The field to which the disclosure generally relates includes hydrogen storage and supply systems.
Hydrogen is a clean and efficient energy source for fuel cells and internal combustion engines. One of the hurdles for adopting hydrogen as a commercially viable fuel is the technical difficulty of building an economical and reliable hydrogen storage and distribution system. Particularly, reliable and economical storage of hydrogen for extended periods of time is technically challenging. Hydrogen storage in compressed gas requires high pressure. At such high pressure, hydrogen gas can diffuse through the container over time. Tank failure and damage can also be a problem in high pressure storage. High pressure containers also add significant mass to a mobile storage unit. Hydrogen can also be stored in the form of metal hydrides. But metal hydrides can contribute to contaminants. Additionally, metal hydrides can add 50 times more weight than that of the stored hydrogen. Liquid hydrogen can be stored at low temperature (<100° K) and relatively low pressure. Due to large temperature differences between the liquid hydrogen and the surrounding environment, natural parasitic heat can leak into a hydrogen storage tank over an extended period of time. Such parasitic heat can cause conversion of some of the liquid hydrogen into hydrogen gas, resulting in a pressure rise inside the tank. Eventually, a certain amount of hydrogen gas may need to be vented in order to avoid overpressure in the tank. As a result, liquid hydrogen storage can experience high boil off rates and short times before a given temperature increase will cause a boil off valve to reach its pressure set-point and open to relieve pressure in the tank.
In one embodiment, a storage device for liquefied or condensed hydrogen is provided. The device comprises an inner tank, an outer jacket, a vacuum insulation between the inner tank and the outer jacket, and a catalyst disposed inside the inner tank. The catalyst is capable of converting para-hydrogen to ortho-hydrogen at temperatures between about 20° K to about 80° K.
In another embodiment, a hydrogen supply system is provided. The hydrogen supply system comprises a storage vessel having a para-hydrogen to ortho-hydrogen conversion catalyst disposed in the inner tank, a liquefied or condensed hydrogen having sufficient contact with the catalyst at a temperature between about 20° K to about 80° K, and a boil off valve that limits the pressure inside the inner tank to the range of about 4 to 30 bar.
Another embodiment includes a process of storing and supplying hydrogen fuel.
Other exemplary embodiments will become apparent from the detailed description provided herein. It should be understood that the detailed description and specific examples, while disclosing exemplary embodiments of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Exemplary embodiments of the present invention will become more fully understood from the detailed description and the accompanying drawings, wherein:
The following description of the embodiments is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses.
One embodiment of a hydrogen storage vessel and supply system is shown schematically in the drawing of
Another embodiment of a hydrogen storage vessel and supply system is shown schematically
As shown in the above two embodiments in
The outer jacket 10 can be made of any material or combination of materials having suitable strength and permeability characteristics. The outer jacket 10 may be impermeable to air and can be chosen such that its strength is sufficient to withstand the stresses created by a vacuum that may exist in the insulation layer 20. Suitable outer jacket materials may include, but are not limited to, plastics, metals, fiber composites, ceramics, other materials, any combination thereof, and in some exemplary embodiments may include multiple layers of the same or different materials.
The inner tank 30 may be made of any material or combination of materials having suitable strength and permeability characteristics. It is preferably at least partially, or substantially completely, impermeable to hydrogen liquid and gas at relatively low pressures (4-60 bars). The material or materials may be selected to have high strength at low temperatures to withstand stresses generated by a potentially large pressure differential between the low pressure vacuum insulation outside the inner tank and high pressure hydrogen inside the inner tank, particularly in embodiments where such a differential exists. Various metals, ceramics, fiber composites and other materials alone or in combination can be used to construct the inner tank. A fiber composite lined with aluminum or an aluminum alloy may be preferred due to the hydrogen barrier properties of aluminum and its alloys and additionally due to its relatively lightweight as a metal. One example of a fiber composite suitable for use in construction of the inner tank includes fibers having high mechanical strength at low temperature, high modulus, and low elongation. Aramide fibers, such as KEVLAR™ marketed by DuPont, fiber glass, and carbon fibers are some non-limiting examples of suitable fibers. Additional details of constructing an exemplary composite vessel material is described in Baur L., 1995, “Composite Pressure Vessel with Metal Liner for Compressed Hydrogen Storage,” Proceedings of the 1st IEA Workshop on Fuel Processing for Polymer Electrolyte Fuel Cells, Paul Scherrer Institut, Villigen, Switzerland, International Energy Agency, Swiss Federal Office of Energy, Sep. 25-27, 1995, p. 45-69. But of course this is only one of several examples of suitable composite material usage in for the inner tank 30.
