperature sensor (16) for measuring a temperature of the storage system, T s .
- a pressure sensor (17) for measuring a storage system pressure, P s
- a temperature sensor (16) for measuring a temperature of the storage system, T s .
- more or less sensors may be included as would be appreciated by one of ordinary skill in the art.
- the system may also include an inlet (15) that fluidly connects a gas fill line to the adsorbed gas container and the compressor.
- the compressor can modulate the pressure of the adsorbed gas container during filling.
- the system includes an additional compressor for modulating the pressure of the adsorbed gas container during filling.
- the additional compressor can be on board a vehicle or external to a vehicle.
- the fuel system further includes a fuel injector in fluid connection between the engine and the compressor.
- the compressor is suitable to extract adsorbed gas from the container at times of low pressure in order to provide gas at a sufficient pressure to the fuel injector for operation of the engine.
- the system works on direct injection into the engine without the need for a fuel injector.
- the compressor is in fluid connection directly with the engine.
- the compressor is adapted to remove gas from the adsorbed gas container when the engine is running and when the container pressure is, e.g., about 250 psi or less; about 200 psi or less; about 150 psi or less; about 125 psi or less; about 100 psi or less; about 75 psi or less, or about 50 psi or less.
- the compressor can facilitate the removal of gas from the adsorbed gas container even when the pressure is at a relatively high pressure as compared to the values above.
- the compressor is adapted to maintain the pressure of compressed gas at the engine (or the fuel injector) when the engine is running at, e.g., about 250 psi or greater; about 200 psi or greater; about 150 psi or greater; or about 100 psi or greater. In certain embodiments, the compressor is adapted to maintain the pressure of compressed gas at the engine (or the fuel injector) at from about 100 psi to about 600 psi when the engine is running.
- the fuel system allows for at least about 70%, at least about 80%, at least about 90%, at least about 95% or at least about 99% utilization of the adsorbed gas capacity of a filled adsorbed gas container.
- the fuel system may also include a control system (20) to modulate the supply pressure to the internal combustion engine based on one or more of storage system pressure (P s ), storage system temperature (T s ), engine supply pressure (P e ), additional parameters, or combinations thereof.
- the control system (20) may be the same or similar to the controller (14) described with respect to Figure 1.
- the control system modulates the supply pressure to the internal combustion engine based on P s and T s and utilizes P e as a direct feedback signal for controllability.
- a compressor to modulate extraction of gas from an adsorbed gas container is not limited to use with internal combustion engines.
- the embodiments disclosed herein can also be utilized in any machine that operates on combustible gas, e.g., an internal combustion engine, or a device that converts chemical energy from a fuel into electricity such as a fuel cell.
- certain embodiments are directed to a fuel system (30) including an internal combustion engine (31), an adsorbed gas container (32) fluidly connected to the internal combustion engine, the adsorbed gas container containing an adsorbent; a gasoline container (33) fluidly connected to the internal combustion engine and the adsorbed gas container; and a compressor (34) capable of extracting gasoline vapor from the gasoline container and depositing the gasoline vapor into the adsorbed gas container.
- a fuel system including an internal combustion engine (31), an adsorbed gas container (32) fluidly connected to the internal combustion engine, the adsorbed gas container containing an adsorbent; a gasoline container (33) fluidly connected to the internal combustion engine and the adsorbed gas container; and a compressor (34) capable of extracting gasoline vapor from the gasoline container and depositing the gasoline vapor into the adsorbed gas container.
- one or more additional adsorbed gas containers may be fluidly connected between the compressor (34) and the engine (31).
- certain embodiments are directed to a fuel system (40) including an internal combustion engine (41), an adsorbed gas container (42) fluidly connected to the internal combustion engine, the adsorbed gas container containing an adsorbent; a gasoline container (43) fluidly connected to the internal combustion engine and the adsorbed gas container; and a compressor (44) capable of extracting gasoline vapor from the gasoline container and depositing the gasoline vapor into an additional container (45) that optionally contains an adsorbent material.
- one or more additional adsorbed gas containers may be fluidly connected between the compressor (44) and the engine (41).
- the vapor can be deposited under pressure into the container(s) as a liquid.
- FIG. 5 is a flow diagram illustrating a method (50) for implementing a fuel system in accordance with an embodiment of the disclosure.
