METHOD AND APPARATUS FOR CONTROLLABLE STORAGE OF HYDROGEN

Abstract

A method and apparatus for controlling hydrogen gas storage in a clathrate hydrate structure through application of an electromagnetic field. The applied field can be used to control release of gas from the clathrate hydrate structure and/or uptake of gas into the clathrate hydrate structure. The electromagnetic field is arranged to promote hopping of gas molecules between and out of retaining pockets in the clathrate lattice by stimulating vibrations in the lattice that cause apertures into the retaining pockets to flex open. Advantageously, the electromagnetic field may have properties that are selected to promote an increase in the rate gas release or gas uptake without causing dissociation of the lattice. In this scenario, the invention can provide an energy-efficient, rechargeable on-demand supply system for any gas that can be retained within a clathrate hydrate structure.

Claims

1. A method for releasably storing hydrogen gas, the method comprising: forming a clathrate hydrate structure within a storage, volume, the clathrate hydrate structure comprising a lattice having a plurality of gas molecule retaining cavities in which molecules of hydrogen gas to be stored are trapped; and applying an electromagnetic field to the storage volume to controllably transfer the hydrogen gas from or to the clathrate hydrate structure, wherein a field strength of the electromagnetic field is selected to avoid dissociation of the clathrate hydrate structure.

2. A method according to claim 1, wherein the electromagnetic field is a microwave electromagnetic field.

3. A method according to claim 1 including adjusting a field strength of the electromagnetic field to control a transfer rate of the hydrogen gas from or to the clathrate hydrate structure.

4. A method according to claim 3, wherein the field strength of the electromagnetic field is non-zero and adjustable in a range up to 1% of an intrinsic field of the clathrate hydrate structure lattice.

5. A method according to claim 3, wherein a root mean square amplitude of the field strength of the electromagnetic field is adjustable within the range 0.000001 to 0.01 V/.

6. A method according to claim 1, wherein a field strength of the electromagnetic field is three or more magnitudes less than an intrinsic field of the clathrate hydrate structure lattice.

7. A method according to claim 1, wherein the electromagnetic field is applied in a pulsed manner.

8. A method according to claim 1 including monitoring temperature and pressure conditions in the storage volume.

9. A method according to claim 8 including determining a release rate of the hydrogen gas based on the temperature and pressure conditions, and providing a feedback signal for controlling the electromagnetic field based on the determined release rate.

10. A method according to claim 8 including detecting a temperature in the storage volume, and operating a coolant system based on the detected temperature to control the temperature condition in the storage volume.

11. A method according to claim 1, wherein the clathrate hydrate comprises an sII polymorph lattice structure having a plurality of larger gas molecule retaining cavities, and a plurality of smaller gas molecule retaining cavities occupied by the hydrogen gas.

12. A method according to claim 11, wherein the plurality of larger gas molecule retaining cavities are occupied by propane, methane or carbon dioxide.

13. An apparatus for releasably storing hydrogen gas, the apparatus comprising: a vessel defining a storage volume for containing a clathrate hydrate structure, the clathrate hydrate structure comprising a lattice having a plurality of gas molecule-retaining cavities in which molecules of hydrogen gas to be stored are trapped; an electromagnetic field generator arranged to emit an electromagnetic field across the storage volume to controllably release the hydrogen gas from the clathrate hydrate structure; and an outlet communicably connectable with the storage volume to permit the released hydrogen gas to exit the vessel, wherein a field strength of the electromagnetic field is selected to avoid dissociation of the clathrate hydrate structure.

14. An apparatus according to claim 13 including a controller arranged to selectively adjust a field strength of the electromagnetic field to control a release rate of the hydrogen, gas from the clathrate hydrate structure.

15. An apparatus according to claim 14 including: a temperature sensor arranged to monitor a temperature of the storage volume; and a pressure sensor arranged to monitor a pressure of the storage volume, wherein the temperature sensor and pressure sensor are communicably connected to the controller, whereby the controller is arranged to adjust the field strength of the electromagnetic field based on detected temperature and pressure conditions in the storage volume.

16. An apparatus according to claim 13 comprising an inlet communicably connectable with the storage volume to introduce a source gas.

17. An apparatus according to claim 13, wherein the outlet is connectable to a mains gas transmission network or to one or more fuel cells.

