Pressure vessels, such as, e.g., gas storage containers and hydraulic accumulators may be used to contain fluids under pressure. It may be desirable to have a pressure vessel with relatively thin walls and low weight. For example, in a vehicle fuel tank, relatively thin walls allow for more efficient use of available space, and relatively low weight allows for movement of the vehicle with greater energy efficiency.
Examples of the present disclosure include a method for increasing the storage capacity of a natural gas tank. An example method includes selecting a container with a service pressure rating of about 3,600 psi to be filled with natural gas to a full tank pressure up to about 3,600 psi. A natural gas adsorbent is incorporated into the container. The container including the adsorbent therein has a maximum fill capacity. The example method further includes cooling the adsorbent by Joule-Thomson cooling during filling of the container with natural gas from a filling source at greater than 3,600 psi. The container is filled to the maximum fill capacity at a fill rate to prevent a bulk temperature of the adsorbent from rising more than about 5° C. above an ambient temperature. A rate of heat transfer from the tank is less than a rate of heating from compression of the natural gas and adsorption during the filling. The natural gas adsorbent adsorbs a higher amount of natural gas than would the adsorbent at temperatures higher than 5° C. above the ambient temperature.
Features and advantages of examples of the present disclosure will become apparent by reference to the following detailed description and drawings, in which like reference numerals correspond to similar, though perhaps not identical, components. For the sake of brevity, reference numerals or features having a previously described function may or may not be described in connection with other drawings in which they appear.
Natural gas automotive vehicles are fitted with on-board storage tanks Adsorbent natural gas (ANG) storage tanks are generally designed as low pressure systems. In an example of such a low pressure system, at about 725 psi (about 50 bar), a vehicle including a 0.1 m3 (i.e., 100 L) natural gas tank filled with a suitable amount of a carbon adsorbent having a BET surface area of about 1000 m2/g, a bulk density of 0.5 g/cm3, and a total adsorption of 0.13 g/g is expected to have about 2.85 GGE (Gallon of Gasoline Equivalent) (for a range of about 85 miles), assuming 30 mpg.
However, examples herein disclose ANG high pressure systems. These high pressure systems may have service pressure ratings ranging from about 200 bar (about 2,901 psi) to about 300 bar (about 4,351 psi); or from about 20,684 kPa (˜207 bar/3,000 psi) to about 24,821 kPa (˜248 bar/3,600 psi). During fueling, the container of the high pressure system storage tank is designed to fill until the tank achieves a pressure within the designated service rated range.
In the examples disclosed herein, the container of the tank is rated for the high pressures, and the adsorbent in the ANG tank, when the tank is filled according to examples of the present method, increases the storage capacity so that the tank is capable of storing and delivering a sufficient amount of natural gas for desired vehicle operation.
However, prior to realizing the advantages of the examples of the method disclosed herein, it would have been expected that including adsorbent in a natural gas tank for high pressure applications would have been a disadvantage. For example, including into a 0.1 m3 (i.e., 100 L) natural gas tank, a carbon adsorbent having a BET surface area of about 1000 m2/g, a bulk density of 0.5 g/cm3, and filling (without utilizing examples of the present method) at about 3,600 psi (about 248 bar) may generally result in a total adsorption of about 0.3 g/g, with an expectation of about 6.6 GGE (for a range of about 197 miles), assuming 30 mpg. For comparison, a 100 L compressed natural gas (CNG) tank without adsorbent filled at 250 bar would have about 8.3 GGE (for a range of about 250 miles), assuming 30 mpg. As such, without using the methods of the present disclosure, the tank with adsorbent would be expected to have about 1.7 GGE less than the same 100 L tank with no adsorbent.
In contrast, examples of the present method may advantageously be used to fill ANG tanks at high pressure fueling stations (e.g., retail or fleet refueling stations), without deleterious loss of tank storage capacity.
Further, in some examples of the present method, depending on the adsorbent selected, it is contemplated as being within the purview of the present disclosure to obtain better performance/higher storage capacity with the adsorbent at 250 bar than would a CNG tank (having no adsorbent) at 250 bar.
It is believed that the adsorption effect of the quantity of adsorbent in the examples disclosed herein is high enough to compensate for any loss in storage capacity due to the skeleton of the adsorbent occupying volume in the container. For the same temperature and pressure, the density of the adsorbed phase is bigger than the density of the gas phase. As such, the adsorbent will maintain or improve the container's storage capacity of compressed natural gas at high pressures.
Increased storage capacity generally leads to obtaining higher vehicle mileage. It is believed that the examples disclosed herein will exhibit higher, or on par natural gas storage capacity and thus higher, or on par vehicle mileage when compared to benchmark compressed gas technology.
