JP6168953B2 - Liquid manufacturing method and liquid manufacturing equipment - Google Patents

Description

  The present disclosure relates to a liquid manufacturing method and a liquid manufacturing facility for manufacturing a liquid from a gaseous raw material.

In fields requiring a temperature environment in a low temperature region such as a cryogenic technique, a low temperature liquid obtained by liquefying a refrigerant gas is used.
As an example of such a liquid production facility, Non-Patent Document 1 describes a helium liquefier. In this helium liquefier, gaseous helium is used as a raw material, and the gaseous raw material in a supercritical state is liquefied by performing an enthalpy expansion with an expansion valve using a refrigeration cycle.

  Patent Document 1 describes a liquefaction control method for a liquefaction refrigeration system in which an expansion stroke of a refrigeration cycle is divided into two stages.

JP-A-60-164182

"Cryogenic Engineering Handbook", Cryogenic Engineering Association, P136

In the case of producing a liquid from a gaseous raw material, it is required to improve the liquefaction rate in order to produce the liquid efficiently.
In order to improve the liquefaction rate, in general, an expansion turbine or the like is used in the expansion stroke as compared with the case where the raw material in a supercritical state is expanded by an enthalpy expansion using an expansion valve or the like as described in Non-Patent Document 1. Therefore, the liquefaction rate becomes higher when isentropic expansion (adiabatic expansion) is performed.
In the liquefaction control method described in Patent Document 1, the expansion stroke of the refrigeration cycle is divided into two stages with the intention of increasing the refrigeration output (corresponding to the “liquefaction rate” described above). That is, in the expansion step, a first expansion process in which the raw material in the supercritical state is isentropically expanded to the supercritical pressure by the expansion turbine, and a second expansion is performed by the pressure regulating valve in the gas-liquid mixing region below the critical pressure. A two-stage expansion stroke including an expansion stroke is performed. In the expansion stroke in this method, the refrigeration output (the above-mentioned “liquefaction rate”) is improved by performing isentropic expansion up to the supercritical pressure instead of performing only the isenthalpy expansion throughout the entire expansion stroke.
However, it is desired to further improve the liquefaction rate.

  In view of such circumstances, an object of at least some embodiments of the present invention is to provide a liquid production method capable of improving the liquefaction rate from a raw material in a gaseous state. Moreover, at least some embodiment of this invention aims at providing the liquid manufacturing equipment which can improve the liquefaction rate from the raw material of a gaseous state.

A liquid production method according to at least one embodiment of the present invention includes:
A method for producing a liquid from a raw material in a gaseous state,
A supercritical process for transferring the raw material from a gaseous state to a supercritical state;
A first expansion step of expanding the raw material so that the supercritical raw material is in a gas-liquid mixed state;
A gas-liquid separation step of separating the raw material in the gas-liquid mixed state after the first expansion step into a first liquid phase portion and a first gas phase portion;
A second expansion step of expanding the first liquid phase portion along an isoenthalpy line to obtain a gas-liquid mixture including a second liquid phase portion at a lower temperature and low pressure than the first liquid phase portion;
And a third expansion step of expanding the first gas phase portion along the isentropic line to obtain a gas-liquid mixture including the third liquid phase portion.

  According to the liquid manufacturing method according to the above-described embodiment, the first liquid phase part and the second liquid phase part separated in the gas-liquid separation process following the first expansion process are divided into the second expansion process and the third expansion process. The enthalpy expansion and the isentropic expansion are performed respectively. Thereby, a liquefaction rate can be improved compared with the case where it is made into an enthalpy expansion in the gas-liquid mixing area | region below a critical pressure (for example, patent document 1).

In some embodiments, in the first expansion step, the raw material in the supercritical state is expanded along an isenthalpy line.
In the first expansion stroke, since the raw material shifts from the supercritical state to the gas-liquid mixed state, the raw material enters a gas-liquid mixed state in which droplets are mixed in the gas phase. Here, the means (for example, expansion valve) which can implement | achieve expansion | swelling along an isoenthalpy line | wire can operate | move without a problem even in a gas-liquid mixing state. Therefore, according to the above-described embodiment, it is possible to employ expansion means suitable for expansion under a gas-liquid mixed state.

