Device for transporting liquid hydrogen

Abstract

The present invention, according to a first aspect, relates to a device for transporting liquid hydrogen, comprising a liquid hydrogen tank and a cooling system, the tank (9) comprising: - a cavity (11) which is delimited by an inner wall (2), the cavity (11) being configured to receive liquid hydrogen at a temperature (TH) of lower than an ambient temperature (TA) of the air around the tank (9); and - a first wall (5, 5') which is arranged around the inner wall (2) and delimits an empty space (8) between the inner wall and the first wall (5, 5'), the cooling system comprising at least one pipe (4) which is in contact with the first wall (5, 5'), the pipe (4) being configured to circulate liquid nitrogen at an intermediate temperature (TI) between the ambient temperature (TA) and the temperature (TH) of the liquid hydrogen.

Description

[0001] DESCRIPTION

[0002] TITLE: Liquid hydrogen transport device

[0003] FIELD OF THE INVENTION

[0004] The invention relates to the storage and transport of liquid hydrogen in tanks, and more particularly to the management of thermal flows between the liquid hydrogen and the ambient air located around the tank.

[0005] STATE OF THE ART

[0006] Hydrogen occurs naturally in its diatomic form (H2), in liquid or gaseous form. In all that follows, the terms "liquid hydrogen" and "gaseous hydrogen" will be used to refer to dihydrogen in its liquid and gaseous form respectively.

[0007] In order to be able to store or transport a large mass of hydrogen in a limited volume, several solutions are known from the state of the art. First, it is possible to store hydrogen in its gaseous form under high pressure, so as to increase its density, and to allow a given mass of hydrogen to be stored in a tank of limited volume. However, compressing hydrogen consumes a lot of energy, and its storage in pressurized form presents risks of leaks, detonation or deflagration, so particularly robust materials to form the tanks and strict control are necessary. In addition, compression presents constraints of use, particularly for large quantities of hydrogen. Filling is particularly long and complex for tanks with a capacity greater than 100 kg.

[0008] It is also known to store or transport hydrogen in liquefied form. Indeed, since the density of gaseous hydrogen is approximately 0.09 g / L, while that of liquid hydrogen is 71 g / L at atmospheric pressure, the volume required to store an equivalent mass of hydrogen in its gaseous form is reduced by nearly 800 times. The volume gain is significantly greater than that obtained by simple pressurization of gaseous hydrogen: at 700 bar, the density of gaseous hydrogen is only approximately 40 g / L. In addition, storing hydrogen in liquid form solves some of the problems discussed previously. In particular, liquid hydrogen can be stored at ambient pressure, reducing the risks associated with the high pressure of pressurized gaseous hydrogen.

[0009] Storing and transporting hydrogen in liquid form, however, has its own drawbacks. The condensation point of hydrogen is approximately 20 Kelvin (equivalent to approximately -253°C) at a pressure of 1 bar (atmospheric pressure). When transporting hydrogen over long distances, the heat flow between the ambient air and the liquid hydrogen through the tank walls, resulting from conductive and radiative phenomena, vaporizes some of the hydrogen. Due to the aforementioned difference in density between liquid and gaseous hydrogen, the pressure in the tank increases due to this evaporation. To limit the increase in pressure in the tank, it is then necessary to regularly degas the tank during hydrogen transport - this is generally referred to as "boil-off" losses.Depending on the tank's structure, it may be necessary to degas every few minutes to a few hours. For example, for a cylindrical tank two meters in diameter and five meters long containing one ton of liquid hydrogen, up to several tens of kilograms of hydrogen can be lost per day.

[0010] A solution envisaged by the state of the art to avoid this evaporation and the degassing that it imposes is to use a cryogenic cooler imposing a temperature of 20 K (or close to 20 K, i.e. between 20 K and 35 K approximately depending on the storage pressures envisaged). Such a cooler makes it possible to absorb the heat inputs coming from the outside, and can also make it possible to recondense the evaporated hydrogen so as to limit the increase in pressure occurring in the tank, and therefore the need for degassing. However, such devices are bulky and consume a lot of electrical energy, which makes their use unsuitable for transporting a tank of liquid hydrogen.

