TW201400415A - Ammonia purification system - Google Patents

Abstract

Provided is an ammonia purification system which can purify ammonia by a simplified method, and which can purify ammonia efficiently by suppressing energy consumption. In this ammonia purification system (100), a first adsorption tower (31) and a second adsorption tower (32) adsorb and remove impurities contained in crude ammonia introduced from a raw material storage tank (1). The first adsorption tower (31) and the second adsorption tower (32) each have a laminated structure comprising a tower top adsorption layer, a first intermediate adsorption layer, a second intermediate adsorption layer and a tower bottom adsorption layer. By partially condensing the ammonia introduced from the first adsorption tower (31) and the second adsorption tower (32) to separate a gas-phase component and a liquid-phase component, a condenser (4) separates and removes highly-volatile impurities as the gas-phase component.

Description

Ammonia purification system

The present invention relates to an ammonia purification system for purifying crude ammonia.

In the semiconductor manufacturing process and the liquid crystal manufacturing process, high-purity ammonia is used as a processing agent used in the production of a nitride film. Such high-purity ammonia is obtained by purifying impurities by purifying crude ammonia.

The crude ammonia contains low-boiling gas such as hydrogen, nitrogen, oxygen, argon, carbon monoxide or carbon dioxide, an organic compound such as a hydrocarbon, water or the like as an impurity, and the purity of the crude ammonia which can be usually obtained is about 98 to 99% by weight.

The organic compound such as a hydrocarbon contained in the crude ammonia is usually mainly a carbon number of 1 to 4, but if the hydrogen used as a synthetic raw material for ammonia is produced, the separation of the oil in the cracked gas is insufficient, or it is received from the pump at the time of manufacture. Oil contamination of the pump oil of the type may also be mixed with hydrocarbons having a higher boiling point and a larger molecular weight. Further, when a large amount of water is contained in the ammonia, the function of a semiconductor or the like produced by the ammonia is greatly reduced. Therefore, it is necessary to reduce the moisture in the ammonia as much as possible.

Although the influence of impurities in ammonia differs depending on the type of the semiconductor manufacturing step and the step of using ammonia in the liquid crystal production step, the purity of ammonia is required to be 99.9999% by weight or more (each impurity concentration is 100 ppb or less), and more preferably It is about 99.99999% by weight. In recent years, in the production of illuminants such as gallium nitride, the water concentration is required to be less than 30 ppb.

As a method of removing impurities contained in the crude ammonia, a method of adsorbing and removing impurities by using an adsorbent such as tannin extract, synthetic zeolite or activated carbon is known. A method of distilling off impurities, and the like. Further, a method of combining adsorption with distillation is also known.

For example, Patent Document 1 discloses an ammonia purification system including a first distillation column in which impurities having a lower volatility are removed from a liquid crude ammonia, and an adsorption column which is subjected to a first distillation by an adsorbent. The impurities (mainly moisture) contained in the gaseous ammonia derived from the tower are adsorbed and removed; and the second distillation column removes the highly volatile impurities from the gaseous ammonia derived from the adsorption tower.

Further, Patent Document 2 discloses a method for purifying ammonia by combining a water adsorption column, a hydrocarbon adsorption column, and a distillation column to obtain high-purity ammonia. Further, Patent Document 3 discloses a method for purifying ammonia, which removes impurities having a low boiling point by a distillation column, and then removes moisture from the gaseous ammonia by an adsorption tower, and separates and removes oxygen by a catalyst portion. This gives high purity ammonia.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-206410

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-505830

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2005-162546

In the technique of purifying ammonia disclosed in Patent Documents 1 to 3, the impurities contained in the crude ammonia are removed by adsorption in an adsorption tower, or removed by a catalyst reaction in a catalyst unit, and further distilled by a distillation column. Remove, by this will Ammonia purification. In the method for purifying ammonia disclosed in Patent Documents 1 to 3 as described above, the purified gaseous ammonia derived from the distillation column is condensed into liquid ammonia and recovered. In other words, in the method for purifying ammonia disclosed in Patent Documents 1 to 3, the impurities contained in the crude ammonia are adsorbed and removed, distilled, and coagulated to obtain purified liquid ammonia, and thus, as a purified ammonia. The method cannot be said to be a simplification, and more energy is required for purifying ammonia.

Accordingly, it is an object of the present invention to provide an ammonia purification system which can purify ammonia by a simplified method and can efficiently purify ammonia by suppressing energy consumption.

The present invention relates to an ammonia purification system which is a crude ammonia purifier containing impurities, characterized by comprising: a storage portion for storing crude ammonia and discharging the stored crude ammonia; and an adsorption portion selected from the group consisting of The adsorbent in the activated carbon, the hydrophilic zeolite, the hydrophobic zeolite, the silicone, and the activated alumina is purified by adsorbing and removing impurities contained in the crude ammonia derived from the storage portion, and purifying the purified ammonia. The portion includes one or a plurality of adsorption portions, and the adsorption portion is laminated with the following adsorbent layers in the flow direction of the crude ammonia: a first adsorbent layer containing a first adsorbent, and a plurality of second adsorbent layers containing types a second adsorbent different from the first adsorbent and a third adsorbent layer containing a third adsorbent different in type from the second adsorbent; a segregation unit that separates and purifies the purified ammonia derived from the adsorption unit into a gas phase component and a liquid phase component, thereby separating and removing the highly volatile impurities in the form of a gas phase component. The form of the component obtained purified ammonia in the form of a liquid.

Further, the ammonia purification system of the present invention preferably further includes a vaporization unit that vaporizes a part of the liquid crude ammonia derived from the storage portion, and exports the gaseous ammonia, and the adsorption unit is configured by the above The adsorption portion adsorbs and removes impurities contained in the gaseous ammonia derived from the vaporization portion.

Further, in the ammonia purification system of the present invention, preferably, the first adsorbent is an adsorbent having a high adsorption capacity for water, and the second adsorbent is higher for an organic compound having a carbon number of less than 5. The adsorbent having an adsorption capacity, the third adsorbent is an adsorbent having a high adsorption capacity for an organic compound having 5 or more carbon atoms and water.

Further, in the ammonia purification system of the present invention, it is preferable that the adsorption portion partially stacks the first adsorbent layer, the plurality of second adsorbent layers, and the above-mentioned first adsorbent layer from the upstream side to the downstream side in the flow direction of the crude ammonia. The third adsorbent layer.

Further, in the ammonia purification system of the present invention, preferably, the adsorption unit includes a plurality of the adsorption portions, and the plurality of adsorption portions are connected in series or in parallel.

According to the present invention, an ammonia purification system is a system for purifying crude ammonia containing impurities, including a storage portion, an adsorption portion, and a segregation portion. Storage department stores crude ammonia And export the crude ammonia it stores. The adsorption unit removes and removes impurities contained in the crude ammonia derived from the storage unit, and includes a first adsorbent layer, a plurality of second adsorbent layers, and a third adsorbent laminated in the flow direction of the crude ammonia. The adsorption portion of the layer. In the adsorption portion of the adsorption unit, the first adsorbent layer is a layer containing a first adsorbent, the second adsorbent layer is a layer containing a second adsorbent, and the third adsorbent layer is a layer containing a third adsorbent. Here, each of the first adsorbent, the second adsorbent, and the third adsorbent is an adsorbent selected from the group consisting of activated carbon, hydrophilic zeolite, hydrophobic zeolite, silicone, and activated alumina.

The ammonia derived from the adsorption portion including at least the first adsorbent layer, the plurality of second adsorbent layers, and the adsorption portion of the third adsorbent layer is supplied to the branching portion. The fractionation unit separates the ammonia derived from the adsorption section into a gas phase component and a liquid phase component, thereby separating and removing the highly volatile impurities in the form of a gas phase component, and obtaining the purified component in the form of a liquid phase component. Liquid ammonia.