In some embodiments, in the first expansion step, the raw material in the supercritical state is expanded along an isentropic line.
In this case, since the first expansion process from the supercritical state to the gas-liquid mixed state is the expansion along the isentropic line, the liquefaction rate can be further improved.

The liquid production facility according to at least one embodiment of the present invention is a facility for producing a liquid from a gaseous raw material,
A supercritical apparatus for transferring the raw material from a gas state to a supercritical state;
A first expander for expanding the raw material so that the supercritical raw material is in a gas-liquid mixed state;
A gas-liquid separator for separating the raw material in a gas-liquid mixed state that has passed through the first expander into a first liquid phase portion and a first gas phase portion;
A second expander for expanding the first liquid phase portion along an isoenthalpy line to obtain a gas-liquid mixture including a second liquid phase portion at a lower temperature and pressure than the first liquid phase portion;
A third expander for expanding the first gas phase portion along the isentropic line to obtain a gas-liquid mixture including the third liquid phase portion.

  According to the liquid manufacturing apparatus according to the above embodiment, the first liquid phase portion and the first gas phase portion separated by the gas-liquid separator following the expansion by the first expander are used as the second expander and the third expander. The enthalpy expansion and the isentropic expansion are performed by the expander, respectively. Thereby, a liquefaction rate can be improved compared with the case where it is made into an enthalpy expansion in the gas-liquid mixing area | region below a critical pressure (for example, patent document 1).

In some embodiments, the first expander is an expansion valve for expanding the raw material in the supercritical state along an isoenthalpy line.
In the expansion by the first expander, since the raw material shifts from the supercritical state to the gas-liquid mixed state, the raw material enters a gas-liquid mixed state in which droplets are mixed in the gas phase. Here, the expansion valve, which is a means capable of realizing expansion along the isoenthalpy, can operate without problems even in a gas-liquid mixed state. Therefore, according to the above-described embodiment, it is possible to employ expansion means suitable for expansion under a gas-liquid mixed state.

In some embodiments, the first expander is an expansion turbine for expanding the raw material in the supercritical state along an isentropic line.
In this case, since the expansion by the first expander from the supercritical state to the gas-liquid mixed state is the expansion along the isentropic line, the liquefaction rate can be further improved.

  According to at least one embodiment of the present invention, in a liquid manufacturing method, the liquefaction rate from a raw material in a gaseous state can be improved.

It is a Ts diagram which shows an example of a general liquefaction cycle. It is a Ts diagram which shows the liquefaction cycle in the liquid manufacturing method which concerns on one Embodiment. It is a figure showing typically composition of liquid manufacture equipment concerning one embodiment. It is a Ts diagram which shows the liquefaction cycle in the liquid manufacturing method which concerns on one Embodiment. It is a figure which shows typically the structure of the gas-liquid separator which concerns on one Embodiment. It is a Ts diagram which shows the liquefaction cycle in the liquid manufacturing method which concerns on one Embodiment. It is a figure which shows typically the structure of the liquid manufacturing apparatus which concerns on one Embodiment.

  Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. However, the dimensions, materials, shapes, relative arrangements, and the like of the components described in this embodiment are not intended to limit the scope of the present invention, but are merely illustrative examples.