18. An apparatus according to claim 13 including a coolant system arranged to deliver a coolant to the vessel to maintain a temperature in the storage volume.

19. An apparatus according to claim 13 including a rocker mechanism arranged to agitate the vessel to promote clathrate hydrate formation.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Embodiments of the invention are described in detail below with reference to the accompanying drawings, in which:

[0033] FIG. 1 shows lattice structure of the sI and sII polymorph clathrate hydrates together with an enlargement of multiply-H.sub.2-occupied cage;

[0034] FIG. 2 is a graph showing how H.sub.2 storage capacity in a clathrate hydrate varies with pressure;

[0035] FIG. 3A is a graph showing a simulated change in the number of hydrate-like water molecules in hydrate cluster upon application of a range of electromagnetic field strengths;

[0036] FIG. 3B is a graph showing the results of mapping the graph of FIG. 3A into a macroscopic scenario;

[0037] FIG. 4 is a schematic diagram of a feedback control system for on-demand hydrogen release from pure/mixed hydrogen hydrates;

[0038] FIG. 5 is a schematic of an experimental set up to demonstrate controllable release and recharge of hydrogen in a clathrate hydrate according to the principles of the present invention; and

[0039] FIG. 6 is a graph showing how H.sub.2 hop rate increases with respect to a zero-field situation with increasing field intensity.

DETAILED DESCRIPTION; FURTHER OPTIONS AND PREFERENCES

[0040] The present invention relates in general to a technique for controlling release and reloading of clathrate hydrates in an energy-efficient manner. The technique is of particular interest for hydrogen storage and release, as it provides an avenue to achieve controllable on-demand hydrogen transfer to and from a clathrate hydrate at a commercially meaningful scale. However, the technique can be applied to gases other than hydrogen.

[0041] As discussed in detail below, the present invention utilises an externally-applied electromagnetic field to promote hydrogen transfer to or from a hydrogen-bearing clathrate hydrates without the need to dissociate the hydrate lattice. Through this technique, the latent heat cost associated with lattice dissociation can be avoided during hydrogen release. Furthermore, by avoiding lattice dissociation, the technique allows for efficient recycling of hydrogen to reload the lattice for subsequent (e.g. long-term or seasonal) storage.

[0042] When considering the energy balance of clathrate storage as a long-term, large scale solution, all steps such as compression of hydrogen, cooling hydrogen (and a THF/water solution for mixed hydrate) need to be considered. Of all these steps, latent-heat dissipation is the largest consideration. For example, at 3 MPa operation for mixed THF-H.sub.2 hydrate formation, this would be 350 kJ/kg, similar to ice, whilst it would be 300 kJ/kg for pure-H.sub.2 sII hydrate formation. This can be scaled up easily and used in large pressurised chambers. Given Winter-Summer variation in European power demand of 100 GW, 3 MPa storage of mixed THF-H.sub.2 hydrate at 1.5 wt % capacity would require only around 35-40 football-pitch-sized storage facilities each 10 m high, or similarly-sized subterranean salt caverns, with blending of the H.sub.2 into the existing natural-gas transmission network possible. As a means of obtaining a natural contribution to the pressure requirement, underwater storage (preferably in freshwater lakes to avoid possible corrosion problems) merits particular attention.

[0043] The principles of the invention are demonstrated below through application of an external electromagnetic field both to a prototype hydrate-formation rig and in a non-equilibrium molecular-dynamics simulation. The discussion below also touches on the microscopic origin of electromagnetic-field enhanced hydrogen release, based on experimental and simulation-based insights, and outlines control strategies for hydrogen release.

[0044] At its most general, the disclosure herein provides a method for controlling a release rate of gas (e.g. hydrogen gas) that is held within a clathrate hydrate structure. As discussed above, the invention is applicable to both pure and mixed hydrates, i.e. hydrates that store only hydrogen and hydrates that store hydrogen in combination with another gas (e.g. THF) that may be present to fill the larger cavities. The method may also be used with propane-hydrogen mixtures. Propane hydrates may form stable lattices at lower pressures (e.g. 1.5 to 2.0 MPa), although the storage capacity of such hydrates increases with pressure, so a balance between pressure costs and stored capacity needs to be struck.