In the ammonia purification system of the present invention, the first adsorbent, the second adsorbent and the third adsorbent which are contained as adsorbents selected from the group consisting of activated carbon, hydrophilic zeolite, hydrophobic zeolite, and silicone are laminated. The adsorbed portion of the adsorbent layer adsorbs and removes impurities contained in the crude ammonia, so that impurities (mainly water and organic compounds) contained in the crude ammonia can be efficiently adsorbed and removed. Further, the segregation unit separates the ammonia derived from the adsorption unit into a gas phase component and a liquid phase component, so that a highly volatile impurity such as hydrogen, nitrogen, oxygen, argon, carbon monoxide or carbon dioxide can be used as a gas phase. The form of the component is separated and removed, and the purified liquid ammonia is obtained in the form of a liquid phase component. Therefore, the ammonia purification system of the present invention does not need to be accompanied by reflux as in the prior art. The distillation is carried out, and the ammonia can be purified by a simplified method, and ammonia can be efficiently purified by suppressing energy consumption.

Further, according to the present invention, the ammonia purification system further includes a gasification portion. The gasification unit vaporizes a part of the liquid crude ammonia derived from the storage unit, and exports the gaseous ammonia. Further, the adsorption unit adsorbs and removes impurities contained in the gaseous ammonia derived from the vaporization unit by the first adsorbent layer, the plurality of second adsorbent layers, and the adsorption portion of the third adsorbent layer. Since the vaporization unit is configured to vaporize a part of the liquid crude ammonia derived from the reservoir and to export the gaseous ammonia, the volatile impurities contained in the crude ammonia (for example, moisture) can be obtained. A hydrocarbon having a carbon number of 6 or more remains in the liquid phase, and a gaseous ammonia having a reduced volatility is derived.

Further, according to the present invention, in the adsorption portion of the adsorption unit, the first adsorbent contained in the first adsorbent layer is an adsorbent having a high adsorption capacity for water, and the second adsorbent layer is included in the second adsorbent layer. The adsorbent is an adsorbent having a high adsorption capacity for an organic compound having a carbon number of less than 5, and the third adsorbent contained in the third adsorbent layer is higher for an organic compound having a carbon number of 5 or more and water. Adsorption capacity of the adsorbent. In this way, the impurities contained in the crude ammonia are adsorbed and removed by the adsorption portion of the adsorbent layer having different adsorption capacities for water, carbon compounds having less than 5 carbon atoms, and organic compounds having a carbon number of 5 or more. Therefore, impurities (mainly water and organic compounds) contained in the crude ammonia can be efficiently adsorbed and removed.

Moreover, according to the present invention, the adsorption portion of the adsorption unit sequentially deposits the first adsorbent layer, the second adsorbent layer, and the third adsorbent layer from the upstream side to the downstream side in the flow direction of the crude ammonia. The crude ammonia supplied to the adsorption section is in the adsorption section The first adsorbent layer, the second adsorbent layer, and the third adsorbent layer flow in this order. Since the first adsorbent layer contains the first adsorbent having a high adsorption capacity for water, the crude ammonia flowing through the adsorbed portion first adsorbs and removes most of the water in the first adsorbent layer. Thereby, the adsorption capacity of the second adsorbent layer and the third adsorbent layer disposed on the downstream side in the flow direction of ammonia with respect to the first adsorbent layer can be sufficiently exhibited, and the adsorption portion can be improved from the crude ammonia. Adsorption removal of impurities.

Further, according to the invention, the adsorption unit includes a plurality of adsorption portions in which the first adsorbent layer, the second adsorbent layer, and the third adsorbent layer are laminated. A plurality of adsorbed portions are connected in series or in parallel. When the adsorption portion includes a plurality of adsorption portions connected in series, the adsorption removal ability of impurities contained in the crude ammonia can be improved. Further, in the case where the adsorption portion includes a plurality of adsorption portions connected in parallel, the plurality of adsorption portions connected in parallel may be introduced into the crude ammonia derived from the storage portion in a state of being separately separated, so that the adsorption portion may be carried out by one adsorption portion. During the adsorption removal, the other adsorbed portions that have been used are subjected to regeneration treatment so that the other adsorbed portions that have been used can be subjected to the adsorption removal operation again.

The objects, features, and advantages of the invention will be apparent from the description and drawings.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings.

Fig. 1 is a view showing the configuration of an ammonia purification system 100 according to a first embodiment of the present invention. The ammonia purification system 100 of the present embodiment is a liquid containing impurities. System for the purification of crude ammonia. The ammonia purification system 100 includes a raw material storage tank 1 as a storage unit, a vaporizer 2 as a vaporization unit, an adsorption unit 3 as an adsorption unit, a condenser 4 as a partial condensation unit, and a recovery tank 5.

The raw material storage tank 1 is used for storing crude ammonia. In the present embodiment, the crude ammonia stored in the raw material storage tank 1 has a purity of 99% by weight or more, preferably 99.0 to 99.9% by weight.

The raw material storage tank 1 is not particularly limited as long as it is a heat-resistant container having pressure resistance and corrosion resistance. The raw material storage tank 1 stores crude ammonia in the form of liquid ammonia and is controlled to a specific temperature and pressure. The raw material storage tank 1 has a cylindrical internal space, and in a state in which liquid ammonia is stored in the internal space thereof, a gas phase is formed in the upper portion of the raw material storage tank 1, and a liquid phase is formed in the lower portion.

An exhaust pipe 80 is connected to the raw material storage tank 1, and the exhaust pipe 80 serves to exchange the raw material storage tank 1 with the outside, and is highly volatile (for example, hydrogen, nitrogen, and oxygen) distributed in the gas phase. , argon, carbon monoxide, carbon dioxide, etc.) are discharged to the external flow path. The exhaust pipe 80 is provided with an exhaust valve 801 that opens or closes a flow path in the exhaust pipe 80. In the ammonia purification system 100 of the present embodiment, the discharge operation of the high-volatility impurities from the crude ammonia stored in the raw material storage tank 1 can be performed by opening the exhaust valve 801. Specifically, after the liquid crude ammonia is stored in the raw material storage tank 1 for 0.5 to 3 days, the exhaust valve 801 is opened for 10 to 300 minutes. Thereby, the highly volatile impurities in the crude ammonia distributed in the gas phase formed in the raw material storage tank 1 can be discharged through the exhaust pipe 80.

The crude ammonia stored in the raw material storage tank 1 is led to the gasifier 2. When the crude ammonia is discharged from the raw material storage tank 1 to the gasifier 2, it is derived as a liquid crude ammonia from the liquid phase formed in the raw material storage tank 1. The crude ammonia of the raw material may have a large variation in impurity concentration depending on the batch of the product. In this case, when the crude ammonia having a large deviation in the impurity concentration is derived from the gas phase of the raw material storage tank 1, the composition of the gas phase has a large variation, and the purity of the ammonia obtained by the final purification is largely deviated. Hey. In the ammonia purification system 100 of the present embodiment, since the liquid crude ammonia is led out from the liquid phase of the raw material storage tank 1, even when crude ammonia having a large variation in impurity concentration is used as a raw material, the final prevention can be prevented. The purity of the ammonia obtained by the purification produces a large deviation.

The first pipe 81 is connected between the raw material storage tank 1 and the gasifier 2, and the liquid crude ammonia derived from the raw material storage tank 1 flows through the first pipe 81 and is supplied to the vaporizer 2. The first pipe 81 is provided with a first valve 811 that opens or closes the flow path in the first pipe 81. When the liquid ammonia is supplied to the vaporizer 2, the first valve 811 is opened, and the liquid crude ammonia flows from the raw material storage tank 1 into the vaporizer 2 through the inside of the first pipe 81.