First, the outline of a liquefaction cycle and “liquefaction rate” in the present specification will be described with reference to FIG.
FIG. 1 is a Ts diagram showing an example of a general liquefaction cycle.
In FIG. 1, a line connecting HDEFG (hereinafter referred to as line HDEFG or the like) and line ABCO are isobars of the raw material, line ABCO is an isobar at a pressure higher than the critical pressure of the raw material, and line HDEFG is the raw material. It is an isobar at a pressure lower than the critical pressure. The source material is not particularly limited, and examples include nitrogen and helium.
The raw material in a high temperature state at point G is compressed into a high temperature and high pressure state at point A. The raw material is cooled by heat exchange along the isobaric line from point A, and reaches point O via BC. Point O is a point at a pressure higher than the critical pressure and a temperature higher than the critical temperature, and the raw material that has reached point O is in a supercritical state. During the period from point A to point O, part of the raw material is expanded by the expander and merges with the low pressure side line (line BF, line CE). The remainder of the raw material is cooled by heat exchange with a part of the raw material whose temperature has decreased due to this expansion, as shown in line ABCO.
The raw material that has reached point O enters the gas-liquid mixing region sandwiched between the liquidus line and the gas phase line through the expansion process, and is liquefied. Here, when the isoenthalpy expansion is performed, the source material expands along the isoenthalpy line and reaches the point P. At point P, the gas phase and the liquid phase coexist, and the liquefaction rate at this time is PD / HD (PD and HD represent the lengths of the isobaric lines PD and HD, respectively, and so on). .
On the other hand, when the source material reaching point O is isentropically expanded (adiabatic expansion), the source material expands along the isentropic line and reaches point Q. The liquefaction rate at this time is QD / HD.
As can be seen from FIG. 1, since QD is longer than PD, the liquefaction rate QD / HD when the isentropic expansion is performed is higher than the liquefaction rate PD / HD when the isentropic expansion is performed. Therefore, in the liquefaction cycle, the liquefaction rate is higher when the isentropic expansion (adiabatic expansion) is performed than when the isenthalpy expansion is performed in the expansion stroke.
After being liquefied from point O through an expansion stroke, the liquid phase portion of the source material is removed (point H), and the gas phase portion returns from point D through line DEFG to the liquefaction cycle.

In the process of conceiving the present invention, the present inventors first examined measures for improving the liquefaction rate as follows.
As described above, in the expansion process of the refrigeration cycle, the liquefaction rate is higher when the isentropic expansion (adiabatic expansion) is performed than the isenthalpy expansion. For this reason, it is also considered that the highest liquefaction rate can be obtained by making all of the expansion strokes an isentropic expansion.
However, since a large expansion ratio cannot be obtained with an expansion turbine that is normally used for isentropic expansion, the efficiency decreases when the entire process is performed with one expansion turbine, so two expansion turbines are prepared. Therefore, measures such as performing an expansion stroke in two stages are considered necessary. On the other hand, if two-stage isentropic expansion is performed using two expansion turbines, the raw material that is in the gas-liquid mixed state from the supercritical state by the first-stage isentropic expansion is introduced into the second expansion turbine. Will be. If it does so, the raw material of the gas-liquid mixed state containing a droplet will be introduce | transduced into a turbine, and the phenomenon (drain attack) which a turbine blade will be damaged by this droplet will occur. Therefore, it is difficult to appropriately perform isentropic expansion in the entire process of the expansion stroke using two expansion turbines.

Therefore, the present inventors diligently studied an expansion method that replaces the method using two expansion turbines. Finally, the expansion stroke of the refrigeration cycle is divided into two stages, and gas-liquid mixing is performed in the first expansion stage. It was found that the liquefaction rate can be improved as a whole of the liquefaction cycle by gas-liquid separation of the raw material in a state and expanding the separated liquid phase part and the gas phase part independently in the second expansion step. .
It is possible to perform isentropic expansion with an expansion turbine or the like for the gas phase portion, and the isenthalpy line is compared to the isentropic line near the liquidus line on the relatively low entropy side in the Ts diagram. This is considered to be because the liquefaction rate is not relatively lowered as a whole in the liquefaction cycle even if the enthalpy expansion is performed for the liquid phase portion after the gas-liquid separation.

  The liquid production method according to some embodiments is based on the above findings by the inventors, and includes a supercritical process for transferring the raw material from a gas state to a supercritical state, and a first expansion step for expanding the raw material. A gas-liquid separation step of separating the raw material in a gas-liquid mixed state into a first liquid phase portion and a first gas phase portion; a second expansion step of expanding the first liquid phase portion along an isoenthalpy line; And a third expansion step of expanding the gas phase portion along the isentropic line.

FIG.2 and FIG.6 is a Ts diagram which respectively shows the liquefaction cycle in the liquid manufacturing method which concerns on one Embodiment.
The supercriticalization process in the exemplary embodiment relating to the liquefaction cycle shown in FIGS. 2 and 6 is a process of introducing the raw material in a gaseous state to a point O that is a pressure higher than the critical pressure and a temperature higher than the critical temperature. It is. In some embodiments, the supercriticalization step may include a step (line GA in FIGS. 2 and 6) of compressing the low-pressure gaseous source material to a pressure equal to or higher than the critical pressure. Further, some embodiments may include a step of cooling the raw material in a gaseous state compressed to a critical pressure or more along the isobaric line ABCO (line ABCO in FIGS. 2 and 6).