[0045] The clathrate hydrate structures may be formed in a conventional manner within a storage vessel subjected to suitable selected temperature and pressure. Hydrogen can diffuse into and be retained by the clathrate hydrate structure. By maintaining the temperature and pressure parameters, hydrogen can be stored within the clathrate hydrate. Depending on the selected temperature and pressure there will be a natural base rate of hydrogen release, typically 0.13 kg/m.sup.3 at 3 MPa and a temperature of 260 K. The technique disclosed herein teaches applying an electromagnetic field across the vessel to promote release of the hydrogen, i.e. to cause the rate of hydrogen transfer to rise significantly above the base level.

[0046] The electromagnetic field may have properties selected to enhance the transfer of hydrogen. The selected properties may include field strength and frequency. As discussed in more detail below, the underlying principle of the invention is to use the external electromagnetic field to stimulate oscillation and stretching of the lattice in a manner that effectively widens one or more apertures into each cage for retaining the hydrogen, such that the hydrogen's ability to hop out of or between cages is enhanced. The frequency of the electromagnetic field may be selected to be stimulate lattice oscillations that cause desired stretching of the cages within the clathrate hydrate structure. For example, the frequency of the electromagnetic field may be of the same order as the natural vibration or libration frequency of the lattice, and in particular of a hexagon facet that makes up each cage within the lattice. The electromagnetic field may be a microwave field, e.g. having a frequency of 1 GHz or more, preferably in the range 1 to 5 GHz, more preferably around 2.45 GHz.

[0047] The field intensity (i.e. field strength) itself is selected to stimulate vibrations. Preferably the field intensity is selected to minimise adverse effects on the lattice, such as dissociation. The field intensity may thus be set to be many (e.g. 3 to 5) orders of magnitude less than the intrinsic field within the lattice structure, which is typically of the order of 1-3 V/.

[0048] The field intensity of the external electromagnetic field may be an adjustable parameter by which the release rate of gas from the clathrate hydrate is controlled. The field intensity may be adjustable within a range from 0.0001% to 1% of the intrinsic field, which may roughly correspond to a range within the range 0.000001 to 0.01 V/.

[0049] FIG. 6 is a graph that shows how hydrogen release rate varies compared with a zero-field situation for increasing field intensity E.sub.rms. An inter-cage hydrogen hopping rate, which governs the transfer rate of hydrogen into and out of the lattice, increases with field intensity within the range discussed above. For values higher than this range, thermal effects may significantly reduce the energy efficiency of the technique. For values lower than the range, the enhancement of release rate above the base leakage rate (i.e. the zero field situation) is negligible.

[0050] The electromagnetic field may be generated by any suitable source, e.g. a magnetron or the like. In one example, the electromagnetic field may be generated by a signal generator having a control module arranged to control the field strength or intensity based on a feedback signal. It may be advantageous to have an intelligently responsive signal generator in order to rapidly react to conditions within the vessel, e.g. to prevent unwanted thermal effects from degrading the hydrate structure or the like. The feedback signal may be derived from a separate temperature and/or pressure monitoring module that is operably connected to the vessel. Alternatively or additionally, the feedback signal may be derived from a signal indicative of rate of gas (e.g. hydrogen) release from the clathrate hydrate.

[0051] A particular advantage of the technique outlined above is that the properties of the external electromagnetic field can be selected to minimise dissociation of the clathrate lattice. Thus the release rate of the hydrogen can be controlled on demand without a concomitant adverse impact on the lattice.

[0052] Whilst it is known that hydrogen may be crudely released simply by depressurising the lattice, this technique provides little control and cannot preserve the lattice structure in a way that allows it to be reloaded with hydrogen.

[0053] By way of background to the invention, FIG. 3A is a graph showing the results of a non-equilibrium molecular dynamics simulation of hydrogen release from a clathrate hydrate lattice in a range of 2.45 GHz electromagnetic field strengths, as could be delivered by a magnetron or the like.

[0054] The simulation for FIG. 3A had an initial set up with 14,000 hydrogen molecules contained within the lattice, and shows the release rate of the molecules as the lattice is melted by various 2.45 GHz field strengths at 10 K above melting point. Line 30 indicates a zero-field situation for comparison. Line 32 indicates a field strength (r.m.s.) of 0.005 V/. Line 34 indicates a field strength of 0.025 V/. Line 36 indicates a field strength of 0.05 V/. Line 38 indicates a field strength of 0.065 V/.