- the method (50) may be performed using any of fuel systems (10), (30), or (40).
- a container pressure of an adsorbed gas container e.g., any of adsorbed gas containers (12), (32), or (42)
- the container pressure may be measured using a pressure sensor (e.g., pressure sensor (17)).
- the threshold pressure value is about 100 psi.
- the engine is fluidly connected to the adsorbed gas container.
- a compressor e.g., any of compressors (13), (34), or (44)
- the compressor is fluidly connected to the adsorbed gas container and the engine.
- a fuel system including: an internal combustion engine; a gas container optionally fluidly connected to the internal combustion engine; a gasoline container fluidly connected to the internal combustion engine and the gas container; and a compressor capable of extracting gasoline vapor from the gasoline container and depositing the gasoline vapor into the gas container.
- the gas container may not contain an adsorbent material and can be a compressed gas container.
- the gas container can be utilized to power the engine or can solely be used to hold the extracted material for later disposal or for alternative use.
- An additional embodiment is directed to a fuel system including: an internal combustion engine; an adsorbed gas container fluidly connected to the internal combustion engine, the adsorbed gas container containing an adsorbent; a gasoline container fluidly connected to the internal combustion engine and optionally the adsorbed gas container; an additional gas container and a compressor capable of extracting gasoline vapor from the gasoline container and depositing the gasoline vapor into the additional gas container.
- the engine powers the compressor when the engine is running.
- the fuel system of the present disclosure may also include a battery that powers the compressor when the engine is off.
- the battery may be external or internal to a vehicle that integrates the fuel system.
- a guard bed may also be included in the systems disclosed herein.
- the gasoline vapor extracted from the gasoline tank by the compressor may be adsorbed into the guard bed, on the adsorbent in the container, or both.
- the guard bed can be incorporated into the adsorbed gas container.
- the vapors extracted from the gasoline tank are typically hydrocarbon gasses such as butane but can also include other gases.
- the compressor for extracting the gasoline vapor may also be capable of filling the adsorbed gas container with a gas from an external source and/or capable to remove gas from the adsorbed gas container during engine operation at times of low pressure (as disclosed above).
- one or more additional compressors can be included in the fuel system for these additional operations.
- the disclosed fuel systems may include containers such as cylinders, tanks or any other container that is suitable for storing adsorbed gas.
- the container can be suitable for adsorption, containment, and/or transportation of natural gas, hydrocarbon gas (e.g., methane, ethane, butane, propane, pentane, hexane, isomers thereof and a combination thereof), air, oxygen, nitrogen, synthetic gas, hydrogen, carbon monoxide, carbon dioxide, helium, or any other gas, or combinations thereof that can be adsorbed in a container for a variety of uses.
- the container may be electrically grounded during filling for safety concerns.
- the container is adapted to contain a quantity of compressed gas to provide a range of operation for a vehicle of about 5 miles or more, of about 10 miles or more, of about 25 miles or more, of about 50 miles or more, of about 100 miles or more, or about 200 miles or more.
- the fuel systems of the present disclosure 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).
- a compressed gas vehicle such as a road vehicle or an off-road vehicle
- 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 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 the fuel systems 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 or 10 containers.
- the ratio of the tapped density of the particles to the ratio of the 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 1000 m 2 /g, at least about 1200 m 2 /g, at least about 1500 m 2 /g, at least about 1700 m 2 /g, at least about 2000 m 2 /g, at least about 5000 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-Teller-Teller)
- Emmett-Teller 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 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 Y0 2 and X2O 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 MOF 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 MOF 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 MOF 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 C 6 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 MOF subunit or MOF-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 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-butene- dicarboxylic 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, 1,3- butadiene- 1
- 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 MOF 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.
- One embodiment is directed to the fuel systems disclosed herein with a containment system including a container suitable for adsorbed gas storage having a capacity of at least 1 liter at least partially filled with metal organic framework particles such that the ratio of the tapped density of the particles to the ratio of the freely settled density of the particles is at least 1.1. Still further embodiments are directed to vehicles including the fuel systems as disclosed herein. Other embodiments are directed to methods of manufacturing such vehicles by integrating a fuel system as disclosed herein into a vehicle.
- the disclosed fuels systems can be part of an assembly of a new vehicle or can be retrofitted into an existing vehicle. Also disclosed herein are methods of operating a vehicle including controlling the amount of gas being utilized by a vehicle including a fuel system as disclosed herein.