  A 1st expansion | swelling process is a process of expanding the said raw material so that the raw material of a supercritical state (point O) may be in a gas-liquid mixed state. In the exemplary embodiment according to the liquefaction cycle shown in FIG. 2, the supercritical material is expanded along the isenthalpy line (line OS in FIG. 2). On the other hand, in the exemplary embodiment according to the liquefaction cycle shown in FIG. 6, the raw material in the supercritical state is expanded along the isentropic line (line OR in FIG. 6).

The point at which the first expansion step ends is not particularly limited, and may be set as appropriate according to the expansion capability of the expander to be used.
Assuming that the pressure at the start of the first expansion step is P ₀ , the pressure at the end of the first expansion step is P ₁ , and the pressure at the end of the second expansion step after the subsequent gas-liquid separation step is P ₂ , in Kano embodiment, the _{P 1, P 0} and _{P 2} of the arithmetic mean _{((P 0 + P 2)} / 2) and geometric mean _(P 0 the square root of _{P 2)} may be.
Also, the higher the rate of expansion along the isentropic line, the higher the liquefaction rate. Therefore, in the exemplary embodiment relating to the liquefaction cycle shown in FIG. 6, in the first expansion step until the pressure is as low as possible. Inflation may be performed. For example, the first expansion step may be performed until the pressure is as low as possible with one expansion turbine within a range in which damage to the turbine blade due to the drain attack does not substantially become a problem.

  In the gas-liquid separation step, the raw material in the gas-liquid mixed state that has undergone the first expansion step is separated into a first liquid phase portion and a first gas phase portion. In the exemplary embodiment according to the liquefaction cycle shown in FIG. 2 and FIG. 6, the gas-liquid mixed state raw material is gas-liquid separated using the gas-liquid separation means, and the liquid phase portion of the gas-liquid mixed state raw material is One liquid phase portion (line SY in FIG. 2 and line RY in FIG. 6), and the gas phase portion of the raw material in the gas-liquid mixed state is defined as the first gas phase portion (line SX in FIG. 2 and line RX in FIG. 6). ).

  In the second expansion step, the first liquid phase portion separated in the gas-liquid separation step is expanded along the isoenthalpy line, and the gas-liquid mixture includes the second liquid phase portion at a lower temperature and lower pressure than the first liquid phase portion. Get. In the exemplary embodiment according to the liquefaction cycle shown in FIGS. 2 and 6, the second expansion step is indicated by line YU. A 2nd liquid phase part is taken out in the point H as a product liquid among the gas-liquid mixtures obtained at the 2nd expansion process. The gas phase portion of the gas-liquid mixture obtained in the second expansion step is returned from the point D to the gaseous raw material liquefaction cycle.

  In the third expansion step, the first gas phase portion separated in the gas-liquid separation step is expanded along the isentropic line to obtain a gas-liquid mixture including the third liquid phase portion. In the exemplary embodiment according to the liquefaction cycle shown in FIGS. 2 and 6, the third expansion step is indicated by line XT. The third liquid phase portion of the gas-liquid mixture obtained in the third expansion step is taken out at point H as the produced liquid. The gas phase portion of the gas-liquid mixture obtained in the third expansion step is returned from the point D to the gaseous raw material liquefaction cycle.

