Patent Grant
10036589
This application is a § 371 of International PCT Application PCT/EP2013/076745, filed Dec. 16, 2013, which claims the benefit of JP2012-288262, filed Dec. 28, 2012, and JP2013-085114, filed Apr. 15, 2013, all of which are herein incorporated by reference in their entireties.
The present invention relates to an apparatus and a method for cooling and compressing a fluid to produce a low-temperature compressed fluid using the cold of a liquefied natural gas (hereafter also referred to as “LNG”), and is particularly useful as a technique for liquefying nitrogen gas that is produced by an air separation apparatus or the like.
Natural gas (NG) is stored as a liquefied natural gas (LNG) for facility in transportation and storage, or the like, and is used mainly for thermal power generation or for city gas after being vaporized. Then, a technique of effectively utilizing the cold of LNG is developed. Generally, as equipment for liquefying nitrogen gas or the like by using the cold of LNG, a process is used such that nitrogen gas is compressed by a compressor up to a pressure such that the nitrogen gas can be liquefied by heat exchange with the LNG, and subsequently the nitrogen gas is subjected to the heat exchange with the LNG in a heat exchanger to vaporize the LNG by raising the temperature and to liquefy the nitrogen gas.
Also, with respect to the electric power for driving the compressor, the tariff at night is set to be lower than the tariff for daytime, so that a gas liquefying process for efficiently liquefying a gas while taking the fluctuation of the supply amount of the above LNG and the difference in the electric power tariff into consideration is proposed. For example, referring to
However, with an apparatus for producing a low-temperature liquefied fluid or the like such as described above, various problems such as the following occurred in some cases.
(i) The amount of LNG supplied to the gas liquefying process may generally fluctuate due to the fluctuation in the demand for thermal power generation, city gas, or the like, and the amount of cold that can be used may also fluctuate. Therefore, there is a demand for an apparatus or a method by which the cold of LNG can be efficiently used so that the amount of production of the liquefied fluid or the like may not be affected even when the supplied LNG decreases in amount.
(ii) In order to pressurize a gas having a normal temperature and a normal pressure in a process for producing a compressed gas, addition of a large amount of energy and the cold for restraining the gas temperature rise accompanying the compression will be needed. In producing a compressed gas for general use that is consumed in a large amount, such as a nitrogen gas, there is a big problem for an efficient use of the cold and a comprehensive reduction of energy.
(iii) With respect to the temperature at which a gas having a normal pressure starts being liquefied, the temperature is about −80° C. for LNG, while the temperature is about −120° C. for nitrogen. For example, in a process for liquefying nitrogen gas at a normal pressure using LNG as the cold, in a state in which the liquefaction of nitrogen has started, the LNG that is subject to heat exchange with this nitrogen is still in a liquid state having a large latent heat, so that, in view of this process alone, the cold of the LNG is not sufficiently used. Also, it is not necessarily easy to use the cold of the residual LNG for other purposes, so that there is a big problem for an efficient use of energy including the cold of LNG in such a liquefaction process.
An object of the present invention is to provide an apparatus and a method for cooling and compressing a fluid to produce a low-temperature compressed fluid that can efficiently use the cold of LNG and can reduce the energy that is needed in producing the low-temperature compressed fluid.
The present inventors and others have made eager studies in order to solve the aforementioned problems and, as a result, have found that the aforementioned object can be achieved by an apparatus and a method for producing a low-temperature compressed fluid described below, thereby completing the present invention.
An apparatus for cooling and compressing a fluid to produce a low-temperature compressed fluid according to the present invention using a Rankine cycle system comprises; a first compression device for adiabatically compressing a heat transfer medium; a first heat exchanger for constant-pressure heating the adiabatically compressed heat transfer medium; an expansion device for adiabatically expanding the heated heat transfer medium; a second heat exchanger for constant-pressure cooling the adiabatically expanded heat transfer medium; a first flow passageway for guiding the heat transfer medium from the second heat exchanger to the first compression device; and at least one second compression device that is coupled to the expansion device; wherein, at the second heat exchanger, a low-temperature liquefied natural gas and the heat transfer medium undergo heat transfer, wherein, at the first heat exchanger, a fed material gas and the heat transfer medium undergo heat transfer to produce a low-temperature fluid from the material gas, and wherein, the low-temperature fluid is thereafter compressed at the second compression device to produce a low-temperature compressed fluid.