- the fuel systems can include a container suitable for adsorbed gas storage having a capacity of at least 1 liter and at least partially filled with metal organic framework particles such that (i) the ratio of the tapped density of the particles to the ratio of the freely settled density of the particles greater than 1 (e.g., 1.1 or more) or (ii) the tapped density is, depending on the selection of materials, e.g., from about .1 g/cm 3 to about 10 g/cm 3 , from about .2 g/cm 3 to about 5 g/cm 3 , from about .3 g/cm 3 to about .8 g/cm 3 or from about .2 g/cm 3 to about 1 g/cm 3 .
- the filling process may include shifting or moving (intermittently or constantly) the container during at least a portion of the filling.
- the filling may include shifting or moving the container after the filling with the metal organic framework particles.
- the shifting or moving of the container may include, e.g., shaking, rolling, vibrating or subjection to centrifugal force.
- the filling process may also include the use of a tube to transfer the metal organic framework particles from a storage vessel to the container.
- the tube can be any suitable dimension such as, e.g., an elongated cylinder.
- a funnel may also be utilized in the filling process.
- the funnel can be incorporated as an integral part of the tube or can be a separate apparatus that is connected with the tube.
- the container can be positioned such that the stream of particles during the filling is downward.
- the stream of particles during the filling is downward at any suitable angle to effect filling, e.g., at an angle of between about 135° and about 225° from a vertical axis.
- the tube can be sealed to the container inlet during the filling, sealed to the storage vessel outlet during the filling or sealed to both the container inlet and the storage vessel outlet during the filling.
- the tube is at an initial position at the start of the filling and the tube is raised upward to a second position at the end of the filling.
- the tube may be raised intermittently or constantly from the initial position to the second position during the filling. Further, the tube may be raised at a fixed rate or at a varied rate from the initial position to the second position during the filling. In still further embodiments, the tube is raised linearly or non-linearly (e.g., in a circular or corkscrew manner) from the initial position to the second position during the filling.
- the filling process may also use a deflector within or in proximity of the inlet of the container in order to maximize the distribution of the particles within the container.
- One or more steps of the filling process may also be performed under an inert atmosphere (e.g., nitrogen) in order to minimize exposure of the materials to contaminants.
- an inert atmosphere e.g., nitrogen
- the filling process may also include the manipulation of the particles in order to facilitate the process.
- manipulations may include, e.g., surface roughness control, low friction coatings, electrostatic charge reduction, or any other suitable parameters that may facilitate loading.
- 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.
- the disclosed fuel systems can include activated adsorption particles (e.g., metal organic framework particles) wherein the adsorption particles are subjected to conditions selected from the group consisting of above ambient temperature, vacuum, an inert gas flow and a combination thereof, for a sufficient time to activate the particles.
- the activation includes the removal of water molecules from the adsorption sites.
- the activation includes the removal of nonaqueous solvent molecules from the adsorption sites that are residual from the manufacture of the particles.
- the activation includes the removal of sulfur compounds or higher hydrocarbons from the adsorption sites.
- a subsequent solvent recovery step is also contemplated.
- the contaminants e.g., water, non-aqueous solvents, sulfur compounds or higher hydrocarbons
- the contaminants are removed from the adsorption material at a molecular level.
- the activation includes the removal of water molecules from the surface area of the particles.
- the particles may have a moisture content of less than about 10%, less than about 8%, less than about 5%, less than about 3%, less than about 1 %, less than about 0.8%, less than about 0.5%, less than about 0.3% or less than about 0.1 % by weight of the particles.
- the available surface area of the adsorption material for adsorption of the intended gas is greater than about 80%, greater than about 85%, greater than about 90%, greater than about 95% or greater than about 98% of the accepted value (i.e., the theoretical surface area free of adsorbed contaminants).
- the 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, non-aqueous 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 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.
- 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 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 1 hour to about 48 hours, from about 2 hours to about 24 hours or from about 4 hours to about 16 hours.
- 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 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, air conditioning unit, brake system, or a combination thereof.
- 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 particles 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.
- 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.
- adsorbent materials such as activated alumina, silica gel, activated carbon, molecular sieve carbon, zeolites (e.g., molecular sieve zeolites), polymers, resins and clays.
