KR20230088936A - Appratus for extracting hydrogen using steam - Google Patents

Abstract

An apparatus for extracting hydrogen using high-temperature steam according to an embodiment of the present invention is an apparatus for extracting hydrogen from a fuel having carbon, comprising: a melting means for reforming the fuel by using high-temperature steam; A heat recovery means that cools the exhaust gas containing hydrogen and carbon dioxide generated after heating to recover waste heat, and extracts only hydrogen using a palladium-coated separator for the gas that moves after being cooled by the heat recovery means. A means for storing liquefied hydrogen by cooling hydrogen below -273℃, and the remaining carbon dioxide dust after hydrogen extraction is collected through a bag filter, and the passed carbon dioxide is cooled to below 31.5℃ and compressed to be stored in liquid form. including facilities that

Description

Hydrogen extraction apparatus using high-temperature steam {Appratus for extracting hydrogen using steam}

The present invention relates to an apparatus capable of separating and extracting hydrogen and carbon dioxide by reforming combustible fuel (waste) using high-temperature pure steam.

Representative methods for producing hydrogen for industrial use include petroleum by-products and naphtha cracking processes. The naphtha cracking center (NCC: NAPHTHA CRACKING CENTER) is a process that produces ethylene (C ₂ H ₄ ) and propylene (C ₂ C ₃ H ₆ ), which are generally basic raw materials for petrochemicals, but is grafted into a connected process for hydrogen production. it did However, the above process is difficult to apply to industries that require only hydrogen as a unit process as well as high energy consumption for hydrogen production. In addition, due to the use of transportation means such as vehicles, it becomes a factor that increases a considerable amount of additional cost.

On the other hand, the thermal chemical vapor deposition type carbon nanotube production method requires a large amount of hydrogen and has a problem in that the quality of the produced carbon nanotubes is deteriorated due to impurities contained in the hydrogen. Therefore, it is necessary to apply the On-Site system that can produce high-purity hydrogen on site and supply it directly to production facilities in order to have productivity. As other methods, various methods such as catalytic decomposition of hydrocarbons and water or electrolysis of water have been tried, but they are still at the technical level of research.

The present invention is to propose a device capable of reforming waste by using a steam generator capable of raising the temperature of water vapor to a high enough temperature to allow reforming of waste, and separating and extracting hydrogen and carbon dioxide therefrom.

An apparatus for extracting hydrogen using high-temperature steam according to an embodiment of the present invention is an apparatus for extracting hydrogen from a fuel having carbon, comprising: a melting means for reforming the fuel by using high-temperature steam; Hydrogen and carbon dioxide are separated by using a heat recovery unit that cools the exhaust gas containing hydrogen and carbon dioxide generated after heating so that heat recovery is performed, and a palladium-coated separator for the moving gas after being cooled by the heat recovery unit. It includes an extraction means, and a hydrogen storage means for storing compressed hydrogen after extraction by the hydrogen extraction means.

And, it further includes a carbon dioxide collecting means for storing after removing dust from the liquefied carbon dioxide after the hydrogen extraction is performed in the hydrogen extracting means.

Further, the melting means includes a fuel tank for storing the fuel, a fixed-rate supply screw for moving the fuel stored in the fuel tank, and a pyrolysis chamber screw for receiving and descending the fuel transferred through the fixed-rate supply screw; A re-transfer screw connected to the end of the pyrolysis chamber screw and lowering the residue remaining after reforming the fuel, a porous cylinder having a plurality of holes formed as a cylinder surrounding the pyrolysis chamber screw, and , A thermal decomposition chamber cylinder formed in a shape surrounding the porous cylinder and spaced apart from the outer circumferential surface of the porous cylinder by a predetermined distance, and a first high-temperature steam supply pipe for supplying steam between the porous cylinder and the thermal decomposition chamber cylinder.

In addition, steam is supplied to a first outer cylinder having a shape surrounding a part of the cylinder of the thermal decomposition chamber, a second outer cylinder having a shape surrounding a part of the first outer cylinder, and a space between the first outer cylinder and the second outer cylinder. Between the connected second high-temperature steam supply pipe, the pyrolysis chamber screw and the retransfer screw, a gas ash separation network for filtering residual fuel remaining after reforming of the fuel, and ash moving downward through the gas ash separation network It further includes an ashes for collection.