Also, a method for cooling and compressing a fluid to produce a low-temperature compressed fluid according to the present invention comprises a Rankine cycle system in which a heat transfer medium that has been adiabatically compressed by first compression device is heated in a first heat exchanger at a constant pressure, thereafter adiabatically expanded by expansion device, and further cooled in a second heat exchanger at a constant pressure, wherein a liquefied natural gas in a low-temperature liquefied state is guided into the second heat exchanger to transfer the cold thereof to the heat transfer medium, and a material gas that has been fed is guided into the first heat exchanger to be cooled by the heat transfer medium and thereafter guided into at least one second compression device that is coupled to the expansion device, so as to be extracted as a low-temperature compressed fluid.
With such a structure, the cold of LNG can be efficiently used in preparing a low-temperature compressed fluid, and reduction of needed energy can be achieved. Specifically, in the process of verifying the present invention, it has been found out that the heat transfer is efficiently carried out by heat exchange with a compressed fluid, and the cold needed in preparing a low-temperature gas is extremely small as compared with the cold needed in preparing a low-temperature fluid under conventional conditions of normal pressure using the cold of LNG. Based on such a knowledge, in the present invention, a Rankine cycle system (hereafter also referred to as “RC”) that can effectively use the heat exchange with a compressed fluid is applied in preparing a low-temperature fluid, whereby the cold of LNG can be used much more efficiently, and the energy needed in transferring the cold can be reduced to a great extent by efficiently transferring the cold of high-pressure LNG via the heat transfer medium of the RC and transferring the cold energy from the adiabatically compressed heat transfer medium to a fed material gas at normal pressure.
An apparatus according to the present invention using the above-described apparatus further comprises; a second flow passageway for guiding the low-temperature compressed fluid from the second compression device to at least one of the first heat exchanger and the second heat exchanger to form a liquefied component, an adjustment valve for adjusting a pressure of the low-temperature compressed fluid from at least one of the first heat exchanger and the second heat exchanger, and a gas-liquid separator into which the low-temperature compressed fluid is guided via the adjustment valve, performing gas-liquid separation so as to permit the liquefied component to be extracted therefrom.
Also, a method according to the present invention uses the above-described method, wherein the low-temperature compressed fluid from the second compression device is cooled in the first heat exchanger or the second heat exchanger and subjected to pressure adjustment by an adjustment valve, and a liquefied component is subjected to gas-liquid separation in a gas-liquid separator and is extracted as a low-temperature liquefied component from the gas-liquid separator.
When the cold of LNG is used in preparing a liquefied fluid such as nitrogen gas, the temperature of the LNG is around −155° C. while the boiling point of nitrogen under ambient air pressure is −196° C., so that this difference in temperature levels must be compensated between these. The present invention realizes such a function with use of a Rankine cycle system. The heat transfer medium used in the Rankine cycle system is cooled to about −150 to −155° C. by using the cold of LNG to ensure the cold to be transferred to nitrogen gas or the like. After the pressure is raised typically to a critical pressure or above (for example, 5 to 6 MPa), the cold is transferred through the first heat exchanger to the nitrogen gas or the like in a normal pressure or in a low-pressurized condition, and further the cold is transferred through the second heat exchanger to the nitrogen gas or the like compressed to a high pressure, whereby a liquefied nitrogen gas can be efficiently prepared. In preparing a liquefied fluid, the cold of the LNG can be used more efficiently, and the energy needed in transferring the cold can be reduced to a great extent.
The present invention relates also to the apparatus for producing a liquefied fluid described above, wherein the apparatus further comprises: a third heat exchanger disposed in a third flow passageway for guiding the heat transfer medium from the first heat exchanger to the expansion device, wherein the heat transfer medium, the liquefied natural gas from the second heat exchanger, and the low-temperature compressed fluid from the second compression device undergo heat exchange at the third heat exchanger.
With such a structure, the cold of the LNG can be used further more efficiently, and preparation of a liquefied fluid having a high energy efficiency can be carried out. In particular, when cooling water is introduced in the third heat exchanger to perform heat exchange by cold energy having a large heat capacity, transfer of preparatory or auxiliary hot heat to the heat transfer medium, the liquefied natural gas, and the low-temperature compressed fluid can be carried out even to transient fluctuation or the like at the time of starting or at the time of stopping, thereby ensuring a stable use of the cold of LNG and a stable energy efficiency.