In some embodiments, the gas-liquid separation process and the subsequent expansion processes (second expansion process and third expansion process) may be performed in multiple stages. That is, a series of processes of the gas-liquid separation process and the subsequent second expansion process and third expansion process may be performed a plurality of times.
In the exemplary embodiment relating to the liquefaction cycle shown in FIG. 4, after the raw material in the supercritical state is subjected to isoenthalpy expansion (line OS ′), the first liquid phase portion and the first gas phase are separated in the first gas-liquid separation step. Separate into phase parts (line S′Y ′ and line S′X ′, respectively).
Here, paying attention to the first liquid phase portion, the first liquid phase portion is expanded along the isoenthalpy line in the first second expansion step, and a gas-liquid mixture including the second liquid phase portion is obtained (line). Y'U '). Then, the gas-liquid mixture including the second liquid phase part is further separated into the second liquid phase part and the gas phase part in the second gas-liquid separation step (line U′Y ″ and line U′X ″). The second liquid phase part is subjected to isoenthalpy expansion in the second second expansion step, and a gas-liquid mixture including a liquid phase part having a lower temperature and a lower pressure than the second liquid phase part is obtained (line Y ″ U ″). . Further, the gas phase portion is isentropically expanded in the second third expansion step, and a gas-liquid mixture including the liquid phase portion is obtained (line X ″ T ″). The liquid phase part of the gas-liquid mixture at points U ″ and T ″ is withdrawn at point H as product liquid.
On the other hand, paying attention to the first gas phase portion, the first gas phase portion is expanded along the isentropic line in the first third expansion step, and a gas-liquid mixture including the third liquid phase portion is obtained (line). X'T '). Then, the gas-liquid mixture including the third liquid phase part is further separated into the third liquid phase part and the gas phase part in the second gas-liquid separation step (line T′Y ″ and line T′X ″). The third liquid phase part is subjected to isoenthalpy expansion in the second second expansion step, and a gas-liquid mixture containing a liquid phase part having a lower temperature and lower pressure than the third liquid phase part is obtained (line Y ″ U ″). . Further, the gas phase portion is isentropically expanded in the second third expansion step, and a gas-liquid mixture including the liquid phase portion is obtained (line X ″ T ″). The liquid phase part of the gas-liquid mixture at points U ″ and T ″ is withdrawn at point H as product liquid.
Thus, the liquefaction rate from the raw material in a gaseous state can be further improved by performing the gas-liquid separation step and the subsequent expansion steps (second expansion step and third expansion step) in multiple stages.

Next, the liquid manufacturing facility according to the embodiment will be described with reference to FIGS. 3 and 7.
3 and 7 are diagrams schematically showing the configuration of the liquid manufacturing apparatus according to the embodiment.

  As shown in FIGS. 3 and 7, the liquid production facility 1 includes a supercritical apparatus 10, a first expander 20, a gas-liquid separator 30, a second expander 40, and a third expander 50. Is provided.

  The supercritical apparatus 10 is configured to shift the raw material from a gaseous state to a supercritical state. In the exemplary embodiment shown in FIG. 3 and FIG. 7, the supercritical apparatus 10 includes a compressor for compressing a gaseous raw material to a supercritical pressure or higher, and heating and cooling the raw material by heat exchange in a liquefaction cycle. The heat exchanger 4 (4a-4e) for performing, and the expander 6 (6a, 6b) for expanding the compressed raw material are included. As shown in FIGS. 3 and 7, the supercritical apparatus 10 is configured so that the raw material expanded by the expander 6 (6a, 6b) into a low-temperature gas returns to the line on the compressor suction side, The compressed high-temperature raw material may be cooled by heat exchange.

The first expander 20 is an expander for expanding the raw material so that the raw material that has become supercritical by the supercritical apparatus 10 is in a gas-liquid mixed state.
In the exemplary embodiment shown in FIG. 3, the first inflator 20 is an expansion valve 20 a that can realize expansion along an isenthalpy line.
On the other hand, in the exemplary embodiment shown in FIG. 7, the expander 20 is an expansion turbine 20 b capable of realizing expansion along the isentropic line. The expansion turbine has a problem that a drain attack occurs when the fluid to be expanded is introduced into the expansion turbine in a gas-liquid mixed state. However, if the fluid to be expanded is a gas or a supercritical fluid at the inlet of the expansion turbine, the expansion turbine 20 b can be adopted as the first expander 20. Other examples of the expander that can realize expansion along the isentropic line include positive displacement expanders such as a reciprocal expander and a scroll expander. In other embodiments, these expanders are replaced with the expansion turbine 20b. An inflator may be employed.

The gas-liquid separator 30 is configured to separate the raw material in the gas-liquid mixed state that has passed through the first expander 20 into a first liquid phase portion and a first gas phase portion.
In some embodiments, the gas-liquid separator 30 is a baffle-type gas-liquid separator using a baffle plate 31, as shown in FIG. Separate into part and liquid phase part.
In another embodiment, a demister-type gas-liquid separator having a demister is used as the gas-liquid separator 30.