[0055] FIG. 3B shows a graph in which the results of FIG. 3A are scaled up over macroscopic times and realistic (i.e. lower) field intensities to provide a prediction for time- and energy-needs associated with clathrate hydrate break up. To do this, the simulation results were fitted with a break-up model shown in FIG. 3B and then scaled using a Transient Time Correlation Function (TTCF) foundation.

[0056] The graph in FIG. 3B shows reduction in mass of hydrate over time for each field intensity examples. Line 40 corresponds to a zero-field situation. Line 42 corresponds to the field strength of 0.005 V/. Line 44 corresponds to the field strength of 0.025 V/. Line 46 corresponds to the field strength of 0.05 V/. Line 48 corresponds to the field strength of 0.065 V/.

[0057] The minimum energy case in FIG. 3B corresponds to line 48 (i.e. the 0.065 V/A (r.m.s.) field intensity). The energy cost associated with release of around 28 g of hydrate in this case is 43 kJ/kg over 1.25 days in a 1 kV/m (10.sup.7 V/) field.

[0058] FIG. 4 is a schematic diagram of a feedback control system for hydrogen release of the system disclosed herein. Output parameter X represents a desired quantity of hydrogen desired. The control agent is the applied electromagnetic field applied (intensity and frequency) in the Laplace domain. Parameter N represents background noise (usually negligible) and function block T represents a transfer function of the controlled-dissociation process discussed above, which varies according to electromagnetic field absorption conditions, and can be found from Laplace transformation of the time-domain differential equations mentioned above. Function block H represents a feedback-loop transfer function, which can be approximated as unity, given that there is little time delay in measuring in-line hydrogen release by industry-standard gas gauges. Parameter R represents change in desired set-point for output parameter X, depending on gas-grid-demand fluctuations and typically changing slowly for seasonal applications. Function block K.sub.c represents the controller (e.g., PID, etc.) for adjusting the properties of the control agent to yield the desired output. Other control strategies, e.g., wave-based control, could also be employed.

[0059] The simulations shown in FIGS. 3A and 3B model gas-hydrate dissociation (and the associated on-demand hydrogen release, e.g. for incorporation into the existing gas-transmission grid via blending). In itself, this work shows that the use of clathrate hydrate structure presents an energetically-feasible means of controlling hydrogen release, with manageable latent-heat handling.

[0060] However, the disclosure herein goes beyond this work in demonstrating non-dissociation of the clathrate upon exposure to electromagnetic fields with parallel partial hydrogen transfer (i.e. net release or net uptake, depending on the circumstances). This technique enhances the principles outlined above to offer even better control over desired release on-demand, e.g., for use with demand-forecasting without the need/cost to provide for (primarily latent-) heat management. This renders the hydrogen-release process an order of magnitude less in energetic cost, leading to great energy savings.

[0061] Using mixed sII propane/hydrogen hydrates, stored initially at 30 bar, with propane in the large cages and hydrogen in the small ones, some 1.8 kg/m.sup.3 or 0.2 GJ/m.sup.3 of hydrogen can be released within 10 hours (corresponding to some 11-12% of hydrogen in singly-occupied small cages at an electromagnetic-field and thermal-management energy cost of as low as 0.027 GJ/m.sup.3 in low-intensity e/m fields). Importantly, this can be done in a multiply-recyclable manner (i.e., with subsequent reloading of the hydrate lattice via exposure to higher-pressure hydrogen gas) without break-up of the lattice.

[0062] The discussion below explains how this has been achieved both experimentally and via non-equilibrium molecular-dynamics simulation.

[0063] FIG. 5 shows a schematic drawing of hydrogen storage and release system 100 that is an embodiment of the invention. The system 100 comprise a vessel 102 for containing the clathrate hydrate under pressurised conditions. In this experiment, the vessel was a 200 bar-rated, 0.3 litre pressure-vessel, but it can be understood that any suitable container can be used, and in particular that the apparatus discussed herein is capable of scaling up to industrial-size systems.