The gasifier 2 vaporizes a part of the liquid crude ammonia derived from the raw material storage tank 1. That is, the vaporizer 2 heats the liquid crude ammonia and vaporizes it at a specific gasification rate, thereby separating into a gas phase component and a liquid phase component, and deriving the gaseous ammonia. The gasifier 2 vaporizes a part of the liquid crude ammonia, so that impurities having low volatility (for example, moisture, hydrocarbons having a carbon number of 6 or more) contained in the crude ammonia remain in the liquid phase. The gaseous ammonia which is reduced by the less volatile impurities is derived.

In the present embodiment, the vaporizer 2 vaporizes the liquid crude ammonia derived from the raw material storage tank 1 at a gasification rate of 90 to 95% by volume to separate into a gas phase component and a liquid phase component. In this case, 90 to 95% by volume of the liquid crude ammonia derived from the raw material storage tank 1 is a gas phase component, and 5 to 10% by volume is a liquid phase component.

The vaporizer 2 is connected to a second pipe 82 provided with a second valve 821 and a discharge pipe 80A provided with a discharge valve 801A. In addition, the second pipe 82 is a pipe through which the gaseous ammonia derived from the gasifier 2 flows to the adsorption unit 3, and is connected to the flow rate adjuster 71. The low-volatility impurities separated from the ammonia in the form of a liquid phase component in the vaporizer 2 are discharged to the outside of the system through the discharge pipe 80A while the discharge valve 801A is opened. In addition, the gaseous ammonia obtained as a gas phase component in the vaporizer 2 flows through the second pipe 82 and is supplied to the flow rate adjuster 71 in a state where the second valve 821 is opened.

A third pipe 83 is connected to the flow rate adjuster 71, and the third pipe 83 is branched from an end portion on the side opposite to the side connected to the flow rate adjuster 71. One branch of the end portion of the third pipe 83 is connected to the fourth pipe 84 connected to the top of the first adsorption tower 31, which will be described later, and the other branch is connected to the top of the tower of the second adsorption tower 32, which will be described later. The fifth pipe 85.

The fourth pipe 84 is provided with a fourth valve 841 that opens or closes the flow path in the fourth pipe 84. Further, the fifth pipe 85 is provided with a fifth valve 851 that opens or closes the flow path in the fifth pipe 85. The gaseous ammonia whose flow rate is adjusted by the flow rate adjuster 71 is supplied to the first adsorption tower 31 in a state where the fourth valve 841 is opened and the fifth valve 851 is closed, and flows through the third pipe 83 and the fourth pipe 84. Again, flow The gaseous ammonia which is adjusted by the flow rate adjuster 71 is supplied to the second adsorption tower 32 while the fifth valve 851 is opened and the fourth valve 841 is closed, and flows through the third pipe 83 and the fifth pipe 85. In other words, the first adsorption tower 31 and the second adsorption tower 32 are connected in parallel via the fourth pipe 84 and the fifth pipe 85.

The adsorption unit 3 purifies and removes impurities contained in the gaseous ammonia derived from the gasifier 2 by adsorption. The adsorption unit 3 includes a first adsorption tower 31 and a second adsorption tower 32 as adsorption portions.

The first adsorption tower 31 has an overhead adsorption layer 311, a first intermediate adsorption layer 312, a second intermediate adsorption layer 313, and a column sequentially stacked from the top of the column to the bottom of the column (upstream from the upstream side to the downstream side in the flow direction of ammonia). The laminated structure of the bottom adsorption layer 314.

The column top adsorption layer 311 is a layer containing a first adsorbent and has a function as a first adsorbent layer. The first adsorbent is a porous adsorbent having a high adsorption capacity for water. Examples of such a first adsorbent include activated carbon, MS-13X (porous synthetic zeolite having a pore size of 9 Å), activated alumina, and the like. In the present embodiment, activated carbon is used as the first adsorbent.

The first intermediate adsorption layer 312 is a layer containing a second adsorbent and has a function as a second adsorbent layer. The second adsorbent is a porous adsorbent having a high adsorption capacity for an organic compound (hydrocarbon, alcohol, ether, etc.) having a carbon number of less than 5. Examples of such a second adsorbent include MS-3A (porous synthetic zeolite having a pore diameter of 3 Å), MS-4A (porous synthetic zeolite having a pore size of 4 Å), and MS-5A (porous having a pore diameter of 5 Å). Hydrophobic zeolite such as synthetic zeolite), MS-13X (porous synthetic zeolite having a pore size of 9 Å), hydrophobic zeolite such as sorghum-type (cerium dioxide/aluminum oxide) zeolite, silicone or the like. Also, the second intermediate adsorption layer Similarly to the first intermediate adsorption layer 312, 313 is a layer containing the second adsorbent and has a function as a second adsorbent layer. However, the first intermediate adsorption layer 312 and the second intermediate adsorption layer 313 are the same layer containing the second adsorbent, but different types of adsorbents are used.

The bottom adsorption layer 314 is a layer containing a third adsorbent and has a function as a third adsorbent layer. The third adsorbent is a porous adsorbent having a high adsorption capacity for an organic compound (hydrocarbon or the like) having a carbon number of 5 or more and water. Examples of such a third adsorbent include activated carbon and MS-13X.

The laminated structure in the first adsorption tower 31 will be described with reference to specific examples. In the first specific example, the column top adsorption layer 311 contains activated carbon (GG, manufactured by Kuraray Chemical Co., Ltd.) as a layer of the first adsorbent, and the first intermediate adsorption layer 312 contains a hydrophilic zeolite (MS-3A, In the second adsorbent layer 313, the second intermediate adsorbing layer 313 contains tantalum (Silbead N, manufactured by Mizusawa Chemical Co., Ltd.) as a layer of the second adsorbent, and the bottom adsorbent layer 314 contains Activated carbon (GG, manufactured by Kuraray Chemical Co., Ltd.) was used as a layer of the third adsorbent.

In the second specific example, the column top adsorption layer 311 contains activated carbon (GG, manufactured by Kuraray Chemical Co., Ltd.) as a layer of the first adsorbent, and the first intermediate adsorption layer 312 contains a hydrophilic zeolite (MS-3A, In the second adsorbent layer 313, the second intermediate adsorbing layer 313 contains tantalum (Silbead N, manufactured by Mizusawa Chemical Co., Ltd.) as a layer of the second adsorbent, and the bottom adsorbent layer 314 contains MS-13X (SA-600A, manufactured by Tosoh Co., Ltd.) was used as a layer of the third adsorbent.

In the third embodiment, the column top adsorption layer 311 contains activated carbon (GG, manufactured by Kuraray Chemical Co., Ltd.) as a layer of the first adsorbent, and the first intermediate adsorption layer 312 contains a hydrophilic zeolite (MS-4A, As a layer of the second adsorbent, the second intermediate adsorption layer 313 contains a hydrophobic zeolite (HSZ-300, cerium oxide/alumina ratio = 10, manufactured by Tosoh Co., Ltd.) as the second adsorption. In the layer of the agent, the bottom adsorption layer 314 contains MS-13X (SA-600A, manufactured by Tosoh Co., Ltd.) as a layer of the third adsorbent.

In the fourth embodiment, the column top adsorption layer 311 contains activated carbon (GG, manufactured by Kuraray Chemical Co., Ltd.) as a layer of the first adsorbent, and the first intermediate adsorption layer 312 contains a hydrophilic zeolite (MS-4A, As a layer of the second adsorbent, the second intermediate adsorption layer 313 contains a hydrophobic zeolite (HSZ-300, cerium oxide/alumina ratio = 10, manufactured by Tosoh Co., Ltd.) as the second adsorption. In the layer of the agent, the bottom adsorption layer 314 is a layer containing a laminate of MS-13X (SA-600A, manufactured by Tosoh Co., Ltd.) and activated carbon (GG, manufactured by Kuraray Chemical Co., Ltd.) as a third adsorbent.