The second expander 40 is an expander for expanding the first liquid phase portion separated by the gas-liquid separator 30 along the isenthalpy line. The third expander 50 is an expander for expanding the first gas phase portion separated by the gas-liquid separator 30 along the isentropic line.
In some embodiments, as in the exemplary embodiment shown in FIGS. 3 and 7, the second expander 40 is an expansion valve and the third expander 50 is an expansion turbine. In another embodiment, a positive displacement expander such as a reciprocal expander or a scroll expander may be used as the third expander 50.

Next, the improvement effect of the liquefaction rate by the liquid manufacturing method according to some embodiments will be shown by calculation.
In the following liquid production method, the liquefaction rate in the case of liquefying by expanding nitrogen in a supercritical state (pressure: 40 atm, temperature: 130K) to pressure: 1 atm was obtained by calculation. In the case of the method according to the above-described embodiment (method 2 and method 3), the first expansion step is ended when the pressure reaches 10 atm.
(Method 1) The liquid production method according to the liquefaction cycle shown in FIG. 1 (expansion stroke is the line OP in FIG. 1), in which the expansion stroke is an expansion along only an enthalpy line using an expansion valve in only one stroke.
(Method 2) Liquid manufacturing method of the embodiment according to the liquefaction cycle shown in FIG. 2 using the liquid manufacturing facility shown in FIG. 3 (the first expansion step is the line OS in FIG. 2 and the second expansion step is the line YU in FIG. 2). The third expansion step is line XT).
(Method 3) Liquid production method of the embodiment according to the liquefaction cycle shown in FIG. 6 using the liquid production facility shown in FIG. 7 (the first expansion step is the line OR in FIG. 6 and the second expansion step is the line YU in FIG. 6). The third expansion step is line XT). However, a reciprocating expander was used as the third expander instead of an expansion turbine.
As a result of calculating the liquefaction rate in the ideal state by each of the liquid manufacturing methods described above, it is 0.21 in the method 1, but 0.30 and 0 in the method 2 and the method 3 according to the embodiment of the present invention, respectively. .43.
From this calculation result, it was confirmed that the liquefaction rate was improved as compared with the conventional method by the liquid manufacturing method according to the embodiment of the present invention.

DESCRIPTION OF SYMBOLS 1 Liquid manufacturing equipment 2 Compressor 4 Heat exchanger 6 Expander 10 Supercritical device 20 1st expander 20a Expansion valve 20b Expansion turbine 30 Gas-liquid separator 40 2nd expander 50 3rd expander

Claims (6)

A method for producing a liquid from a raw material in a gaseous state,
A supercritical process for transferring the raw material from a gaseous state to a supercritical state;
A first expansion step of expanding the raw material so that the supercritical raw material is in a gas-liquid mixed state;
A gas-liquid separation step of separating the raw material in the gas-liquid mixed state after the first expansion step into a first liquid phase portion and a first gas phase portion;
A second expansion step of expanding the first liquid phase portion along an isoenthalpy line to obtain a gas-liquid mixture including a second liquid phase portion at a lower temperature and low pressure than the first liquid phase portion;
A third expansion step of expanding the first gas phase portion along an isentropic line to obtain a gas-liquid mixture including the third liquid phase portion.   The liquid production method according to claim 1, wherein in the first expansion step, the raw material in the supercritical state is expanded along an isoenthalpy line.   The liquid manufacturing method according to claim 1, wherein in the first expansion step, the raw material in the supercritical state is expanded along an isentropic line. A facility for producing a liquid from a raw material in a gaseous state,
A supercritical apparatus for transferring the raw material from a gas state to a supercritical state;
A first expander for expanding the raw material so that the supercritical raw material is in a gas-liquid mixed state;
A gas-liquid separator for separating the raw material in a gas-liquid mixed state that has passed through the first expander into a first liquid phase portion and a first gas phase portion;
A second expander for expanding the first liquid phase portion along an isoenthalpy line to obtain a gas-liquid mixture including a second liquid phase portion at a lower temperature and pressure than the first liquid phase portion;
And a third expander for expanding the first gas phase portion along the isentropic line to obtain a gas-liquid mixture including the third liquid phase portion.   The liquid production facility according to claim 4, wherein the first expander is an expansion valve for expanding the raw material in the supercritical state along an isoenthalpy line.   The liquid production facility according to claim 4, wherein the first expander is an expansion turbine for expanding the raw material in the supercritical state along an isentropic line.

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