[0011] STATEMENT OF THE INVENTION

[0012] One objective of the present application is to enable the transport of liquid hydrogen over long distances in a tank, while limiting the evaporation of hydrogen and the resulting mass losses during degassing of the tank. Another objective of the application is to provide a liquid hydrogen transport solution that is compact and has limited energy consumption while limiting the losses of liquid hydrogen by evaporation which are of the order of 1% per day for cryogenic storage with vacuum insulation and multi-layer insulation (or MLI, for "Multi-Layer Insulation") according to the state of the art.

[0013] To this end, the present disclosure relates, according to a first aspect, to a device for transporting liquid hydrogen, comprising a liquid hydrogen tank and a cooling system, the tank comprising: a cavity delimited by an internal wall, the cavity being configured to receive liquid hydrogen at a temperature lower than an ambient temperature of the air around the tank, a first wall arranged around the internal wall and delimiting an empty space between the internal wall and the first wall, the cooling system comprising at least one pipe in contact with the first wall, the pipe being configured to circulate liquid nitrogen at an intermediate temperature between the ambient temperature and the temperature of the liquid hydrogen.

[0014] According to one embodiment, the liquid hydrogen transport device comprises a plurality of liquid hydrogen tanks, each tank comprising a first wall, the cooling system comprising a single pipe in contact with the first wall of each tank, the pipe being configured to circulate liquid nitrogen from a liquid nitrogen tank.

[0015] According to one embodiment, the liquid hydrogen transport device comprises a plurality of liquid hydrogen tanks, and each tank comprises a first wall, the cooling system comprising several pipes, each pipe being in contact with the first wall of a tank, each pipe being configured to circulate liquid nitrogen from the same liquid nitrogen tank. According to one embodiment, the first wall is an external wall of the tank having an internal surface facing the internal wall and an external surface, an insulating foam surrounding the first wall on its external surface.

[0016] According to one embodiment, the first wall is an intermediate wall located between the inner wall and an outer wall of the tank, an empty space being interposed between the first wall and the outer wall.

[0017] According to one embodiment, the pipeline is in fluid connection with at least one liquid nitrogen tank adapted to be maintained at the intermediate temperature.

[0018] According to one embodiment, the cooling system comprises a cryogenic machine configured to maintain the nitrogen circulating in the pipeline at the intermediate temperature and / or to allow condensation of nitrogen vapors in the pipeline.

[0019] According to one embodiment, the hydrogen tank and the at least one liquid nitrogen tank are arranged in the same cryostat.

[0020] According to one embodiment, the cooling system comprises several pipes, each pipe being connected to a respective liquid nitrogen tank, each pipe being in contact with a different portion of the first wall.

[0021] According to one embodiment, the liquid hydrogen transport device further comprises a second pipe located outside the cavity and in contact with the internal wall and configured to circulate liquid nitrogen at an internal wall temperature, the internal wall temperature being greater than or equal to the temperature of the hydrogen and less than ambient temperature, the internal wall temperature preferably being substantially equal to the temperature of the hydrogen.

[0022] A second aspect of the present disclosure relates to a method for cooling a liquid hydrogen tank, the tank comprising: a cavity delimited by an internal wall, the cavity being configured to receive liquid hydrogen at a temperature lower than an ambient temperature of the air around the tank, a first wall arranged around the internal wall, delimiting an empty space between the internal wall and the first wall, the method comprising cooling the first wall by circulating liquid nitrogen in a pipe in contact with the first wall, the liquid nitrogen having an intermediate temperature between the temperature of the hydrogen and the ambient temperature.

[0023] According to one implementation, the method is a method of cooling a plurality of hydrogen tanks, each tank of the plurality of tanks comprising a first wall, the first wall being located between the inner wall and an outer wall of the tank, an empty space being interposed between the first wall and the outer wall, the method comprising cooling the first wall by circulating liquid nitrogen in a single pipe in contact with each first wall of each tank of the plurality of tanks, the single pipe being supplied by a single tank of liquid nitrogen.

[0024] According to one implementation, the method is a method of cooling a plurality of hydrogen tanks, each tank of the plurality of tanks comprising a first wall, the first wall being located between the inner wall and an outer wall of the tank, an empty space being interposed between the first wall and the outer wall, the method comprising cooling each first wall by circulating liquid nitrogen in a separate pipe in contact with the first wall, the pipes being supplied by the same liquid nitrogen tank.