The second adsorption tower 32 has an overhead adsorption layer 321 , a first intermediate adsorption layer 322 , a second intermediate adsorption layer 323 , and a tower sequentially stacked from the top of the tower to the bottom of the tower (upstream from the upstream side to the downstream side in the flow direction of ammonia). The laminated structure of the bottom adsorption layer 324.

The column top adsorption layer 321 is a layer containing the first adsorbent, which is configured in the same manner as the column top adsorption layer 311 of the first adsorption column 31 described above, and has a function as a first adsorbent layer. The first intermediate adsorption layer 322 is combined with the first absorption described above The layer containing the second adsorbent configured in the same manner as the first intermediate adsorption layer 312 of the tower 31 has a function as a second adsorbent layer. The second intermediate adsorption layer 323 has a second adsorbent-containing layer configured in the same manner as the second intermediate adsorption layer 313 of the first adsorption tower 31 described above, and has a function as a second adsorbent layer. The bottom adsorption layer 324 is a layer containing a third adsorbent which is configured in the same manner as the bottom adsorption layer 314 of the first adsorption tower 31 described above, and has a function as a third adsorbent layer.

The first adsorbent, the second adsorbent, and the third adsorbent used in the first adsorption tower 31 and the second adsorption tower 32 can be treated by any one of heating, decompression, heating, and decompression to adsorb the impurities. (Organic compounds such as moisture and hydrocarbons) are detached and regenerated. For example, when the impurities adsorbed to the adsorbent are removed by heat treatment, heating may be carried out at a temperature of 200 to 350 °C.

Further, in the ammonia purification system 100 of the present embodiment, the first adsorption tower 31 and the second adsorption tower 32 control the temperature to 0 to 60 ° C and the pressure control to 0.1 to 1.0 MPa. When the temperature of the first adsorption tower 31 and the second adsorption tower 32 is less than 0 ° C, it is necessary to perform cooling for removing the adsorption heat generated when the impurities are adsorbed and removed, and the energy efficiency is lowered. When the temperature of the first adsorption tower 31 and the second adsorption tower 32 exceeds 60 ° C, the adsorption capacity of the adsorbent for impurities is lowered. Further, when the pressures of the first adsorption tower 31 and the second adsorption tower 32 are less than 0.1 MPa, there is a possibility that the adsorption capacity of the adsorbent to the impurities is lowered, and when the pressure exceeds 1.0 MPa, more energy is required. Maintained at a fixed pressure, there is a drop in energy efficiency.

Further, the linear velocity of the first adsorption tower 31 and the second adsorption tower 32 is preferably 0.1 to 10.0 m/s. At a line speed of less than 0.1 m/s When the adsorption of impurities is removed for a long time, it is not preferable. When the linear velocity exceeds 10.0 m/s, the adsorption heat generated by the adsorption removal of impurities is not sufficiently removed, and the adsorption capacity of the adsorbent for impurities is lowered. After that. In addition, the linear velocity is obtained by converting the amount of gaseous ammonia supplied to the first adsorption tower 31 or the second adsorption tower 32 per unit time to NTP (normal temperature and pressure). The volume of gas under pressure is divided by the cross-sectional area of the empty towers of each of the adsorption columns 31, 32.

Further, in the ammonia purification system 100 of the present embodiment, it is preferable to analyze the concentration of impurities contained in the ammonia derived from the first adsorption tower 31 and the second adsorption tower 32. As a device for analyzing the concentration of impurities contained in ammonia, a gas chromatography analyzer (GC-PDD: pulse discharge type detector) can be cited. Specific examples of the gas chromatography analysis apparatus include, for example, GC-4000 manufactured by GL Science Co., Ltd. The condensation condition (setting of the condensation rate, etc.) of the condenser 4 to be described later can be set based on the analysis result obtained by the gas chromatography analyzer.

The sixth pipe 86 is connected to the bottom of the tower of the first adsorption tower 31, and the sixth pipe 86 is branched from the end portion on the side opposite to the side connected to the first adsorption tower 31. One of the ends of the sixth pipe 86 is branched and connected to the seventh pipe 87 connected to the condenser 4 to be described later, and the other branch is connected to the eighth pipe 88 connected to the top of the tower of the second adsorption tower 32.

The seventh pipe 87 is provided with a seventh valve 871 that opens or closes the flow path in the seventh pipe 87. Further, the eighth pipe 88 is provided with an eighth valve 881 that opens or closes the flow path in the eighth pipe 88. The gaseous ammonia which is adsorbed and removed by the first adsorption tower 31 causes the seventh valve 871 to be opened and the eighth valve 881 to be closed. In the state, it flows through the sixth pipe 86 and the seventh pipe 87 and is supplied to the condenser 4. In addition, the gaseous ammonia which is adsorbed and removed by the first adsorption tower 31 is supplied to the sixth pipe 881 and the eighth valve 871 is closed, and flows through the sixth pipe 86 and the eighth pipe 88. To the second adsorption tower 32. In other words, the first adsorption tower 31 and the second adsorption tower 32 are connected in series via the sixth pipe 86 and the eighth pipe 88.

Further, a ninth pipe 89 is connected to the bottom of the tower of the second adsorption tower 32, and an end of the ninth pipe 89 opposite to the side connected to the second adsorption tower 32 is connected to the condenser 4. The ninth valve 89 is provided with a ninth valve 891 that opens or closes the flow path in the ninth pipe 89. The ninth pipe 89 is provided with a tenth pipe 90 branched from the ninth pipe 89 on the downstream side in the flow direction of the ammonia of the ninth valve 891. The tenth pipe 90 is provided with a tenth valve 901 that opens or closes the flow path in the tenth pipe 90. Further, the end of the tenth pipe 90 opposite to the side connected to the ninth pipe 89 is connected to the top of the tower of the first adsorption tower 31.

The gaseous ammonia which is adsorbed and removed by the second adsorption tower 32 flows through the ninth pipe 89 and is supplied to the condenser 4 in a state where the ninth valve 891 is opened and the tenth valve 901 is closed. In addition, the gaseous ammonia which is adsorbed and removed by the second adsorption tower 32 is supplied to the ninth pipe 89 and the tenth pipe 90 in a state where the ninth valve 891 is opened and the tenth valve 901 is opened. To the first adsorption tower 31.

In the adsorption unit 3 configured as described above, the connection between the first adsorption tower 31 and the second adsorption tower 32 can be changed in four modes.

In the first connection mode, the fourth valve 841 and the seventh valve 871 are opened, and the fifth valve is opened. 851, the eighth valve 881, the ninth valve 891, and the tenth valve 901 are closed. In the first connection mode, the gaseous ammonia which is led out from the gasifier 2 and whose flow rate is adjusted by the flow rate adjuster 71 flows through the fourth pipe 84 and is supplied to the first adsorption tower 31. Then, the purified gaseous ammonia derived from the first adsorption tower 31 flows through the sixth pipe 86 and the seventh pipe 87 and is supplied to the condenser 4. In the first connection mode, the gaseous ammonia derived from the gasifier 2 is purified only by the first adsorption tower 31. During the adsorption removal by the first adsorption tower 31, the second adsorption tower 32 that has been used can be regenerated so that the adsorption removal operation can be performed again by the used second adsorption tower 32.