The present invention relates also to the apparatus for producing a liquefied fluid described above, wherein first pressure-raising device, a first branching flow passageway, second pressure-raising device, and a second branching flow passageway are disposed in a fourth flow passageway through which the material gas is guided to the first heat exchanger; a fourth heat exchanger and a third branching flow passageway are disposed in a fifth flow passageway through which the liquefied component from the gas-liquid separator is guided; which has a sixth flow passageway through which a gas component from the gas-liquid separator is guided to the first branching flow passageway via the first heat exchanger or the second heat exchanger, and a seven flow passageway through which the liquefied component that has been branched at the third branching flow passageway is guided to the second branching flow passageway via the fourth heat exchanger and the first heat exchanger or the second heat exchanger, where the liquefied component from the gas-liquid separator is extracted therefrom via the fourth heat exchanger.
It is known in the art that, by compressing the material gas in multiple stages, the material gas can be efficiently fed, and the heat exchange efficiency in the heat exchanger into which such a material gas is introduced will be improved. The present invention has made it possible to supply a liquefied fluid in a stable condition and with a good energy efficiency by providing compressors in plural stages as material gas feeding device and returning the liquefied fluid in a stable condition immediately before being extracted to mix the liquefied fluid with the material gas thereof.
The present invention relates also to the apparatus for producing a liquefied fluid described above, wherein the Rankine cycle system is comprised with a plurality of Rankine cycle systems using a plurality of heat transfer media having different boiling points or heat capacities, where the material gas from the first heat exchanger is guided into the first heat exchanger after being compressed by second compression device that is coupled to the expansion device involved in one Rankine cycle system using a heat transfer medium having a low boiling point or a small heat capacity, and thereafter the material gas from the first heat exchanger is guided into the first heat exchanger after being compressed by second compression device that is coupled to the expansion device involved in another Rankine cycle system using a heat transfer medium having a high boiling point or a large heat capacity.
In many cases, an apparatus for producing a liquefied fluid is used in line in semiconductor production equipment or the like, so that a continuous supply of gas is demanded, and also the amount of supply, the pressure of supply, and the like thereof may largely fluctuate. Also, as described before, there are cases in which the stable supply of LNG is not necessarily ensured. The present invention has made it possible to supply a liquefied fluid in a stable condition and with a good energy efficiency by constructing with a plurality of Rankine cycle systems using a plurality of heat transfer media having different boiling points or heat capacities for the heat transfer medium that carries out the transfer of the cold of LNG and adjusting the control elements that can be easily controlled, such as the flow rate and the pressure of the heat transfer medium, in each Rankine cycle system with regard to the fluctuating elements in these cases.
These and other features, aspects, and advantages of the present invention will become better understood with regard to the following description, claims, and accompanying drawings. It is to be noted, however, that the drawings illustrate only several embodiments of the invention and are therefore not to be considered limiting of the invention's scope as it can admit to other equally effective embodiments.
An apparatus for cooling and compressing a fluid to produce a low-temperature compressed fluid according to the present invention (hereafter referred to as “present apparatus”) using a Rankine cycle system (RC) comprises; a first compression device for adiabatically compressing a heat transfer medium, a first heat exchanger for constant-pressure heating the adiabatically compressed heat transfer medium; an expansion device for adiabatically expanding the heated heat transfer medium; a second heat exchanger for constant-pressure cooling the adiabatically expanded heat transfer medium; a (first) flow passageway for guiding the heat transfer medium from the second heat exchanger to the first compression device; and at least one second compression device that is coupled to the expansion device; wherein, at the second heat exchanger, a low-temperature liquefied natural gas (LNG) and the heat transfer medium undergo heat transfer, wherein, at the first heat exchanger, a fed material gas and the heat transfer medium undergo heat transfer to produce a low-temperature fluid from the material gas, and wherein, the low-temperature fluid is thereafter compressed at the second compression device to produce a low-temperature compressed fluid. Hereafter, the embodiments of the present invention will be described with reference to the attached drawings. Here, in the present embodiments, cases in which nitrogen gas is the gas to be liquefied may be exemplified; however, the present invention can be applied similarly to liquefaction of other gases, for example, air, argon, and the like. Also, conditions such as the temperature, the pressure, and the flow rate of each section can be suitably changed in accordance with other conditions such as the type of the gas and the flow rate.