The vacuum insulation 20 is preferably a multilayer vacuum super insulation (MLVSI), as described in Aceves, S. M., Berry, G. D., 1998, “Thermodynamics of Insulated Pressure Vessels for Vehicular Hydrogen Storage,” ASME Journal of Energy Resources Technology, June, Vol. 120, pp. 137-142. The vacuum inside the insulation is preferably less than about 0.01 Pascal. Microsphere, foamed materials, and/or certain insulating fibers can be used to form such multilayer vacuum insulation.
Liquid hydrogen has a boiling point of 20.28° K. It can be stored at about 20°-50° Kelvin. The temperature requirements for liquid hydrogen storage necessitate expending a great deal of energy to compress and chill the hydrogen into its liquid state.
Hydrogen may also be adsorbed onto solid adsorbents such as activated carbon, carbon nanotubes, metal organic frameworks and graphite fibers at cryogenic temperatures. Hydrogen adsorbed on solid adsorbent at cryogenic temperatures is referred to herein as condensed hydrogen. Condensed hydrogen can be stored at relative higher temperatures than liquid hydrogen.
A boil off safety valve 50 may be connected to the inner tank to limit the hydrogen storage pressure between about 2 bar and about 60 bars, and preferably, between about 4 and about 30 bars. When the pressure inside the inner tank rises to the upper limit set for the boil off valve, the valve can automatically open to vent hydrogen gas away from the inner tank. Such venting process not only reduces the pressure in the inner tank for safety reasons, but also cools the inner tank. The resultant cooling due to gas expansion and evaporation of liquid hydrogen can slow any pressure rise in the tank. The margin of safety concerning liquid or condensed hydrogen storage is a function of maintaining tank integrity and preserving the temperatures that liquid or condensed hydrogen requires. The venting mechanism of the boil off valve can be controlled mechanically or electronically. Any pressure regulating vent valves known in the art can be used as the boil off valve.
The spins of the atomic nuclei in a hydrogen molecule can be coupled in two distinct ways: with nuclear spins parallel (ortho-hydrogen) or nuclear spins anti-parallel (para-hydrogen). Because molecular spins are quantized, ortho- and para-hydrogen exist in different quantum states. As a result, there are differences in many properties of the two forms of hydrogen. In particular, those properties that involve heat, such as enthalpy, entropy, and thermal conductivity, can show definite differences for ortho- versus para-hydrogen. Para-hydrogen is the lower energy form of hydrogen at liquid state.
As can be seen in
When temperature rises during extended period of storage, para-hydrogen in a storage tank does not get converted into the equilibrium composition of ortho- and para-hydrogen in the absence of a catalyst. In some known storage systems where evaporated hydrogen is cooled and recycled into liquid hydrogen, it may be desirable to maintain para-hydrogen composition in storage even when the temperature fluctuates over 20° to 80° K range. In those types of systems, contact of stored hydrogen with a catalyst is necessarily avoided.