In the second connection mode, the fifth valve 851 and the ninth valve 891 are opened, and the fourth valve 841, the seventh valve 871, the eighth valve 881, and the tenth valve 901 are closed. In the second connection mode, the gaseous ammonia which is led out from the gasifier 2 and whose flow rate is adjusted by the flow rate adjuster 71 flows through the fifth pipe 85 and is supplied to the second adsorption tower 32. Then, the purified gaseous ammonia derived from the second adsorption tower 32 flows through the ninth piping 89 and is supplied to the condenser 4. In the second connection mode, the gaseous ammonia derived from the gasifier 2 is purified only by the second adsorption tower 32. During the adsorption removal by the second adsorption tower 32, the used first adsorption tower 31 can be regenerated so that the adsorption removal operation can be performed again by the used first adsorption tower 31.

In the third connection mode, the fourth valve 841, the eighth valve 881, and the ninth valve 891 are opened, and the fifth valve 851, the seventh valve 871, and the tenth valve 901 are closed. In the third connection mode, the gaseous ammonia derived from the vaporizer 2 and adjusted in flow rate by the flow rate adjuster 71 flows through the fourth pipe 84 and is supplied to the first adsorption tower 31. The purified gaseous ammonia derived from the first adsorption tower 31 flows through the sixth pipe 86 The eighth pipe 88 is supplied to the second adsorption tower 3 . Then, the purified gaseous ammonia derived from the second adsorption tower 32 flows through the ninth piping 89 and is supplied to the condenser 4. In the third connection mode, the gaseous ammonia derived from the vaporizer 2 is purified by the first adsorption tower 31 and the second adsorption tower 32. Since the impurities contained in the gaseous ammonia derived from the vaporizer 2 can be adsorbed and removed by the first adsorption tower 31 and the second adsorption tower 32 connected in series, the adsorption and removal ability to impurities can be improved.

In the fourth connection mode, the fourth valve 841, the eighth valve 881, the ninth valve 891, and the tenth valve 901 are opened, and the fifth valve 851 and the seventh valve 871 are closed. In the fourth connection mode, the gaseous ammonia which is led out from the gasifier 2 and whose flow rate is adjusted by the flow rate adjuster 71 flows through the fourth pipe 84 and is supplied to the first adsorption tower 31. The purified gaseous ammonia derived from the first adsorption tower 31 is supplied to the second adsorption tower 32 through the sixth pipe 86 and the eighth pipe 88. The purified gaseous ammonia derived from the second adsorption tower 32 flows through the ninth piping 89 and the tenth piping 90 and is again supplied to the first adsorption tower 31, and the first adsorption tower 31 and the second adsorption tower 32 are repeated. The adsorption removal operation is performed. Then, at the time when the open tenth valve 901 is closed, the gaseous ammonia derived from the second adsorption tower 32 flows through the ninth pipe 89 and is supplied to the condenser 4. In the fourth connection mode, the gaseous ammonia derived from the vaporizer 2 can be repeatedly purified by the first adsorption tower 31 and the second adsorption tower 32.

The gaseous ammonia derived from the first adsorption tower 31 or the second adsorption tower 32 is supplied to the condenser 4. The condenser 4 separates the gaseous ammonia derived from the first adsorption tower 31 or the second adsorption tower 32 into a gas phase component and a liquid phase component, thereby hydrogen, nitrogen, oxygen, and argon contained in the ammonia. Gas, carbon monoxide, dioxide The highly volatile impurities such as carbon are separated and removed in the form of a gas phase component, and the purified liquid ammonia is obtained as a liquid phase component.

Examples of the condenser 4 include a multitubular condenser and a plate heat exchanger. In the present embodiment, a multitubular condenser is used as the condenser 4. The condenser 4 condenses 70 to 99% by volume of the gaseous ammonia derived from the first adsorption tower 31 or the second adsorption tower 32, and separates it into a gas phase component and a liquid phase component. In this case, the gas phase component and the liquid phase component are separated by being condensed so that one part to 30% by volume of the gaseous ammonia derived from the first adsorption tower 31 or the second adsorption tower 32 is a gas phase component. Thereby, the highly volatile impurities contained in the gaseous ammonia after the adsorption removal can be separated and removed in the form of a gas phase component, and the purified liquid form can be obtained in a good yield in the form of a liquid phase component. ammonia.

In addition, the condensation condition in the condenser 4 is not particularly limited as long as it is a condition that a part of the gaseous ammonia which can be derived from the first adsorption tower 31 or the second adsorption tower 32 is liquid, and the temperature is appropriately set. , pressure and time can be. In the present embodiment, the condenser 4 is preferably configured such that the gaseous ammonia derived from the first adsorption tower 31 or the second adsorption tower 32 is condensed at a temperature of -77 to 40 ° C to be separated into a gas phase component and Liquid phase composition. Thereby, the gaseous ammonia derived from the first adsorption tower 31 or the second adsorption tower 32 can be efficiently condensed to obtain purified liquid ammonia, and the purity of the liquid ammonia can be improved. When the temperature at which the gaseous ammonia in the condenser 4 is condensed is less than -77 ° C, cooling requires more energy, which is not preferable. When the temperature exceeds 40 ° C, a part of ammonia is condensed to obtain The concentration of impurities contained in the liquid ammonia is high, which is not preferable.

Further, the condenser 4 is preferably configured such that the gaseous ammonia derived from the first adsorption tower 31 or the second adsorption tower 32 is condensed under a pressure of 0.007 to 2.0 MPa to be separated into a gas phase component and a liquid phase component. When the pressure at the time of coagulation of the gaseous ammonia in the condenser 4 is less than 0.007 MPa, the temperature at which the ammonia is condensed becomes low, so that cooling requires more energy, and thus is not preferable, in the case of exceeding 2.0 MPa. At this time, since the temperature at which the ammonia is condensed becomes high, the concentration of impurities contained in the liquid ammonia obtained by partially coagulation of ammonia becomes high, which is not preferable.

In the ammonia purification system 100 of the present embodiment, the condenser 4 partially condenses a part of the gaseous ammonia derived from the first adsorption tower 31 or the second adsorption tower 32, and separates it into a gas phase component and a liquid phase component. The highly volatile impurities are separated and removed in the form of a gas phase component, and the purified liquid ammonia is obtained as a liquid phase component. Therefore, even if the distillation section is not provided as in the prior art, the ammonia can be purified by a simplified system.

When the impurities contained in the crude ammonia are separated and removed by precision distillation, since the distillation is carried out by reflux, the operation is repeated as follows: the liquid ammonia is heated and evaporated by the distillation column to become a gaseous ammonia. On the other hand, the gaseous ammonia from the rectification column is condensed by the condenser at the top of the column of the distillation column to form a liquid ammonia. Therefore, a large amount of energy is put into the operation in the rectification operation.

On the other hand, when the impurities contained in the ammonia are separated and removed by the condensation of the condenser 4, since only the gaseous ammonia is condensed once, the energy required is small. Thus, it can be seen that the purification method using the condensation of the condenser 4 can be performed not only in a short time but also in the purification method using the ammonia of the rectification. High purity ammonia is obtained, and it also has great advantages in terms of energy.

In order to obtain high-purity ammonia, it is necessary to rapidly extract the liquid ammonia obtained in the form of a liquid phase component by the condensation of the condenser 4 from the condenser 4, and only the uncondensed gas exists inside the condenser 4. The phase composition is such that the condenser 4 is operated.

The eleventh pipe 91 provided with the eleventh valve 911 and the twelfth pipe 92 provided with the twelfth valve 921 are connected to the condenser 4. Further, the eleventh pipe 91 is connected between the condenser 4 and the recovery tank 5.