Referring now to
The container 12 may be made of any material that is suitable for a reusable pressure vessel having a service rating up to about 3,600 psi. Examples of suitable container 12 materials include high strength aluminum alloys and high strength low alloy (HSLA) steels. Examples of high strength aluminum alloys include those in the 7000 series, which have relatively high yield strength. The 7000 series is a naming convention for wrought alloys, from the International Alloy Designation System. 7000 series aluminum alloys are alloyed with zinc, and can be precipitation hardened to the highest strengths of any aluminum alloy. One specific example includes aluminum 7075-T6 which has a tensile yield strength of about 73,000 psi. Examples of high strength low alloy steel generally have a carbon content ranging from about 0.05% to about 0.25%, and the remainder of the chemical composition varies in order to obtain the desired mechanical properties. Examples of HSLA steel are: ASTM International A572-50 (yield strength=50,000 psi); A516-70 (yield strength=38,000 psi); and A588 (yield strength=50,000 psi).
While the shape of the container 12 shown in
In the example shown in
While not shown, it is to be understood that the container 12 may be configured with other containers so that the multiple containers are in fluid (e.g., gas) communication through a manifold or other suitable mechanism.
As illustrated in
In general, the adsorbent 14 has a high surface area and is porous. The size of the pores is generally greater than the effective molecular diameter of at least the methane compounds in the natural gas. In an example, the pore size distribution is such that there are pores having an effective molecular diameter of the smallest compounds to be adsorbed and pores having an effective molecular diameter of the largest compounds to be adsorbed. In an example, the adsorbent 14 has a Brunauer-Emmett-Teller (BET) surface area greater than about 50 square meters per gram (m2/g) and up to about 2,000 m2/g, and includes a plurality of pores having a pore size from about 0.20 nm (nanometers) to about 50 nm.
Examples of suitable adsorbents 14 include carbon (e.g., activated carbons, super-activated carbon, carbon nanotubes, carbon nanofibers, carbon molecular sieves, zeolite templated carbons, etc.), zeolites, metal-organic framework (MOF) materials, porous polymer networks (e.g., PAF-1 or PPN-4), and combinations thereof. Examples of suitable zeolites include zeolite X, zeolite Y, zeolite LSX, MCM-41 zeolites, silicoaluminophosphates (SAPOs), and combinations thereof. Examples of suitable metal-organic frameworks include HKUST-1, MOF-74, ZIF-8, and/or the like, which are constructed by linking tetrahedral clusters with organic linkers (e.g., carboxylate linkers).
The volume that the adsorbent 14 occupies in the container 12 will depend upon the density of the adsorbent 14. In an example, the density of the adsorbent 14 may range from about 0.1 g/cc to about 0.9 g/cc. A well-packed adsorbent 14 may have a density of about 0.5 g/cc. In an example, a 100 L container may include an amount of adsorbent that occupies about 50 L. For example, an amount of adsorbent that occupies about 50 L means that the adsorbent would fill a 50L container. It is to be understood, however, that there is space available between the particles of adsorbent, and having an adsorbent that occupies 50 L in a 100 L container does not reduce the capacity of the container for natural gas by 50 L.
The tank 10 may also include a guard bed (not shown) positioned at or near the opening 22 of the container 12 so that introduced natural gas passes through the guard bed before reaching the adsorbent 14. In examples, the guard bed may be to filter out certain components (e.g. contaminants) so that only predetermined components (e.g., methane and other components that are reversibly adsorbed on the adsorbent 14) reach the adsorbent 14. It is contemplated that any adsorbent that will retain the contaminants may be used as the guard bed. For example, the guard bed may include an adsorbent material that will remove higher hydrocarbons (i.e. hydrocarbons with more than 4 carbon atoms per molecule) and catalytic contaminants, such as hydrogen sulfide and water. In an example, the guard bed may include adsorbent material that retains one or more of the contaminants while allowing clean natural gas to pass therethrough. By retaining the contaminants, the guard bed protects the adsorbent 14 from exposure to the contaminants. The level of protection provided by the guard be depends on the effectiveness of the guard bed in retaining the contaminants. The pore size of the adsorbent in the guard bed may be tuned/formulated for certain types of contaminants so that the guard bed is a selective adsorbent.
In some instances, the adsorbent 14 may be regenerated, so that any adsorbed components are released, and the adsorbent 14 is cleaned. In an example, regeneration of adsorbent 14 may be accomplished either thermally or with inert gases. For one example, hydrogen sulfide may be burned off when the adsorbent is treated with air at 350° C. In another example, contaminants may be removed when the adsorbent is flushed with argon gas or helium gas. After a regeneration process, it is believed that the original adsorption capacity of adsorbent 14 is substantially, if not completely, recovered.
In an example of the method of making the natural gas storage tank, the container 12 may be formed and then the adsorbent 14 may be operatively disposed in the container 12. In another example of the method, the adsorbent 14 may be introduced during the manufacturing of the container 12.