The basic structure of the present apparatus will be schematically exemplified in
The LNG of a predetermined flow rate is supplied to the second heat exchanger 4, whereby a predetermined amount of cold is ensured. By controlling the supply flow rate of the LNG, the cold that is transferred to the material gas can be easily adjusted. A material gas of a desired flow rate is supplied to the first heat exchanger 2 by a feed pump 5, whereby a predetermined amount of cold is transferred to the material gas to cool the material gas to a desired temperature. Further, the material gas is guided into the compressor 6 which is second compression device so as to be compressed to a desired pressure and is extracted as a desired low-temperature compressed fluid. By such a structure, a desired low-temperature compressed fluid can be produced in a stable condition. Also, the energy efficiency can be improved to a great extent as compared with a conventional apparatus in which the cold of LNG and the material gas are subjected to direct heat exchange.
As described above, the low-temperature compressed fluid is produced in such a condition that, in the present apparatus in which a Rankine cycle system (RC) is formed, a liquefied natural gas in a low-temperature liquefied state is guided into the second heat exchanger 4 to transfer the cold thereof to the heat transfer medium, and the material gas that is fed by the feed pump 5 is guided into the first heat exchanger 2 to be cooled by the heat transfer medium and thereafter guided into at least one second compression device (compressor) 6 that is coupled to the expansion device (turbine) 3, so as to be extracted as a low-temperature compressed fluid.
Specifically, an example will be assumed in which a mixture obtained by blending ethane and propane in an equal molar ratio as a major component, for example, is used as the heat transfer medium of the RC; LNG of about 6 MPa is guided into the second heat exchanger 4; and nitrogen gas is fed as a material gas. In the example, the heat transfer medium guided at about 0.05 MPa into the second heat exchanger 4 is guided out after being cooled to about −115° C., adiabatically compressed to about 1.8 MPa by the compression pump 1, guided into the first heat exchanger 2, guided out after being heated by heat exchange with the material gas, adiabatically expanded by the turbine 3, and guided at about −45° C. and under about 0.05 MPa into the second heat exchanger 4. The nitrogen gas guided at about 2.1 MPa into the first heat exchanger 2 is guided out after being cooled to about −90° C., compressed to about 5 MPa by the compressor 6 coupled to the turbine 3, and extracted as a low-temperature compressed nitrogen gas having a temperature of about −90° C. and a pressure of about 5 MPa.
A case in which a low-temperature compressed nitrogen gas was prepared using the present apparatus was compared with a case in which a low-temperature compressed nitrogen gas was prepared using a conventional method, so as to verify the energy efficiency thereof. As will be described below, an improvement of about 50% or more could be achieved by using the present apparatus.
(i) A case in which a low-temperature compressed nitrogen gas was prepared using a conventional method
Assuming that LNG was supplied at 1 ton/h and a compressor was operated at an electric power of 15.7 kWh, a nitrogen gas of 677 Nm3/h, for example, could be pressurized from 20 bar to 37 bar. During this time, the entrance temperature of the compressor was 40° C., and the exit temperature thereof was 111° C.
(ii) A case in which a low-temperature compressed nitrogen gas was prepared using the present method
The amount of LNG needed to obtain a similar low-temperature compressed nitrogen gas, that is, to pressurize a nitrogen gas of 677 Nm3/h from 20 bar to 37 bar, was 0.485 ton/h.
(iii) When the two cases were compared, it had been found out that the electric power could be reduced by about 8 kWh, that is, by about 52%, from the following formula 1.