The hydrogen extraction means includes a cylindrical palladium-coated separator and a hydrogen extraction outer cylinder formed of a cylinder surrounding the palladium-coated separator, and the gas that moves after being cooled by the heat recovery means is coated with the palladium. It is configured to move to the space between the separation membrane and the hydrogen extraction outer cylinder.

With the proposed hydrogen extraction device, there is no problem of environmental pollution by reforming carbon-containing fuel (waste) using high-temperature steam, and hydrogen and carbon dioxide can be separated/extracted efficiently and at low cost There are advantages to being

1 and 2 are views showing the overall configuration of a hydrogen extraction device according to an embodiment of the present invention.
3 and 4 are views showing high-temperature steam generating means constituting the hydrogen extraction device of this embodiment.

Hereinafter, the embodiments disclosed in this specification will be described in detail with reference to the accompanying drawings, but the same or similar elements are given the same reference numerals regardless of reference numerals, and redundant description thereof will be omitted. The suffixes "module" and "unit" for components used in the following description are given or used together in consideration of ease of writing the specification, and do not have meanings or roles that are distinct from each other by themselves. In addition, in describing the embodiments disclosed in this specification, if it is determined that a detailed description of a related known technology may obscure the gist of the embodiment disclosed in this specification, the detailed description thereof will be omitted. In addition, the accompanying drawings are only for easy understanding of the embodiments disclosed in this specification, the technical idea disclosed in this specification is not limited by the accompanying drawings, and all changes included in the spirit and technical scope of the present invention , it should be understood to include equivalents or substitutes.

It is understood that when an element is referred to as being "connected" or "connected" to another element, it may be directly connected or connected to the other element, but other elements may exist in the middle. It should be. On the other hand, when an element is referred to as “directly connected” or “directly connected” to another element, it should be understood that no other element exists in the middle.

1 and 2 are views showing the overall configuration of a hydrogen extraction device according to an embodiment of the present invention.

The present invention relates to an apparatus for separating/extracting hydrogen and carbon dioxide by reforming various types of fuel (waste), respectively. Referring to FIGS. A melting means for reforming using steam, a heat recovery means 2 for heat recovery (necessary steam) by cooling the exhaust gas containing hydrogen and carbon dioxide that is heated and reformed by the melting means and transported, A hydrogen extraction means (3) for separating hydrogen and carbon dioxide from the gas cooled by the heat recovery means (2) using a palladium-coated separator (301), and storing the hydrogen extracted by the hydrogen extraction means (3) It includes a hydrogen storage means (4) and a carbon dioxide collecting means (5) for storing dust after removing dust from carbon dioxide remaining after hydrogen extraction in the hydrogen extraction means (3).

Each means constituting the hydrogen extraction device of the present invention will be described in detail.

First, the melting means reforms fuel (waste) using high-temperature steam and transfers the heat to the heat recovery means 2 including a boiler capable of generating steam in gaseous form, and fuel container 11 in which waste, which is fuel, is stored. And, a fixed amount supply screw 21 for moving a certain amount of fuel in the fuel tank 11 at a constant speed, receiving the fuel transferred in a fixed amount through the fixed amount supply screw 21 and transferring it downward to be reformed It includes a thermal decomposition chamber screw 22 and a re-transfer screw 23 connected to an end of the thermal decomposition chamber screw 22 to lower and move the residue remaining after reforming the fuel, and these screws 21, 22, 23) is composed of a motor that provides power so that each rotation is made.

The residue descended by the re-transfer screw 23 is collected in the re-tub 12 configured on one side.

The device of the present invention is for extracting hydrogen from fuel such as carbon-containing waste, and extracting hydrogen using electricity, which is a conventional general method, requires enormous costs, whereas in the present invention, high-temperature steam It is used to reform fuel to extract hydrogen.

In addition, the thermal decomposition chamber screw 22 is disposed in a thermal decomposition chamber in which reforming is performed through high-temperature steam while lowering the fuel supplied in a fixed quantity. A porous cylinder 51 having a plurality of holes formed to allow steam to move to the pyrolysis chamber screw 22, and a shape surrounding the porous cylinder 51 and spaced a predetermined distance from the outer circumferential surface of the porous cylinder 51 A pyrolysis chamber cylinder 52 formed to be formed, a first outer cylinder 53 formed to surround a part of the pyrolysis chamber cylinder 52, and a second outer cylinder formed to surround a part of the first outer cylinder 53 ( 54).