[0064] The vessel 102 is provided within a coolant system (e.g. a Julabo refrigeration unit), where flow of a cooling agent around a coolant circuit from a coolant source 104 is controlled to maintain a temperature within the vessel 102. The cooling agent flows along an inflow line 105 and an outflow line 107.

[0065] The vessel 102 defines an internal volume for containing the clathrate hydrate. In this example, the internal volume has a gas inlet 110 connected to a gas distribution unit 111, e.g. for introducing a gas or gas mixture to be stored within the clathrate hydrate, such as hydrogen, propane, THF or the like. The gas or gases to be introduced may be supplied to the distribution unit 111 from any suitable source. In FIG. 5, there is a propane source 141, a hydrogen source 143 and a methane source 145. A vacuum pump 114 is connected to the distribution unit 111 to drive gas flow around the circuit, e.g. to purge pipes following the introduction of gas into the vessel.

[0066] The temperature of the internal volume can be monitored by a thermocouple 108, which in turn sends a feedback signal to a controller 106 that is operably connected to the coolant source 104. The internal volume is also in fluid communication with pressure monitoring apparatus 122, which is arranged to send a feedback signal to the controller 106.

[0067] The gas inlet 110 has attached to it a valve 112 for prevent back flow from the vessel and a flowmeter 113 for measuring a flow rate of gas introduced into the internal volume. The internal volume may also have a liquid inlet (not shown) for introducing the liquid (e.g. water) used to form the clathrate structure. The liquid inlet may include its own control valve. In other arrangements, the liquid may be introduced into the vessel through a top surface therefore, which is then closed by a suitable cover. The gas inlet 110 may be in the cover.

[0068] In use, gases are supplied to the vessel through the distribution unit, with line-cleaning before purging the desired gas, by way of mass-flow controller and accurate measurement of gas loading into the internal volume (which in this example is pre-loaded with the liquid to form the lattice of the clathrate hydrate). The system can operates under either isobaric or constant-gas-mole-number modes, with a back-pressure cylinder 120 for isobaric operation. For the constant-mole-number case, the inlet valve 112 is closed upon reaching the desired pressure. Pressure can be logged digitally via the pressure gauge 122 periodically (e.g. every 2 to 10 seconds).

[0069] The internal volume further has an outlet 118 extending from a upper side thereof. The outlet 118 is in fluid communication with a gas release pipe 130. Gas released from the clathrate hydrate and other exhaust gases can flow through the outlet 118 and be directed for further use via the gas release pipe 130.

[0070] In this example, the vessel 102 is mounted on a rocker mechanism 142 for agitating the contents of the internal volume (e.g. at a frequency of 30 Hz or the like) to facilitate formation of the clathrate lattice. A magnetic stirrer may also be provided to agitate fluid within the internal volume, thereby enabling a fast rate of hydrate formation via mass transfer and diffusion. Although these components assist in forming the clathrate, they may not be essential for operation of the invention.

[0071] To apply an electromagnetic field within the internal volume, one or more planar conductive coils 138 are disposed in or around the internal volume. In this example there are three planar coils distributed in a vertical orientation within the internal volume, but it can be understood that any suitable distribution of radiating elements may be used having regard to the size and shape of the internal volume of the vessel being used.

[0072] The coils are electrically connected to a field generator 140, e.g. a magnetron or the like, via high-a current electrical isolation valves or glands (not shown) for safety. This arrangement allows exposure of the vessel interior to roughly uniform electromagnetic fields in the microwave-frequency range. With this system, it was possible to study the effect of low-intensity electromagnetic field exposure in terms of hydrogen liberation without any dissociation of the hydrate. The field generator 140 is communicably connected to the controller 106 to allow adjustment of the field strength based on the detected temperature and pressure.

[0073] By agitation on the rocker, a pure propane hydrate was prepared at 260 K at initial 5.5 bar 99.5% pure-propane exposure, using 100 ml of deionised water in contact with propane. Changes in temperature and pressure monitored by the thermocouple 108 and pressure gauge 122 were used to confirm the formation of gas hydrates. Data-acquiring software was used to register/record pressure evolution as a function of time, to show the take-up or release of gas. By evolution of the gas-phase pressure, it was found that there was 90% of maximum theoretical occupancy (based on large-cavity occupation in sII hydrate).