The highly volatile impurities which are separated from the ammonia in the form of a gas phase component in the condenser 4 are discharged to the outside of the system through the 12th pipe 92 while the 12th valve 921 is opened. In addition, the liquid ammonia obtained as a liquid phase component in the condenser 4 is supplied to the recovery tank 5 through the eleventh pipe 91 while the eleventh valve 911 is opened.

The recovery tank 5 stores the liquid ammonia obtained by the condenser 4 in the form of a liquid phase component. The collection tank 5 is connected to a thirteenth pipe 93 that communicates the recovery tank 5 with the outside to form a flow path for discharging the gas phase component to the outside. The thirteenth pipe 931 is provided with a thirteenth valve 931 that opens or closes the flow path in the thirteenth pipe 93. In the ammonia purification system 100 of the present embodiment, the third valve 931 is opened while the eleventh valve 911 is closed, and the volatility can be realized from the liquid ammonia stored in the recovery tank 5. The discharge of high impurities is removed and removed. By performing the discharge operation in the recovery tank 5, the purity of the liquid ammonia stored in the recovery tank 5 can be further improved.

Further, the recovery tank 5 controls the temperature and pressure under certain conditions to store ammonia in a liquid state. The recovery tank 5 and the condenser 4 are passed through the 14th piping 94. A coolant liquid supply device 72 is connected. The coolant sent from the coolant liquid supply device 72 flows through the fourth pipe 94, and the recovery tank 5 and the condenser 4 are maintained at a specific temperature by the cooling capacity of the coolant.

The charging device 6 is connected to the recovery tank 5 via a 15th pipe 95 provided with a 15th valve 951. The liquid ammonia stored in the recovery tank 5 is supplied to the filling device 6 through the 15th pipe 95 by opening the 15th valve 951. The ammonia supplied to the filling device 6 in this manner is filled into the product filling container or the like by the filling device 6.

In the ammonia purification system 100 of the present embodiment configured as described above, the adsorbent layer having different adsorption capacities for water, an organic compound having a carbon number of less than 5, and an organic compound having a carbon number of 5 or more is laminated. Since the first adsorption tower 31 and the second adsorption tower 32 adsorb and remove impurities contained in the crude ammonia, impurities (mainly water and organic compounds) contained in the crude ammonia can be efficiently removed by adsorption. Further, the condenser 4 separates the ammonia derived from the first adsorption tower 31 or the second adsorption tower 32 into a gas phase component and a liquid phase component, so that hydrogen, nitrogen, oxygen, argon, carbon monoxide, carbon dioxide, or the like can be used. The highly volatile impurities are separated and removed in the form of a gas phase component, and the purified liquid ammonia is obtained as a liquid phase component. Therefore, in the ammonia purification system 100 of the present embodiment, it is not necessary to carry out distillation with reflux as in the prior art, and the ammonia can be purified by a simplified method, and ammonia can be efficiently purified by suppressing energy consumption.

Further, in the first adsorption tower 31 and the second adsorption tower 32 of the adsorption unit 3, the column top adsorption layers 311 and 321 containing the first adsorbent are sequentially stacked from the upstream side to the downstream side in the flow direction of the crude ammonia. The first intermediate adsorption of the second adsorbent The layers 312 and 322 include the second intermediate adsorption layers 313 and 323 of the second adsorbent and the bottom adsorption layers 314 and 324 containing the third adsorbent. Since the top adsorption layers 311 and 321 contain the first adsorbent having a high adsorption capacity for water, the crude ammonia flowing through the first adsorption tower 31 and the second adsorption tower 32 is first applied to the adsorption adsorption layers 311 and 321 at the top. Most of the water in the middle of the adsorption is removed. Thereby, the first intermediate adsorption layers 312 and 322 disposed on the downstream side in the flow direction of ammonia with respect to the column top adsorption layers 311 and 321 , the second intermediate adsorption layers 313 and 323 , and the bottom adsorption layers 314 and 324 are organic compounds. The adsorption capacity can be sufficiently exerted, and the adsorption removal property of the first adsorption tower 31 and the second adsorption tower 32 from impurities by the crude ammonia can be improved.

In the present embodiment, as described above, the first adsorption tower 31 and the second adsorption tower 32 have an adsorption property in which an organic compound having water, a carbon number of less than 5, and an organic compound having a carbon number of 5 or more are laminated. The layered structure of the agent layer. The adsorption tower having the same adsorption and removal ability as the first adsorption tower 31 and the second adsorption tower 32, which exhibits adsorption and removal of impurities contained in ammonia, can be considered to have an adsorption adsorption layer containing a first adsorbent. And an adsorption tower in which the top adsorption layer is disposed on the downstream side of the flow direction of the crude ammonia, and the mixed layer of the second adsorbent and the third adsorbent is mixed.

In such an adsorption tower having an adsorption layer and a mixed layer, the second adsorbent and the third adsorbent constituting the mixed layer are filled in the layer in a state of being uniformly dispersed, so that it is not necessary to fill each adsorbent layer.

In addition, as for the adsorption and removal ability of the impurities contained in ammonia, which are the same as those of the first adsorption tower 31 and the second adsorption tower 32, it is also possible to separately fill the first adsorbent and the second adsorbent separately. And a plurality of third adsorbents The structure of the adsorption tower series connection. This method also has no effect on the adsorption and removal of impurities. In the configuration in which a plurality of adsorption towers are connected in series, if the plurality of adsorption towers are arranged in series in the horizontal direction, there is a problem that the installation area becomes large. However, if they are arranged in series in the vertical direction, There is no problem that the setting area becomes large. When a plurality of adsorption towers are connected in series, the configuration of the adsorption tower may be selected in consideration of the equipment cost such as the size of the adsorption tower, the increase in the number of towers, and the length of the connection piping.

Fig. 2 is a view showing the configuration of an ammonia purification system 150 according to a second embodiment of the present invention. The ammonia purification system 150 of the present embodiment is similar to the above-described ammonia purification system 100, and the same reference numerals will be given to the corresponding parts, and the description will be omitted. In the ammonia purification system 150, the configuration of the adsorption unit 151 is different from that of the above-described adsorption unit 3, and is the same as the ammonia purification system 100.

The adsorption unit 151 purifies and removes impurities contained in the gaseous ammonia derived from the gasifier 2 by adsorption. In the present embodiment, the adsorption unit 151 includes the first adsorption tower 1511, the second adsorption tower 1512, and the third adsorption tower 1513.

The first adsorption tower 1511, the second adsorption tower 1512, and the third adsorption tower 1513 are configured in the same manner as the first adsorption tower 31 described above. Specifically, the first adsorption tower 1511 has an overhead adsorption layer 15111, a first intermediate adsorption layer 15112, and a second intermediate adsorption layer sequentially stacked from the top of the column to the bottom of the column (upstream from the upstream side to the downstream side in the flow direction of ammonia). 15113, and a laminated structure of the bottom adsorption layer 15114.

The column top adsorption layer 15111 is a layer containing a first adsorbent and has a function as a first adsorbent layer. The first adsorbent has a high adsorption capacity for water Porous adsorbent. Examples of such a first adsorbent include activated carbon and the like.

The first intermediate adsorption layer 15112 is a layer containing a second adsorbent and has a function as a second adsorbent layer. The second adsorbent is a porous adsorbent having a high adsorption capacity for an organic compound (hydrocarbon, alcohol, ether, etc.) having a carbon number of less than 5. Examples of such a second adsorbent include MS-3A (porous synthetic zeolite having a pore diameter of 3 Å), MS-4A (porous synthetic zeolite having a pore size of 4 Å), and MS-5A (porous having a pore diameter of 5 Å). Hydrophobic zeolite such as synthetic zeolite), MS-13X (porous synthetic zeolite having a pore size of 9 Å), hydrophobic zeolite such as sorghum-type (cerium dioxide/aluminum oxide) zeolite, silicone or the like. In addition, the second intermediate adsorption layer 15113 is a layer containing the second adsorbent similarly to the first intermediate adsorption layer 15112, and has a function as a second adsorbent layer. However, although the first intermediate adsorption layer 15112 and the second intermediate adsorption layer 15113 are the same layer containing the second adsorbent, the adsorbents having different types are used.