And, in order to supply high-temperature steam to the thermal decomposition chamber cylinder 52, the first high-temperature steam supply pipe 41 and the steam supplied through the first high-temperature steam supply pipe 41 are further heated as needed. It includes a hydrogen burner (31).

Steam supplied through the first high-temperature steam supply pipe 41 is supplied between the porous cylinder 51 and the pyrolysis chamber cylinder 52 via the hydrogen burner 31 in the pyrolysis chamber. Since two holes are formed, the supplied high-temperature steam is supplied to contact the pyrolysis chamber screw 22, that is, the fuel. High-temperature steam of about 1,300° C. is supplied to the pyrolysis chamber screw 22 to reform the fuel.

That is, a plurality of perforated networks are formed in the perforated cylinder 51 so that high-temperature steam directly contacts the fuel. Reformation can take place. At this time, the carbon of the fuel becomes a catalyst and is changed to CO by exotherm, and is converted back to CO ₂ by the formed OH group, undergoing an endothermic reaction, and oxygen is removed from the supplied steam, leaving hydrogen. That is, while changing into CO ₂ by the reaction of carbon and high-temperature steam of the fuel, hydrogen remains, and the remaining ash moves downward.

Then, while turning downward with hydrogen and carbon dioxide gas, the steam meets the steam rising from the lower part through the hydrogen burner 31 again and rises.

In addition, in this embodiment, in addition to the reforming of the fuel using the high-temperature steam supplied through the first high-temperature steam supply pipe 41, the second high-temperature steam supply pipe 42 is used to further reform the remaining fuel. Further, an additional hydrogen burner 32 capable of further heating the steam supplied through the second high-temperature steam supply pipe 42 is coupled to the end of the second high-temperature steam supply pipe 42 .

The steam supplied through the second high-temperature steam supply pipe 42 and the steam heated by the hydrogen burner 32 are configured to be supplied to the space between the first outer cylinder 53 and the second outer cylinder 54, and are approximately at that temperature. is made at a temperature of 800 ° C to 1,000 ° C. Then, the residual fuel remaining in the lower side of the re-transfer screw 23 and the cone 62 at the lower side of the pyrolysis chamber 52 is additionally reformed, and then rises again. In addition, the reformed gas that has undergone reforming of the fuel by high-temperature steam in the pyrolysis chamber 52 also moves to the lower gas material separation network 61, together with the reformed gas in the cone 62. While turning and moving along the inside of the first outer cylinder 53, it moves to the heat recovery means 2 through the connecting pipe.

The gas ash separation network 61 configured below the pyrolysis chamber screw 22 serves to separate ash such as dust remaining after reforming fuel and residual fuel that has not been reformed, and the gas ash A re-transfer screw 23 is configured below the separation network 61, and the ash passing through the gas ash separation network 61 moves downward along the re-transfer screw 23 and is collected in the re-tub 12.

As shown, the second outer cylinder 54 at the location where the gas material separation network 61 is configured is configured to have a part in the shape of a cone 62, and is collected by the receptacle 12. It is configured so that additional reforming using the ash that has not been partially reformed before the step, the steam supplied through the second high-temperature steam supply pipe 42, and the steam heated in the hydrogen burner 32 is continued.

Next, the steam used for reforming the fuel (steam supplied through the first high-temperature steam supply pipe and the second high-temperature steam supply pipe) is converted into CO ₂ and H ₂ gas after reforming, and the heat recovery means (2 ), and cooled by the water supply 205 in the heat recovery means 2, that is, steam is made.

The heat recovery means 2 cools the carbon dioxide and hydrogen gas moving along the connecting pipe at a temperature of about 800 ° C with water 205, recovers heat to the heat transfer area below 100 ° C, and serves to have a required amount of steam, , a heat recovery boiler 200 in which a water 205 injection part is installed, a safety valve 201, a recycle bin 202, a steam outlet part 203, and a boiler auxiliary burner 204.