In storage and supply systems such as those shown in
The catalyst may include any materials that are capable of catalyzing the conversion of para-hydrogen to ortho-hydrogen in the temperatures between about 20° K and about 80° K. Suitable catalysts include, but are not limited to, iron oxide (especially iron(III) oxide), platinum, rhenium, ruthenium, rhodium phosphine complexes, Group IV-VI transition metal nitrides, samarium copper, potassium-triphenylene complex, titanium carbide, manganese carbides, chromia-alumina, molybdenum-alumina, sodium hydride, chromium potassium sulfate, copper-nickel zeolite, cobalt zeolite, manganese oxide, carbonaceous substances such as graphite, and any combination/mixtures thereof. The catalyst should be relatively pure, and should not contribute to any gaseous contaminants such as carbon monoxide, ammonia, sulfur compounds or other contaminants. In one embodiment as shown in
One effect of the catalyst on hydrogen storage according to the invention can be described with reference to
The curve for para-hydrogen represents the condition where liquefied para-hydrogen is filled in a tank without any catalyst. Because, as explained above, the conversion process from para- to ortho-hydrogen is very slow, the hydrogen remains in its pure para-hydrogen state without any significant conversion to ortho-hydrogen in the temperature range of 20° K-60° K. As indicated in
Where a catalyst is included in the inner tank as in the embodiments shown and described in
When the exemplary storage vessels described herein are initially filled with liquefied para-hydrogen at about 20.2° K in the presence of the catalyst, it is converted to equilibrium hydrogen. As a result, it takes much more parasitic heat leak to raise the temperature from 20.2° K to 50° K due to the increase in heat capacity of the stored hydrogen. The increase in heat capacity for equilibrium hydrogen at temperature range of 20°-50° K is due to the additional energy required for the conversion of a portion of para-hydrogen to ortho-hydrogen. Such dramatic increase in heat capacity can significantly slow temperature and pressure rises in the inner tank, thus extending the dormancy time of the stored hydrogen. In one embodiment, the temperature of stored hydrogen is in the range of 20°-80° K, and preferably 20°-60° K. As also shown in
The beneficial effect of the hydrogen storage and supply system described herein can also be demonstrated with reference to
Loss free dormancy time of the hydrogen storage and supply system can calculated at different boil off pressures and compared to a similar system without the use of a catalyst. Loss free dormancy time as used herein is defined as the time for a storage system starting at 26° K at 4 bar to reach a pre-set boil off pressure. Relative dormancy gain is the calculated percentage increase in loss free dormancy time of the storage and supply system that includes a catalyst, and is thus storing hydrogen in its equilibrium state, compared to that of a similar system without a catalyst, which would be storing hydrogen in its para-state. Relative dormancy gain curves of different filling levels (indicated in g/l) and boil off pressures (indicated in MPa) are shown in
By way of example and explanation of the chart in
Filling level is the weight of filled hydrogen per unit volume of the storage space in the inner tank. A filling level of 5 to about 60 gram/liter is suitable. As shown in
Since most of the heat leaks occur through the wall of the inner tank, the catalyst coating on the interior surface of the inner tank is most efficient in converting the heat leak into energy for para- to ortho-hydrogen transformation. The catalyst coating can be easy produced by spray coating, dip coating, vapor deposition, sputtering, and other methods known in the art.
The storage vessel and system may also include other features and components. The access and vacuum port 70, for example, can be used to provide and maintain high vacuum for the insulation. It can also serve as the port for repairs and for placing temperature and pressure monitoring probes. To further extend the loss free dormancy time, an evaporative vapor shield can also be provided. The storage and supply system may have a separate discharging line and filling line. The discharging line can provide hydrogen gas output and the filling line can allow the inflow of liquefied hydrogen to fill the inner tank.
The hydrogen storage and supply system is especially suitable as a mobile unit to supply hydrogen fuel to an internal combustion engine or a fuel cell. In one embodiment, the storage and supply system can be filled initially with liquefied hydrogen that was previously catalytically converted into greater than 90% para-hydrogen at about 20°-30° K. The storage and supply system is then connected to the fuel line of a fuel cell or an internal combustion engine. For example, the embodiments as shown in
The above description of embodiments of the invention is merely exemplary in nature and, thus, variations thereof are not to be regarded as a departure from the spirit and scope of the invention.