The bottom adsorption layer 15114 is a layer containing a third adsorbent and has a function as a third adsorbent layer. The third adsorbent is a porous adsorbent having a high adsorption capacity for an organic compound (hydrocarbon or the like) having a carbon number of 5 or more and water. Examples of such a third adsorbent include activated carbon and MS-13X.

The second adsorption tower 1512 has an overhead adsorption layer 15121, a first intermediate adsorption layer 15122, a second intermediate adsorption layer 15123, and a column sequentially stacked from the top of the column to the bottom of the column (upstream from the upstream side to the downstream side in the flow direction of ammonia). The laminated structure of the bottom adsorption layer 15124.

The column top adsorption layer 15121 is a layer containing the first adsorbent, which is configured in the same manner as the column top adsorption layer 311 of the first adsorption column 31 described above, and has 1 function of the adsorbent layer. The first intermediate adsorption layer 15122 is a layer containing the second adsorbent and configured to be the same as the first intermediate adsorption layer 312 of the first adsorption tower 31 described above, and has a function as a second adsorbent layer. The second intermediate adsorption layer 15123 is a layer containing the second adsorbent, which is configured in the same manner as the second intermediate adsorption layer 313 of the first adsorption tower 31 described above, and has a function as a second adsorbent layer. The bottom adsorption layer 15124 is a layer containing a third adsorbent which is configured in the same manner as the bottom adsorption layer 314 of the first adsorption tower 31 described above, and has a function as a third adsorbent layer.

In the present embodiment, the 15A pipe 152, the 15B pipe 153, and the 15C pipe 154 branched from the third pipe 83 are connected to the third pipe 83 through which the gaseous ammonia derived from the gasifier 2 flows.

The 15A pipe 152 is branched from the third pipe 83 and connected to the top of the tower of the first adsorption tower 1511. The 15A valve 15a is provided with a 15A valve 1521 that opens or closes the flow path in the 15A pipe 152. The 15B pipe 153 is branched from the third pipe 83 and connected to the top of the tower of the second adsorption tower 1512. The 15B valve 1531 is provided with a 15B valve 1531 that opens or closes the flow path in the 15B pipe 153. The 15C pipe 154 is branched from the third pipe 83 and connected to the top of the third adsorption tower 1513. A 15C valve 1541 that opens or closes the flow path in the 15Cth pipe 154 is connected to the 15C pipe 154.

Further, a 15D pipe 155 through which the gaseous ammonia derived from the first adsorption tower 1511 flows is connected to the bottom of the first adsorption tower 1511. The 15D valve 155 is provided with a 15D valve 1551 that opens or closes the flow path in the 15D pipe 155. The second adsorption tower 1512 is connected to the bottom of the tower to make the second adsorption The 15E pipe 156 through which the gaseous ammonia derived from the column 1512 flows. The 15E valve 156 is provided with a 15E valve 1561 that opens or closes the flow path in the 15E pipe 156. A 15F pipe 157 through which the gaseous ammonia derived from the third adsorption column 1513 flows is connected to the bottom of the third adsorption column 1513. The 15Fth pipe 157 is provided with a 15F valve 1571 that opens or closes the flow path in the 15Fth pipe 157.

Further, a 15G pipe 158 branched from the 15D pipe 155 is connected to the 15D pipe 155. The 15G branch pipe 158 is branched from the 15D pipe 155 and connected to the 15B pipe 153, and is a flow path for introducing the gaseous ammonia derived from the first adsorption tower 1511 into the second adsorption tower 1512. The 15G valve 1581 is provided with a 15G valve 1581 that opens or closes the flow path in the 15Gth pipe 158. A 15H pipe 159 branched from the 15G pipe 158 is connected to the 15G pipe 158. The 25H pipe 159 is branched from the 15G pipe 158 and connected to the 15C pipe 154, and is a flow path for introducing the gaseous ammonia derived from the first adsorption tower 1511 into the third adsorption tower 1513. The 15Hth pipe 159 is provided with a 15H valve 1591 that opens or closes the flow path in the 15Hth pipe 159.

Further, the 15th pipe 160 and the 15th pipe 161 branched from the 15E pipe 156 are connected to the 15E pipe 156. The 15I pipe 160 is branched from the 15E pipe 156 and connected to the 15A pipe 152, and is a flow path for introducing the gaseous ammonia derived from the second adsorption tower 1512 into the first adsorption tower 1511. The 15Ith pipe 1601 is provided with a 15I valve 1601 that opens or closes the flow path in the 15I pipe 160. The 15th pipe 161 is branched from the 15E pipe 156 and connected to the 15C pipe 154 to be used to be discharged from the second adsorption tower 1512. The gaseous ammonia is introduced into the flow path of the third adsorption column 1513. The 15Jth pipe 1611 is provided with a 15Jth valve 1611 that opens or closes the flow path in the 15Jth pipe 161.

Further, a 15Kth pipe 162 branched from the 15F pipe 157 is connected to the 15F pipe 157. The 15Kth pipe 162 is branched from the 15F pipe 157 and connected to the 15A pipe 152, and is a flow path for introducing the gaseous ammonia derived from the third adsorption tower 1513 into the first adsorption tower 1511. The 15Kth pipe 162 is provided with a 15K valve 1621 that opens or closes the flow path in the 15Kth pipe 162. A 15L pipe 163 branched from the 15K pipe 162 is connected to the 15Kth pipe 162. The 15L L pipe 163 is branched from the 15K pipe 162 and connected to the 15B pipe 153, and is a flow path for introducing the gaseous ammonia derived from the third adsorption tower 1513 into the second adsorption tower 1512. The 15th L1 pipe 1631 is provided with a 15L valve 1631 that opens or closes the flow path in the 15L L pipe 163.

In the 15D pipe 155, the 15E pipe 156, and the 15F pipe 157, the 15th M pipe 164 is connected to the downstream end portion in the flow direction of the gaseous ammonia. The 15M pipe 164 is supplied with gaseous ammonia derived from any one of the first adsorption tower 1511, the second adsorption tower 1512, and the third adsorption tower 1513. Further, the 15th M pipe 164 is provided with a 15Nth pipe 165 branched from the 15M pipe 164 and connected to the condenser 4.

In the ammonia purification system 150 configured as described above, the connection of the first adsorption column 1511, the second adsorption column 1512, and the third adsorption column 1513 has the following six connection modes.

The first connection mode is such that the gaseous ammonia derived from the gasifier 2 is sequentially passed. The connection mode of the first adsorption tower 1511 and the second adsorption tower 1512. In the first connection mode, the 15A valve 1521, the 15E valve 1561, and the 15G valve 1581 are opened, and the 15B valve 1531, the 15C valve 1541, the 15D valve 1551, the 15F valve 1571, and the 15H valve 1591 are opened. The 15th valve 1601, the 15Jth valve 1611, the 15Kth valve 1621, and the 15Lth valve 1631 are closed.

In this way, the gaseous ammonia derived from the gasifier 2 is introduced into the first adsorption column 1511 via the 15A pipe 152, and the gaseous ammonia derived from the first adsorption column 1511 flows through the 15D pipe 155 and the 15G. The piping 158 is introduced into the second adsorption tower 1512, and the gaseous ammonia derived from the second adsorption tower 1512 flows through the 15E pipe 156 and is supplied to the 15M pipe 164, and the gaseous ammonia is introduced from the 15M pipe 164. To condenser 4.