- disclosure herein with respect to adsorbent particles is also contemplated to be applicable to monoliths of the material where applicable.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Filling Or Discharging Of Gas Storage Vessels (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
Dans certains modes de réalisation, l'invention concerne des procédés pour améliorer des rendements de systèmes de combustible gazeux adsorbé, et pour récupérer des vapeurs provenant de récipients d'essence. Certains modes de réalisation visent à fournir des systèmes pour accéder à un gaz dans des systèmes de gaz adsorbé pendant des périodes de basse pression. Certains modes de réalisation concernent un système de combustible gazeux adsorbé comprenant un moteur à combustion interne ; un récipient de gaz adsorbé relié fluidiquement à l'injecteur de carburant, le récipient de gaz adsorbé contenant des particules d'adsorption ; un compresseur relié fluidiquement au moteur à combustion interne et au récipient de gaz adsorbé, le compresseur étant conçu pour éliminer un gaz du récipient de gaz adsorbé ; et un système de commande pour moduler la pression d'alimentation du moteur à combustion interne.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US201361883704P | 2013-09-27 | 2013-09-27 | |
US61/883,704 | 2013-09-27 |
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WO2015048489A1 true WO2015048489A1 (fr) | 2015-04-02 |
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PCT/US2014/057780 WO2015048491A1 (fr) | 2013-09-27 | 2014-09-26 | Procédé pour accroître les rendements de systèmes à gaz par l'extraction de vapeurs d'essence |
PCT/US2014/057778 WO2015048489A1 (fr) | 2013-09-27 | 2014-09-26 | Procédé pour améliorer des rendements de systèmes de gaz à l'aide d'un compresseur |
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PCT/US2014/057780 WO2015048491A1 (fr) | 2013-09-27 | 2014-09-26 | Procédé pour accroître les rendements de systèmes à gaz par l'extraction de vapeurs d'essence |
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AR (1) | AR097788A1 (fr) |
WO (2) | WO2015048491A1 (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2017023224A1 (fr) * | 2015-08-03 | 2017-02-09 | Tofas Turk Otomobil Fabrikasi Anonim Sirketi | Système de gaz naturel adsorbé pour véhicules |
US10556801B2 (en) | 2015-02-12 | 2020-02-11 | Basf Se | Process for the preparation of a dealuminated zeolitic material having the BEA framework structure |
Citations (2)
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US20060099398A1 (en) * | 2004-11-09 | 2006-05-11 | Basf Aktiengesellschaft | Shaped bodies containing metal-organic frameworks |
US20090101118A1 (en) * | 2007-10-23 | 2009-04-23 | Gm Global Technology Operations, Inc. | Fuel supply system with a gas adsorption device |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
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ES2640910T3 (es) * | 2000-10-27 | 2017-11-07 | Air Products And Chemicals, Inc. | Sistemas y procesos para proporcionar hidrógeno a células de combustible |
CN102099217B (zh) * | 2008-02-13 | 2015-07-29 | 尼尔·杨 | 混合电动车辆及其制造方法 |
US8425674B2 (en) * | 2008-10-24 | 2013-04-23 | Exxonmobil Research And Engineering Company | System using unutilized heat for cooling and/or power generation |
-
2014
- 2014-09-26 WO PCT/US2014/057780 patent/WO2015048491A1/fr active Application Filing
- 2014-09-26 WO PCT/US2014/057778 patent/WO2015048489A1/fr active Application Filing
- 2014-09-26 AR ARP140103576A patent/AR097788A1/es unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060099398A1 (en) * | 2004-11-09 | 2006-05-11 | Basf Aktiengesellschaft | Shaped bodies containing metal-organic frameworks |
US20090101118A1 (en) * | 2007-10-23 | 2009-04-23 | Gm Global Technology Operations, Inc. | Fuel supply system with a gas adsorption device |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10556801B2 (en) | 2015-02-12 | 2020-02-11 | Basf Se | Process for the preparation of a dealuminated zeolitic material having the BEA framework structure |
WO2017023224A1 (fr) * | 2015-08-03 | 2017-02-09 | Tofas Turk Otomobil Fabrikasi Anonim Sirketi | Système de gaz naturel adsorbé pour véhicules |
Also Published As
Publication number | Publication date |
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AR097788A1 (es) | 2016-04-13 |
WO2015048491A1 (fr) | 2015-04-02 |
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