(1−0.485)×0.515=8.09 [kWh]
8.09/15.7=0.52 (formula 1)
Apparatus for producing a liquefied fluid using the present apparatus
A basic exemplary structure (first exemplary structure) of an apparatus (hereafter referred to as “present liquefaction apparatus”) for producing a liquefied fluid using the present apparatus will be schematically shown in
In other words, the low-temperature compressed fluid from the second compression device 6 is cooled in the second heat exchanger 4 and is subjected to pressure adjustment by the adjustment valve 7, and the liquefied component is subjected to gas-liquid separation in the gas-liquid separator 8 and extracted as a low-temperature liquefied component from the gas-liquid separator 8. At this time, when the material gas is, for example, ethane or propane having a comparatively higher boiling point than nitrogen or oxygen, the low-temperature compressed fluid can be liquefied by being guided into the first heat exchanger 2, as is exemplified in
Similarly as the specific example in the above-described present apparatus, a specific example will be assumed in which a mixture obtained by blending ethane and propane in an equal molar ratio as a major component, for example, is used as the heat transfer medium of the RC; LNG of about 6 MPa is guided into the second heat exchanger 4; and nitrogen gas is fed as a material gas. A material gas that has been guided at about 2.1 MPa into the first heat exchanger 2 becomes a low-temperature compressed nitrogen gas of about −90° C. and about 5 MPa by passing through the compressor 6. This low-temperature compressed nitrogen gas is further guided into the second heat exchanger 4 to be cooled to about −153° C. and then is expanded via the adjustment valve 7 to be cooled to about −179° C., whereafter the liquefied nitrogen gas mainly containing a liquefied component is guided into the gas-liquid separator 8. The liquefied component that has been subjected to gas-liquid separation in the gas-liquid separator 8 is extracted as a liquefied nitrogen gas of about −179° C. and about 0.05 MPa.
Similarly as in the verification test in the above-described present apparatus, a case in which a liquefied nitrogen gas was prepared using the present liquefaction apparatus was compared with a case in which a liquefied nitrogen gas was prepared using a conventional method, so as to verify the energy efficiency thereof. As will be described below, an improvement of about 25% or more could be achieved by using the present apparatus.
(i) A case in which a liquefied nitrogen gas was prepared using a conventional method
LNG was supplied at 1 ton/h, and an energy of 0.28 kWh/Nm3 was needed in preparing a liquefied nitrogen gas of about 0.05 MPa.
(ii) A case in which a liquefied nitrogen gas was prepared using the present method
An energy of 0.21 kWh/Nm3 was sufficient in preparing a liquefied nitrogen gas of about 0.05 MPa under the conditions of the specific example in the above-described present liquefaction apparatus.
(iii) When the two cases are compared, it has been found out that the electric power could be reduced by about 25%, from the following formula 1.
(0.28−0.21)/0.28=0.25 (formula 1)
Another exemplary structure (second exemplary structure) of the present liquefaction apparatus will be schematically shown in
In other words, in the third heat exchanger 9, the cold of the LNG can be used further more efficiently by using the residual cold of the LNG for cooling the heat transfer medium that has been heated in the first heat exchanger 2 and the low-temperature compressed fluid that has been compressed to have an increased heat quantity. Also, a structure in which cooling water is introduced in the third heat exchanger 9 will be exemplified here. Heat exchange with cold energy having a large heat capacity can be carried out, and quick transfer of hot heat can be achieved to the heat transfer medium, the liquefied natural gas, and the low-temperature compressed fluid. Even to transient fluctuation or the like at the time of starting or at the time of stopping, preliminary or auxiliary transfer of hot energy can be achieved to the heat transfer medium, the liquefied natural gas, and the low-temperature compressed fluid, whereby stable use of the cold of the LNG and stable energy efficiency can be ensured.
The third exemplary structure of the present liquefaction apparatus will be schematically shown in
In the third exemplary structure, a structure will be exemplified in which a second adjustment valve 12 is disposed in the third branching flow passageway S3, and part of the liquefied fluid from the fourth heat exchanger 11 is again guided into the fourth heat exchanger 11 via the second adjustment valve 12. Though having a low pressure, a liquefied fluid having a further lower temperature is prepared by adiabatically expanding the low-temperature liquefied fluid with the second adjustment valve 12 and can be allowed to function as the cold in the fourth heat exchanger 11.
The temperature and the pressure of the gas or liquid in each flow passageway in the case in which liquefied nitrogen gas was prepared using the liquefaction apparatus according to the third exemplary structure were verified. The verification results are exemplified in Table 1.