[0025] According to one implementation of the method, the temperature of the hydrogen is substantially 20 Kelvin and the intermediate temperature is substantially 80 Kelvin.

[0026] A third aspect of the present disclosure relates to a container comprising a hydrogen transport device as described above, the container being configured to be placed on board a vehicle, the vehicle being chosen in particular from a truck, a train or a boat.

[0027] A fourth aspect of the present disclosure relates to a liquid hydrogen transport vehicle comprising a liquid hydrogen transport device as defined above, or a container as defined above.

[0028] DESCRIPTION OF FIGURES

[0029] Other characteristics, aims and advantages of the invention will emerge from the following description, which is purely illustrative and non-limiting, and which must be read in conjunction with the appended drawings in which:

[0030] - Figure 1 schematically illustrates a liquid hydrogen transport device according to a first aspect of the invention,

[0031] - Figure 2 schematically illustrates a liquid hydrogen transport device according to a second aspect of the invention,

[0032] - Figure 3 schematically illustrates a liquid hydrogen transport device according to a third aspect of the invention.

[0033] - Figure 4 schematically illustrates a liquid hydrogen transport vehicle according to a fourth aspect of the invention.

[0034] - Figure 5 schematically illustrates an embodiment of a liquid hydrogen transport vehicle.

[0035] - Figure 6 schematically illustrates an embodiment of a liquid hydrogen transport vehicle. In all the figures, identical reference signs designate the same elements.

[0036] DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

[0037] A first aspect of the invention relates to a liquid hydrogen transport device 1 as shown in FIG. 1. It comprises a reservoir 9 provided with an internal cavity 11, configured to accommodate, at least in a portion of the cavity 11, a volume of liquid hydrogen at a temperature T lower than the ambient temperature TA of the air surrounding the reservoir 9. Another portion of the internal cavity 11 can accommodate gaseous hydrogen, in particular resulting from the evaporation of the liquid hydrogen contained in the cavity 11. The internal cavity 11 is delimited by an internal wall 2.

[0038] In order to prevent the inner wall 2 from being subjected to a significant temperature gradient between, on the one hand, the temperature of the external ambient air TA and the temperature T of the hydrogen in the inner cavity 1 1 , a first wall 5, 5' surrounds the inner wall 2 so that an empty space 8 exists between the inner wall 2 and the first wall 5, 5'. This empty space makes it possible to create a buffer zone between the inner cavity 1 1 and the ambient air, this buffer zone having a temperature between the temperature of the liquid hydrogen T and the ambient temperature TA, and ensuring thermal insulation between the liquid hydrogen and the air surrounding the first wall 5, 5'.

[0039] Alternatively, the empty space 8 can be filled with perlite beads, which also provide thermal insulation between the inner wall 2 and the first wall 5, 5'.

[0040] According to a first embodiment, illustrated by FIG. 1, the first wall 5 is an external wall 12 of the tank 9. In order to provide additional thermal insulation and to further limit thermal transfers between the ambient air and the external wall 12, the external wall 12 can be covered with an insulating foam 3, in particular a polyurethane foam.

[0041] According to a second embodiment, illustrated by figure 2, the first wall 5' is an intermediate wall arranged between the internal wall 2 and the external wall 12 of the tank 9. A second empty space 8' then exists between the intermediate wall 5' and the external wall 12, also providing thermal insulation and making it possible to limit the temperature of the intermediate wall 5' to a temperature between those of the internal wall 2 and the external wall 12.

[0042] Radiative thermal insulation such as multi-layer insulation (MLI) can be used to limit radiative heat flows between walls of different temperatures, in particular between the first wall 5 and the internal wall 2. Other equivalent radiative insulation systems can also be used.