[0074] Upon exposure to hydrogen, a similar occupancy ratio was found for hydrogen in the now-mixed hydrate (based on single occupation of sII small cavities). By setting pressure to 3 MPa and maintaining temperature at 260 K with refrigeration-thermostatting control, the sample was then exposed to a 2.45 GHz electromagnetic field with estimated field intensity of 265 V/m.

[0075] Based on recorded pressure evolution, this step led to the release of 1.8 kg/m.sup.3 or 0.2 GJ/m.sup.3 of hydrogen within 10 hours. This corresponds to 11-12% of the hydrogen stored in singly-occupied small cages. The energy cost of the electromagnetic field generation and refrigeration-thermostatting control was around 0.027 GJ/m.sup.3.

[0076] This release rate compares to only 0.13 kg/m.sup.3 released with initial 3 MPa storage pressure under zero-field conditions.

[0077] After the experiment, the hydrate was weighed, and no dissociation of the lattice was confirmed: the mass measurements correlated with pressure-in-fixed volume rise in terms of the liberated hydrogen gas. This offers prima facie proof-of-concept evidence of the viability of the proposed energy-efficient scheme, which can easily be incorporated with a control system for hydrogen-demand management as discussed above with reference to FIG. 4.

[0078] Upon exposure to higher-pressure hydrogen gas after electromagnetic field-mediated partial release of hydrogen, it was found that the hydrogen could be recycled, or reloaded, into the lattice again and the e/m-field exposure and partial release repeated with reasonable reproducibility.

[0079] For non-equilibrium MD, a TIP4P-2005 water model was used for intermolecular water-water interactions. The charge and Lennard-Jones (LJ) parameter-set defined by Alavi et al. in Molecular-dynamics study of structure II hydrogen clathrates (J Chem Phys 2005, 123: 024507) was used for intermolecular H.sub.2-H.sub.2, together with their combining rules for water-H.sub.2. These intermolecular potentials have proven reasonable for describing hydrate structural, dynamical and H.sub.2-diffusion properties, making calculations with these models useful for comparison with previous studies. It has also been shown that the Alavi intermolecular water-H.sub.2 surface can give good predictions of the measured incoherent neutron scattering data for various transitions. Also, it has been shown that TIP4P-2005 provides reasonable agreement with neutron-scattering derived phonon spectra for sI and sII hydrates.

[0080] All simulations used a 555 sII propane-H.sub.2 clathrate hydrate unit cell (with single occupation of small cages by H.sub.2) with vanishingly-small dipole, in contact with an equivalent volume of free space in the laboratory z-axis, under periodic boundary conditions, with the lattice 110 surface orientation towards the vacuum layer. In the simulation, electromagnetic fields having a frequency of 2.45 GHz were applied using the TTCF approach at a r.m.s. intensity of 2.65 kV/m over 0.5 s, while the temperature was maintained under NVT conditions with a Ewald electrostatics and Nose-Hoover thermostat set at 0.5 s and 260 K.

[0081] The initial pressure was set at 3 MPa and the hydrate remained stable throughout, but the release rate stabilised at only about three times higher than the experimental one (when rescaled for field intensity and exposure time). This indicates the utility of NEMD to capture the essential details semi-quantitatively of electromagnetic-field-enhanced H.sub.2 hopping release mechanisms. It was observed that the modus operandi of this process lies in roto-translational coupling, in that the water dipoles' rotational coupling and oscillation with the applied field enhances the librational (rotation-oscillation) dynamics of the cage faces in the sII lattice. This causes larger-amplitude stretching of the cage faces allows for enhanced squeezing through the cages (lowering the free-energy barriers for inter-cage migration), and enhancing H.sub.2-hopping diffusion and, ultimately, partial H.sub.2 release from the hydrate itself.

[0082] Based on non-equilibrium molecular dynamics (NEMD) simulation and experimental evidence, the disclosure herein provides a method and apparatus for electromagnetic-field controlled hydrogen release from clathrate hydrates (especially lower-pressure mixed hydrates). The especially exciting discovery is the possibility of non-dissociation of the lattice, and re-loading and re-cycling of hydrogen for repeated cycles, thereby enabling energy-efficient and easily-controlled partial hydrogen release to manage grid demand. This accelerates kinetics substantially, and obviates the need for energy- and operationally-demanding heat management.