The steam discharged from the heat recovery means 2 may be supplied to the first high-temperature steam supply pipe 41 and the second high-temperature steam supply pipe 42 again, and the first and second high-temperature steam supply pipes 41 have separate The high-temperature steam hydrogen burners 31 and 32 are further connected to stably receive high-temperature steam. This high-temperature steam generating means will be described in detail below along with drawings.

In the heat recovery means (2), carbon dioxide and hydrogen are transferred to the hydrogen extraction means (3) for extracting hydrogen at a lower temperature after recovering heat, and the hydrogen extraction means (3) is a cylindrical palladium-coated separator (301). ) and a hydrogen extraction outer cylinder 302 formed of a cylinder surrounding the palladium-coated separator 301, by sucking and compressing hydrogen moving downward through the inside of the palladium-coated separator 301 (cooling). and) the hydrogen extraction pressure pump 311 transported to the hydrogen storage tank 400, and the carbon dioxide moving to the space between the palladium-coated separator 301 and the hydrogen extraction outer cylinder 302. By inhaling and compressing (cooling) carbon dioxide It includes a carbon dioxide capture pressure pump 312 that transfers to the transfer pipe 511.

In particular, carbon dioxide and hydrogen transported from the heat recovery means 2 are configured to be supplied to the space between the palladium-coated separator 301 and the hydrogen extraction outer cylinder 302, and the palladium-coated separator 301 has a molecular size due to the nature of palladium. While allowing small hydrogen to pass through, carbon dioxide does not pass through, so that only hydrogen is collected inside the palladium-coated separator 301, and a hydrogen extraction pressure pump 311 is configured below it to compress and store hydrogen. It is cooled and stored in the hydrogen storage tank 400 in a liquefied state. The hydrogen extraction pressure pump compresses to 75 atm or more or cools to -273 ° C or less, and the compressed or cooled hydrogen is stored in the hydrogen reservoir 400 in a liquefied state.

In addition, the carbon dioxide moving downward in the space between the palladium-coated separator 301 and the hydrogen extraction outer cylinder 302 is sucked and pressurized by the carbon dioxide collecting pressure pump 312, and the liquefied carbon dioxide is transferred to the carbon dioxide moving pipe ( 511) is transferred to the carbon dioxide collecting means 5. The carbon dioxide collecting pressurizing pump 312 cools the carbon dioxide to 31.5° C. or less, compresses it, and stores it in the carbon dioxide collecting container 510 as a liquid.

The carbon dioxide collecting unit 5 includes a cyclone 500 including a bag filter while generating centrifugal force to remove/collect dust included in the carbon dioxide transported, a dust bin 501 for storing dust collected from the lower side, and , and a carbon dioxide collection container 510 for storing the dust-removed carbon dioxide.

3 and 4 are views showing high-temperature steam generating means constituting the hydrogen extraction device of this embodiment.

As shown in FIGS. 3 and 4, the high-temperature steam generator is a device capable of generating and discharging high-temperature steam in the range of about 300 ° C to 1,500 ° C, and the generated high-temperature steam is generated in the first thermal decomposition chamber (52 , inside the cylinder of the pyrolysis chamber) and/or to the second pyrolysis reforming chamber (54, inside the second outer cylinder).

The temperature, pressure, and amount of the high-temperature exhaust steam can be controlled using the temperature, pressure, and amount of hydrogen and oxygen gases introduced.

The high-temperature steam generating means has a structure in which fuel gas is input to one side (left side in the drawing) and high-temperature steam is discharged as exhaust gas to the other side (right side in the drawing), and the inner cylinder 620 includes a combustion chamber in which high-temperature combustion takes place. ), an outer cylinder 610 formed in a shape surrounding the inner cylinder 620 and forming an external shape, a main turning passage formed between the inner cylinder 620 and the outer cylinder 610, and the inner cylinder 620, A hydrogen inlet pipe 621 through which target hydrogen gas is supplied, and an oxygen whirling cylinder having a shape surrounding the hydrogen inlet pipe 621 so that the oxygen gas moves along the outer circumferential surface of the hydrogen inlet pipe 621 while turning. 622, a steam swirling cylinder 623 formed in a shape surrounding a part of the oxygen swirling cylinder 622 and allowing steam to move along the outer circumferential surface of the oxygen swirling cylinder 622 while swirling, and the inner cylinder 620 A spark plug 624 installed inside to ignite hydrogen gas introduced through the hydrogen injection pipe 621, and high-temperature steam generated after combustion of hydrogen and oxygen in the inner cylinder 620 is discharged It includes a discharge part 603.