[0043] In addition to the tank 9, the transport device 1 comprises a liquid nitrogen circulation cooling system. The cooling system comprises a pipe 4 configured to circulate the nitrogen in contact with the first wall 5, 5' at an intermediate temperature Ti between the ambient air temperature TA and the liquid hydrogen temperature T H. The pipe 4 comprises an inlet portion 6 through which the liquid nitrogen comes into contact with the first wall 5, 5' and an outlet portion 7 through which the liquid nitrogen is discharged. The cooling system thus makes it possible to maintain the intermediate temperature Ti at a desired value. In accordance with the Stefan-Boltzmann law, the radiative heat transfer between an object of absolute temperature T and its environment of absolute temperature T E is proportional to the difference between the fourth powers of these temperatures (T 4 - T E 4 ). Thus, thanks to the cooling system, the radiative heat transfer between the hydrogen and the first wall 5, 5' is proportional to the value (Ti 4 - T 4 ), whereas in the absence of the cooling system, it is proportional to the value (TA 4 - T 4) which can be considerably higher. A lower proportion of the hydrogen therefore evaporates per unit time, and degassing is less frequently required, with the resulting mass losses. Furthermore, supplying liquid nitrogen at a temperature intermediate between the liquid hydrogen temperature T and ambient temperature TA is thermodynamically easier than supplying liquid nitrogen at a temperature closer to the hydrogen temperature T to directly cool the inner wall, and therefore allows for higher thermal efficiency.

[0044] According to one embodiment, the pipe 4 is fluidically connected to at least one liquid nitrogen tank 10 maintained at the intermediate temperature Ti. Thus, the transport device 1 can itself carry a nitrogen reserve allowing the operation of the cooling system, for example on board a vehicle transporting the transport device 1. The liquid nitrogen tank 10 can possibly be rechargeable during transport, so as to limit its volume for journeys made over long distances. It is possible to provide several liquid nitrogen tanks 10, each being fluidically connected to a pipe 4 of its own. The pipes 4 connected to the different liquid nitrogen tanks 10 can then be in contact with different parts of the first wall 5, 5'.

[0045] When the first wall is an intermediate wall 5', the intermediate wall 5' may be common to several liquid hydrogen transport devices 1, and be cooled by the same cooling system as defined previously, or by several separate cooling systems. The fact of providing several hydrogen transport devices comprising respective tanks 9, the tanks 9 having the same intermediate wall 5', makes it possible to limit the space occupied by the transport device. Indeed, it is then possible to limit the number of sources of liquid nitrogen necessary for cooling the tanks, because it is not necessary to provide a separate nitrogen source for each tank 9. In particular, the same liquid nitrogen tank 10 may then be used to cool a plurality of separate tanks 9 comprising the same intermediate wall 5'.Such a configuration is particularly advantageous for the transport of liquid hydrogen by rail, ship or truck, as these vehicles have limited available volume for the transport device.

[0046] According to an alternative embodiment, each tank 9 has its own intermediate wall 5', and the intermediate walls 5' of each tank 9 are configured to be able to be cooled by the same liquid nitrogen tank 4 to the intermediate temperature Ti.

[0047] As shown in Figure 5, the same pipe 4 supplied by the liquid nitrogen tank 10 can be in contact with each intermediate wall 5'. This results in a liquid hydrogen transport device that is as compact as possible, because it comprises a single liquid nitrogen tank 10 and a single pipe 4 for cooling a large quantity of liquid hydrogen, corresponding to the sum of the quantities of liquid hydrogen present in all the tanks 9. In the case where the transport device 1 is mounted on board a vehicle 14, the space occupied on board the vehicle 14 is thus minimized.

[0048] Alternatively, and as shown in Figure 6, each intermediate wall 5' of a tank 9 is cooled by a pipe 4 of its own, the pipes 4 all being connected to the same liquid nitrogen tank 10. Although slightly larger than the transport device of Figure 5, this transport device remains compact due to the single liquid nitrogen tank, while ensuring the most efficient possible cooling of each tank 9: in fact, unlike the embodiment of Figure 4, each pipe 4 carries liquid nitrogen coming directly from the liquid nitrogen tank 10, this nitrogen therefore not having been heated or very little heated before its arrival in the part of the pipe 4 which is in contact with the intermediate wall 5'.

[0049] According to an embodiment shown in Figure 3, a second pipe 13, independent of the pipe 4, is in contact with the internal wall 2, outside the internal cavity 11. This second pipe 13 is optionally fluidically connected to a source of liquid nitrogen, either separate from that supplying the pipe 4, or to the liquid nitrogen reservoir 10 which supplies the pipe 4. The second pipe 13 is configured for the circulation of liquid nitrogen at an internal wall temperature T Pi between ambient temperature TA and liquid hydrogen temperature T H . The internal wall temperature T Pi is lower than the intermediate temperature T i, and preferably substantially equal to the temperature of liquid hydrogen T H. When filling the empty tank 9 with liquid hydrogen, before transporting the device 1, the pipe 13 makes it possible to maintain the temperature of the internal wall 2 at a value close to the temperature of the hydrogen T and therefore to minimize the heat transfer from the internal wall 2 to the hydrogen. This prevents a significant portion of the hydrogen from evaporating during such filling, which generates mass losses even before the transport of the liquid hydrogen.