The fourth exemplary structure of the present liquefaction apparatus will be schematically shown in
The plurality of heat transfer media having different boiling points or heat capacities as referred to herein include not only a case in which the substances themselves are different and a case in which the substances constituting the mixtures or compounds are different but also a case in which the composition of the mixture of a plurality of substances is different. For example, two Rankine cycle systems having different characteristics can be constructed by forming one heat transfer medium with a mixture of 20% of methane, 40% of ethane, and 40% of propane and forming the other heat transfer medium with a mixture of 2% of methane, 49% of ethane, and 49% of propane. By a combination thereof, transfer of the cold or the cold energy that matches with various fluctuating elements can be achieved, and efficient transfer of energy to the compression device coupled with the expansion device can be achieved.
Also, when heat transfer media having different components are used, a heat transfer function of a further wider range can be formed. In other words, there is a restriction on the temperature band in which the cold of the LNG can be used because of the relationship between the temperature of the cold of the LNG and the boiling point of the material gas or the temperature of the compressed gas (fluid) as described above, so that the cold of the LNG can be used in a plurality of temperature bands by arranging one Rankine cycle system RCa and another Rankine cycle system RCb in series as in the fourth exemplary structure. For example, the cold energy of the LNG can be thermally transferred in a plurality of temperature bands by using a mixture of “methane+ethane+propane” in one Rankine cycle system RCa and using a mixture of “ethane+propane+butane” in another Rankine cycle system RCb. The cold energy of the LNG can be efficiently used by arranging one Rankine cycle system RCa and another Rankine cycle system RCb in series as in the fourth exemplary structure and by using the cold energy of the LNG, for example, in a range of −150 to −100° C. in the one Rankine cycle system RCa and using the cold energy of the LNG, for example, in a range of −150 to −100° C. in the other Rankine cycle system RCb. Also, when this is used as an energy for compressing the nitrogen gas, the energy (consumed electric power) needed per liquefied nitrogen production amount can be greatly reduced.
As shown above, each exemplary structure has been described on the basis of each descriptive view; however, the present apparatus or the present liquefaction apparatus is not limited to these but is constructed with a wider concept including a combination of the constituent elements thereof or a combination with other related known constituent elements.
While the invention has been described in conjunction with specific embodiments thereof, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications, and variations as fall within the spirit and broad scope of the appended claims. The present invention may suitably comprise, consist or consist essentially of the elements disclosed and may be practiced in the absence of an element not disclosed. Furthermore, if there is language referring to order, such as first and second, it should be understood in an exemplary sense and not in a limiting sense. For example, it can be recognized by those skilled in the art that certain steps can be combined into a single step.
The singular forms “a”, “an” and “the” include plural referents, unless the context clearly dictates otherwise.
“Comprising” in a claim is an open transitional term which means the subsequently identified claim elements are a nonexclusive listing (i.e., anything else may be additionally included and remain within the scope of “comprising”). “Comprising” as used herein may be replaced by the more limited transitional terms “consisting essentially of” and “consisting of” unless otherwise indicated herein.
“Providing” in a claim is defined to mean furnishing, supplying, making available, or preparing something. The step may be performed by any actor in the absence of express language in the claim to the contrary.
Optional or optionally means that the subsequently described event or circumstances may or may not occur. The description includes instances where the event or circumstance occurs and instances where it does not occur.
Ranges may be expressed herein as from about one particular value, and/or to about another particular value. When such a range is expressed, it is to be understood that another embodiment is from the one particular value and/or to the other particular value, along with all combinations within said range.
All references identified herein are each hereby incorporated by reference into this application in their entireties, as well as for the specific information for which each is cited.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2012-288262 | Dec 2012 | JP | national |
| 2013-085114 | Apr 2013 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2013/076745 | 12/16/2013 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2014/102084 | 7/3/2014 | WO | A |
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| 3892103 | Antonelli | Jul 1975 | A |
| 4054433 | Buffiere et al. | Oct 1977 | A |
| 4444015 | Matsumoto | Apr 1984 | A |
| 5137558 | Agrawal | Aug 1992 | A |
| 8236193 | Fukushima | Aug 2012 | B2 |
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| 814 209 | Jun 1959 | GB |
| A0545050 | Feb 1993 | JP |
| WO 2007 144103 | Dec 2007 | WO |
| Entry |
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| International Search Report for PCT/EP2013/076745, dated Apr. 28, 2015. |
| Number | Date | Country | |
|---|---|---|---|
| 20160109180 A1 | Apr 2016 | US |