The discharge unit 603 may be configured to be connected to the first high-temperature steam supply pipe 41 and/or the second high-temperature steam supply pipe 42 .

In addition, an oxygen injection pipe 720 and a first steam injection pipe 730 respectively move oxygen and steam moving toward the inner cylinder 620 while swirling in the oxygen swirling cylinder 622 and the steam swirling cylinder 623 It is connected to the oxygen vortex 622 and the steam vortex 623.

In addition, a second steam injection pipe 810 for supplying steam to the main turning passage formed between the outer cylinder 610 and the inner cylinder 620 is included.

The hydrogen gas to be burned is introduced into the inner cylinder 620 through the hydrogen injection pipe 621, and combustion is performed using oxygen injected through the oxygen swirling cylinder 622, using steam at about 120 ° C. This can lower the temperature inside the combustion chamber. Since the device may be damaged if it is maintained at a very high temperature through the combustion of hydrogen, combustion is performed at a temperature that the material of the device can withstand using steam supplied to the combustion chamber by turning.

The inlet tubes 720, 730, and 810 are installed so that the gas inflow direction is formed in a direction consistent with the tangential direction of the outer walls of the oxygen circulating cylinder 622, the steam circulating cylinder 623, and the inner cylinder 620/outer cylinder 610, Each gas moves while having a centrifugal force inside the cylinder, and gradually rises (rightward direction in the drawing) while maintaining the centrifugal force.

For example, the oxygen inlet pipe 720 is coupled to the oxygen circulating cylinder 622 in a tangential direction with respect to the outer wall (outer circumferential surface) of the hydrogen inlet pipe 621 . Also, it can be said that the oxygen inlet pipe 720 is coupled in a tangential direction with respect to the outer wall (outer circumferential surface) of the oxygen circulating cylinder 622 . The coupling positions of the injection tubes, that is, the direction in which gas is supplied, are all installed so that they can move while turning inside.

While swirling along the inside of the oxygen circulating cylinder 622 and the steam circulating cylinder 623, oxygen and steam gradually moving toward the inner cylinder 620 where the spark plug 624 is located are mixed with hydrogen gas supplied through the hydrogen injection pipe 621. It is ignited together, and combustion begins.

In addition, the steam of about 120° C. supplied through the second steam injection pipe 810 is supplied in the tangential direction of the outer wall of the inner cylinder 620, along the main swirling passage between the inner cylinder 620 and the outer cylinder 610. While turning, it gradually moves to the discharge unit 603. Here, the first rising steam, which gradually moves toward the discharge part 603 while turning along the main swirling passage, changes its movement path at the end of the outer cylinder 610, and gradually moves along the inner wall of the inner cylinder 620 to the spark plug. It becomes the descending steam moving towards the inlet where 624 is located.

That is, a space is formed at the end of the inner cylinder and the outer cylinder so that the steam moving while turning along the main swirling passage moves along the inner circumferential surface of the inner cylinder, so that the steam hitting the end of the outer cylinder turns along the inner circumferential surface of the inner cylinder.

And, the falling steam (b) becomes the second rising steam that rises toward the discharge part 603 from the space where combustion takes place, that is, the center of the inner cylinder 620. That is, the second rising steam is moved toward the discharge unit 603 while turning around the hydrogen combustion fire generated when combustion is started by the spark plug 624 .

The movement of the first rising steam while turning along the outer circumferential surface of the inner cylinder 620, the movement of the descending steam while turning along the inner circumferential surface of the inner cylinder 620, and the movement of the second rising steam gradually turning in the combustion space at the center of the inner cylinder 620. Through a process such as upward movement, the contact time with the combustion steam inside the inner cylinder 620 constituting the combustion chamber is greatly increased, and as a result, very high temperature steam can be produced.

In particular, since ignition and combustion of a mixture of hydrogen, oxygen, and steam are performed at the inlet side of the inner cylinder 620, there is no problem with environmental pollution due to the use of nitrogen, and as described above, The amount, pressure, and temperature of high-temperature steam discharged through the discharge unit 603 may be adjusted by adjusting the amount, pressure, and temperature of hydrogen, oxygen, and steam. In addition, by adjusting the amount of steam supplied through the first steam injection pipe 730 and the second steam injection pipe 810, the temperature and amount of the discharged steam may be adjusted.