[0050] The cooling system may comprise a cryogenic machine, configured to maintain the liquid nitrogen circulating in the pipe 4 at the intermediate temperature Ti. The cryogenic machine may in particular be configured to reliquefy liquid nitrogen which has evaporated in the pipe 4 so as to ensure optimal operation of the cooling system. This configuration is particularly suitable for long-term transports, during which a significant proportion of the liquid nitrogen circulating in the pipe may evaporate.

[0051] According to one embodiment, the hydrogen tank 9 and the liquid nitrogen tank 10 are arranged in the same cryostat, so as to limit the volume and mass of the hydrogen transport device 1.

[0052] For a tank 9 of 2 meters in diameter and 5 meters in length, capable of containing approximately one ton of liquid hydrogen, the transport device 1 makes it possible to reduce the mass losses of hydrogen by almost five times - we go from 10-20 kg / day of mass losses for a transport device according to the state of the art, to approximately 2-4 kg / day for the transport device 1.

[0053] Another aspect of the invention relates to a method for cooling a liquid hydrogen tank as described above. The proposed method comprises cooling the first wall 5, 5' by circulating liquid nitrogen at the intermediate temperature Ti in the pipe 4. This method can be implemented during transport of hydrogen on board a vehicle, so as to limit heat transfers between the ambient air and the liquid hydrogen, and thus to minimize the evaporation of hydrogen in the internal cavity 11, and the mass losses of hydrogen by degassing.

[0054] According to one implementation of the process, liquid hydrogen has a temperature T of approximately 20 Kelvin. This temperature, close to the boiling point of hydrogen, allows the hydrogen to be kept in a liquid state while minimizing heat transfer between it and the ambient air.

[0055] The intermediate temperature Tl can be approximately 80 Kelvin. This intermediate temperature between the hydrogen temperature T of 20 Kelvin and the ambient temperature TA of approximately 300 Kelvin makes it possible to limit the heat transfers on both sides of the first wall 5, 5', on one side between the liquid hydrogen and the first wall 5, 5' and on the other side between the first wall 5, 5' and the air at ambient temperature TA.

[0056] Another aspect of the invention, shown in Figure 4, relates to a transport vehicle 14, such as a truck, comprising a hydrogen transport device 1 as previously described. With reference to Figures 4 to 6, the transport device 1 may be arranged in a container 16. The container may be adapted to be mounted on a truck trailer. The container may also be adapted to be placed on a vehicle traveling on railways. The container may also be adapted to be placed on a boat. Thus, it is possible to easily switch from one mode of transport to another.

[0057] The transport device 1 and the method for cooling a tank have been described in relation to liquid hydrogen. However, they can also be applied to liquid helium or liquid argon.

Claims

CLAIMS 1. Liquid hydrogen transport device, comprising a liquid hydrogen tank and a cooling system, the tank (9) comprising: o a cavity (11) delimited by an internal wall (2), the cavity (11) being configured to receive liquid hydrogen at a temperature (T H ) lower than an ambient temperature (TA) of the air around the tank (9), o a first wall (5, 5') arranged around the internal wall (2) and delimiting an empty space (8) between the internal wall and the first wall (5, 5'), the cooling system comprising at least one pipe (4) in contact with the first wall (5, 5'), the pipe (4) being configured to circulate liquid nitrogen at an intermediate temperature (Ti) between the ambient temperature (TA) and the temperature (T H ) liquid hydrogen.

2. Liquid hydrogen transport device according to claim 1, the first wall (5) being an external wall (12) of the tank having an internal surface facing the internal wall (2) and an external surface, an insulating foam (3) surrounding the first wall (5) on its external surface.

3. Liquid hydrogen transport device according to claim 1, the first wall (5') being an intermediate wall located between the internal wall (2) and an external wall (12) of the tank, an empty space (8') being interposed between the first wall (5') and the external wall (12).