Referring now to
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In the description of
Examples of the present disclosure may be implemented by using a refueling station to control a rate of flow of the natural gas into the container 12. Other examples may be implemented by using an electronic control unit 28 mounted on the vehicle to control valve mounted on the vehicle that, in turn, controls a rate of flow of the natural gas into the container 12. Still other examples may be implemented using temperature sensitive materials to control the vehicle mounted valve.
The present inventors have unexpectedly and fortuitously discovered that selectively utilizing/manipulating a similar effect on a container 12 containing an adsorbent 14 may lead to higher gas uptake. Adsorption-based natural gas (ANG) technology relies on physisorption. Adsorption becomes more significant when the temperature decreases. During the early part of the filling event, the in-container gas temperature can drop by over 10K which results in higher gas uptake from the adsorbent than what would be observed without a temperature change. The in-container gas temperature will then increase when the compression and conversion of supply enthalpy energy to container internal energy overcomes the Joule Thomson cooling effect, which becomes smaller as the container pressure increases. Although the gas in the tank may experience a temperature increase, the temperature of the adsorbent may take time to reach an equilibrium temperature with the gas. Since the adsorption capacity of the adsorbent is greater at cooler temperatures, the adsorbent adsorbs more natural gas during refueling. As the temperature of the adsorbent warms to equilibrium with the gas in the tank, some of the adsorbed gas is released. However, in examples of the present disclosure, it takes more time to warm the adsorbent than it takes to refuel. Therefore, the total mass of natural gas loaded into the tank is increased.
It is to be understood that examples of the present disclosure are distinct from systems and methods that use slow fill techniques. Slow fill may take hours for the temperature to equilibrate to fill a tank to capacity. Fast fill generally takes no longer to load natural gas in a vehicle than it would take to pump gasoline in a similar vehicle. In sharp contrast to examples of the present disclosure, conventional, uncompensated refueling stations filling conventional natural gas fuel tanks generally load more fuel in the tank with slow fill than fast fill. One reason that slow fill can add more fuel into a conventional fuel tank than fast fill is that the heat of compression of the gas in the tank is dissipated to the environment as quickly as the heat is generated. Another method of slow fill is to dissipate the heat of compression from the tank and “top off” the tank with diminishingly smaller amounts of natural gas when the tank temperature is at ambient.
Unlike examples of the present disclosure, some fuel fill methods use a fill rate that is slow enough that the adsorbent temperature rises as high as 10 degrees C. over ambient. As such, the adsorbent adsorbs less natural gas than the cooler adsorbent of examples of the present disclosure. In examples of the present disclosure, the fill rate may be increased by increasing the flow capacity of the tubing and valves between the refueling source and the container 12.
Advantages of examples of the present disclosure include higher storage capacity in tank 10, that could result in higher mileage when used as an on board storage and fuel delivery system.
It is to be understood that the ranges provided herein include the stated range and any value or sub-range within the stated range. For example, a range from about 0.1 g/cc to about 0.9 g/cc should be interpreted to include not only the explicitly recited limits of about 0.1 g/cc to about 0.9 g/cc, but also to include individual values, such as 0.25 g/cc, 0.49 g/cc, 0.8 g/cc, etc., and sub-ranges, such as from about 0.3 g/cc to about 0.7 g/cc; from about 0.4 g/cc to about 0.6 g/cc, etc. Furthermore, when “about” is utilized to describe a value, this is meant to encompass minor variations (up to +/−10%) from the stated value.
In describing and claiming the examples disclosed herein, the singular forms “a”, “an”, and “the” include plural referents unless the context clearly dictates otherwise.
It is to be understood that the terms “connect/connected/connection” and/or the like are broadly defined herein to encompass a variety of divergent connected arrangements and assembly techniques. These arrangements and techniques include, but are not limited to (1) the direct communication between one component and another component with no intervening components therebetween; and (2) the communication of one component and another component with one or more components therebetween, provided that the one component being “connected to” the other component is somehow in operative communication with the other component (notwithstanding the presence of one or more additional components therebetween).
Furthermore, reference throughout the specification to “one example”, “another example”, “an example”, and so forth, means that a particular element (e.g., feature, structure, and/or characteristic) described in connection with the example is included in at least one example described herein, and may or may not be present in other examples. In addition, it is to be understood that the described elements for any example may be combined in any suitable manner in the various examples unless the context clearly dictates otherwise.
While several examples have been described in detail, it will be apparent to those skilled in the art that the disclosed examples may be modified. Therefore, the foregoing description is to be considered non-limiting.
This application claims the benefit of U.S. Provisional Patent Application Ser. No. 61/806,170 filed Mar. 28, 2013, which is incorporated by reference herein in its entirety.
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Number | Date | Country | |
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20140290789 A1 | Oct 2014 | US |
Number | Date | Country | |
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61806170 | Mar 2013 | US |