The high-temperature steam supplied through the first steam injection pipe 730 and the second steam injection pipe 810 serves to burn hydrogen to adjust the steam temperature inside the combustion chamber to 300 ° C to 1,500 ° C or more.

In general, reforming takes place only when the steam is raised to 700 ° C or higher. It is raised to a high pressure (30 bar to 40 bar) up to 300 ~ 400 ° C using a superheater, but in the case of heating to a higher temperature, an additional heater was used. . If carbon is used for combustion, CO ₂ is generated, and when air is used for combustion, exhaust gas after heating is a problem such as nitrogen oxides are generated.

In order to prevent environmental pollution caused by exhaust gas while reforming during such combustion, hydrogen is mixed with steam at a high temperature of about 120 ° C. can

Claims (6)

An apparatus for extracting hydrogen from a carbon-containing fuel, comprising:
Melting means for reforming the fuel by using high-temperature steam;
Heat recovery means for recovering waste heat by cooling the exhaust gas containing hydrogen and carbon dioxide generated after heating the fuel by the melting means;
A hydrogen extraction means for extracting only hydrogen from the moving gas cooled by the heat recovery means using a palladium-coated separator and storing the extracted hydrogen;
Hydrogen extraction device using high-temperature steam comprising a carbon dioxide collecting means for collecting and removing dust from the gas remaining after hydrogen extraction by the hydrogen extracting means and then storing carbon dioxide. According to claim 1,
The melting means,
A fuel tank in which the fuel is stored, a fixed-rate supply screw for moving the fuel stored in the fuel tank, a pyrolysis chamber screw for receiving and descending the fuel transferred through the fixed-rate supply screw, and at an end of the pyrolysis chamber screw A re-transfer screw connected to move the residue left after reforming of the fuel downwardly, a porous cylinder having a plurality of holes formed as a cylinder surrounding the pyrolysis chamber screw, and a shape surrounding the porous cylinder. A thermal decomposition chamber cylinder formed to be spaced apart from the outer circumferential surface of the porous cylinder by a predetermined distance, a first high-temperature steam supply pipe through which steam is supplied in a swirling manner between the porous cylinder and the thermal decomposition chamber cylinder, and between the thermal decomposition chamber screw and the re-transfer screw A hydrogen extraction device using high-temperature steam including a gas material separation network for filtering out residues remaining after reforming of fuel. According to claim 2,
A first outer cylinder having a shape surrounding a part of the cylinder of the thermal decomposition chamber, a second outer cylinder having a shape surrounding a part of the first outer cylinder, and a first outer cylinder connected so that steam is supplied to the space between the first outer cylinder and the second outer cylinder. 2 High-temperature steam supply pipe, a cone disposed between the re-transfer screw and the pyrolysis chamber screw to collect the ash that has moved downward through the gas ash separation network, and a ash container that can contain the ash that is being moved. Hydrogen extraction device using steam. According to claim 3,
A hydrogen extraction device using high-temperature steam, characterized in that it further comprises a steam production boiler for receiving high-temperature reformed gas through a passage connected from the second outer cylinder and recovering heat, wherein the steam production boiler produces steam through water supply . According to claim 4,
Carbon dioxide and hydrogen, which are gases cooled by the heat recovery means, are swirled and introduced into the hydrogen extraction means,
The hydrogen extraction unit includes a cylindrical palladium-coated separator and a hydrogen extraction outer cylinder made of a cylinder surrounding the palladium-coated separator, and the hydrogen moving downward through the inside of the palladium-coated separator is reduced to 75 atmospheres or more. A hydrogen extraction device using high-temperature steam including a hydrogen extraction pressure pump that compresses or cools to -273 ° C or less, and a hydrogen storage tank that stores compressed or cooled hydrogen. According to claim 5,
The carbon dioxide collecting means is a carbon dioxide collecting pressurized pump that compresses carbon dioxide after cooling it to 31.5 ° C or lower, a cyclone including a bag filter while generating centrifugal force to remove dust contained in the transferred carbon dioxide, and the cooled carbon dioxide is stored A hydrogen extraction device using high-temperature steam including a carbon dioxide collection cylinder.

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