4. Liquid hydrogen transport device according to any one of claims 1 to 3, the pipe (4) being in fluid connection with at least one liquid nitrogen tank (10) adapted to be maintained at the intermediate temperature (Ti).

5. Liquid hydrogen transport device according to any one of claims 1 to 4, the cooling system comprising a machine cryogenic configured to maintain the nitrogen circulating in the pipeline (4) at the intermediate temperature (Ti) and / or to allow the condensation of nitrogen vapors in the pipeline (4).

6. Liquid hydrogen transport device according to any one of claims 4 and 5, the hydrogen tank (9) and the at least one liquid nitrogen tank (10) being arranged in the same cryostat.

7. Liquid hydrogen transport device according to any one of claims 4 to 6, the cooling system comprising several pipes (4), each pipe (4) being connected to a respective liquid nitrogen tank (10), each pipe (4) being in contact with a different part of the first wall (5, 5').

8. Liquid hydrogen transport device according to any one of claims 1 to 7, further comprising a second pipe (13) located outside the cavity (11) and in contact with the internal wall (2) and configured to circulate liquid nitrogen at an internal wall temperature (T pi ), the internal wall temperature being greater than or equal to the hydrogen temperature (T H ) and lower than the ambient temperature (TA), the internal wall temperature (T pi ) being preferably substantially equal to the temperature of hydrogen (T H ).

9. A liquid hydrogen transport device according to any one of claims 3 to 8, comprising a plurality of liquid hydrogen tanks (9) and wherein each tank (9) comprises a first wall (5'), the cooling system comprising a single pipe (4) in contact with the first wall (5') of each tank (9), the pipe (4) being configured to circulate liquid nitrogen from a liquid nitrogen tank (10).

10. Liquid hydrogen transport device according to any one of claims 3 to 8, comprising a plurality of liquid hydrogen tanks (9) and in which each tank (9) comprises a first wall (5'), the cooling system comprising several pipes (4), each pipe (4) being in contact with the first wall (5') of a tank (9), each pipe being configured to circulate liquid nitrogen from the same liquid nitrogen tank (10). 1 1. Method for cooling a tank (9) of liquid hydrogen, the tank comprising: - a cavity (11) delimited by an internal wall (2), the cavity (11) being configured to receive liquid hydrogen at a temperature (T H ) lower than an ambient temperature (TA) of the air around the tank (9), - a first wall (5, 5') arranged around the inner wall (2), delimiting an empty space (8) between the inner wall (2) and the first wall (5, 5'), the method comprising cooling the first wall by circulating liquid nitrogen in a pipe (4) in contact with the first wall (5, 5'), the liquid nitrogen having an intermediate temperature (Ti) between the temperature of hydrogen (T H ) and ambient temperature (AT).

12. Method according to claim 11, the temperature of the hydrogen (T H ) being approximately 20 Kelvin and the intermediate temperature (Ti) being approximately 80 Kelvin.

13. A method according to any one of claims 1 1 and 12, the method being a method of cooling a plurality of hydrogen tanks (9), each tank (9) of the plurality of tanks comprising a first wall (5'), the first wall (5') being located between the inner wall (2) and an outer wall (12) of the tank, an empty space being interposed between the first wall (5') and the outer wall (12), the method comprising cooling the first wall (5') by circulating liquid nitrogen in a single pipe (4) in contact with each first wall (5') of each tank (9) of the plurality of tanks, the single pipe (4) being supplied by a single liquid nitrogen tank (10).

14. A method according to any one of claims 11 and 12, the method being a method of cooling a plurality of hydrogen tanks (9), each tank (9) of the plurality of tanks comprising a first wall (5'), the first wall (5') being located between the inner wall (2) and an outer wall (12) of the tank (9), an empty space being interposed between the first wall (5') and the outer wall (12), the method comprising cooling each first wall (5') by circulation of liquid nitrogen in a separate pipe (4) in contact with the first wall (5'), the pipes (4) being supplied by the same liquid nitrogen tank (10).

15. Container (16) comprising a hydrogen transport device according to any one of claims 1 to 10, the container being configured to be placed on board a vehicle, the vehicle being chosen in particular from a truck, a train or a boat.

16. Vehicle (14) for transporting liquid hydrogen comprising a container (16) according to claim 15 or a hydrogen transport device according to any one of claims 1 to 10.

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