In the first connection mode, the impurities contained in the gaseous ammonia can be adsorbed and removed by the first adsorption tower 1511 and the second adsorption tower 1512, so that the adsorption and removal ability to impurities can be improved. Further, in the first connection mode, since the adsorption removal operation of the third adsorption column 1513 is not performed, the third adsorption column 1513 can be regenerated.

In the second connection mode, the gaseous ammonia derived from the gasifier 2 is sequentially passed through the connection mode of the first adsorption column 1511 and the third adsorption column 1513. In the second connection mode, the 15A valve 1521, the 15F valve 1571, and the 15H valve 1591 are opened, and the 15B valve 1531, the 15C valve 1541, the 15D valve 1551, the 15E valve 1561, and the 15G valve 1581 are opened. The 15th valve 1601, the 15Jth valve 1611, the 15Kth valve 1621, and the 15Lth valve 1631 are closed.

By this, the gaseous ammonia derived from the gasifier 2 is introduced into the first adsorption tower 1511 through the 15A pipe 152, and the gas is discharged from the first adsorption tower 1511. The ammonia flows through the 15D pipe 155, the 15G pipe 158, and the 15H pipe 159, and is introduced into the third adsorption column 1513. The gaseous ammonia derived from the third adsorption column 1513 flows through the 15F pipe 157 and is supplied to the 15M. The pipe 164 introduces gaseous ammonia into the condenser 4 from the 15M pipe 164.

In the second connection mode, the impurities contained in the gaseous ammonia can be adsorbed and removed by the first adsorption column 1511 and the third adsorption column 1513, so that the adsorption and removal ability to impurities can be improved. Further, in the second connection mode, since the adsorption removal operation of the second adsorption tower 1512 is not performed, the second adsorption tower 1512 can be regenerated.

In the third connection mode, the gaseous ammonia derived from the gasifier 2 is sequentially passed through the connection mode of the second adsorption column 1512 and the first adsorption column 1511. In the third connection mode, the 15B valve 1531, the 15D valve 1551, and the 15th valve 1601 are opened, and the 15A valve 1521, the 15C valve 1541, the 15E valve 1561, the 15F valve 1571, and the 15G valve 1581 are opened. The 15th H valve 1591, the 15th J valve 1611, the 15Kth valve 1621, and the 15th L valve 1631 are closed.

By this, the gaseous ammonia derived from the gasifier 2 is introduced into the second adsorption tower 1512 via the 15B pipe 153, and the gaseous ammonia derived from the second adsorption tower 1512 flows through the 15E pipe 156 and the 15I. The piping 160 is introduced into the first adsorption tower 1511, and the gaseous ammonia derived from the first adsorption tower 1511 flows through the 15D pipe 155 and is supplied to the 15M pipe 164, and the gaseous ammonia is introduced from the 15M pipe 164. To condenser 4.

In the third connection mode, the impurities contained in the gaseous ammonia can be adsorbed and removed by the first adsorption tower 1511 and the second adsorption tower 1512, so that the adsorption and removal ability to impurities can be improved. Furthermore, in the third connection mode, Since the adsorption removal operation of the third adsorption column 1513 is not performed, the third adsorption column 1513 can be regenerated.

In the fourth connection mode, the gaseous ammonia derived from the gasifier 2 is sequentially passed through the connection mode of the second adsorption column 1512 and the third adsorption column 1513. In the fourth connection mode, the 15B valve 1531, the 15Fth valve 1571, and the 15th J valve 1611 are opened, and the 15A valve 1521, the 15C valve 1541, the 15D valve 1551, the 15E valve 1561, and the 15G valve 1581 are opened. The 15th H valve 1591, the 15th valve 1601, the 15Kth valve 1621, and the 15Lth valve 1631 are closed.

By this, the gaseous ammonia derived from the gasifier 2 is introduced into the second adsorption tower 1512 via the 15B pipe 153, and the gaseous ammonia derived from the second adsorption tower 1512 flows through the 15E pipe 156 and the 15J. The pipe 161 is introduced into the third adsorption column 1513, and the gaseous ammonia derived from the third adsorption column 1513 flows through the 15F pipe 157 and is supplied to the 15M pipe 164, and the gaseous ammonia is introduced from the 15M pipe 164. To condenser 4.

In the fourth connection mode, the impurities contained in the gaseous ammonia can be adsorbed and removed by the second adsorption column 1512 and the third adsorption column 1513, so that the adsorption and removal ability to impurities can be improved. Further, in the fourth connection mode, since the adsorption removal operation of the first adsorption column 1511 is not performed, the first adsorption column 1511 can be subjected to regeneration treatment.

In the fifth connection mode, the gaseous ammonia derived from the gasifier 2 is sequentially passed through the connection mode of the third adsorption column 1513 and the first adsorption column 1511. In the fifth connection mode, the 15th C valve 1541, the 15D valve 1551, and the 15Kth valve 1621 are opened, and the 15A valve 1521, the 15B valve 1531, the 15E valve 1561, the 15F valve 1571, and the 15G valve 1581 are opened. 15H valve 1591, 15I valve 1601, 15J valve 1611 and 15L valve 1631 are closed.

In this way, the gaseous ammonia derived from the gasifier 2 is introduced into the third adsorption column 1513 via the 15C pipe 154, and the gaseous ammonia derived from the third adsorption column 1513 flows through the 15F pipe 157 and the 15K. The piping 162 is introduced into the first adsorption tower 1511, and the gaseous ammonia derived from the first adsorption tower 1511 flows through the 15D pipe 155 and is supplied to the 15M pipe 164, and the gaseous ammonia is introduced from the 15M pipe 164. To condenser 4.

In the fifth connection mode, the impurities contained in the gaseous ammonia can be adsorbed and removed by the first adsorption column 1511 and the third adsorption column 1513, so that the adsorption and removal ability to impurities can be improved. Further, in the fifth connection mode, since the adsorption removal operation of the second adsorption tower 1512 is not performed, the second adsorption tower 1512 can be regenerated.

In the sixth connection mode, the gaseous ammonia derived from the gasifier 2 is sequentially passed through the connection mode of the third adsorption column 1513 and the second adsorption column 1512. In the sixth connection mode, the 15Cth valve 1541, the 15Eth valve 1561, and the 15Lth valve 1631 are opened, and the 15A valve 1521, the 15B valve 1531, the 15D valve 1551, the 15F valve 1571, and the 15G valve 1581 are opened. The 15th H valve 1591, the 15th valve 1601, the 15th J valve 1611, and the 15Kth valve 1621 are closed.

In this way, the gaseous ammonia derived from the gasifier 2 is introduced into the third adsorption column 1513 via the 15C pipe 154, and the gaseous ammonia derived from the third adsorption column 1513 flows through the 15F pipe 157, 15K. The pipe 162 and the 15L pipe 163 are introduced into the second adsorption tower 1512, and the gaseous ammonia derived from the second adsorption tower 1512 flows through the 15E pipe 156 and is supplied to the 15M pipe 164, and the 15M pipe 164 is supplied from the 15M pipe 164. The gaseous ammonia is introduced into the condenser 4.

In the sixth connection mode, the impurities contained in the gaseous ammonia can be adsorbed and removed by the second adsorption column 1512 and the third adsorption column 1513, so that the adsorption and removal ability to impurities can be improved. Further, in the sixth connection mode, since the adsorption removal operation of the first adsorption tower 1511 is not performed, the first adsorption tower 1511 can be regenerated.

Fig. 3 is a view showing the configuration of an ammonia purification system 200 according to a third embodiment of the present invention. The ammonia purification system 200 of the present embodiment is similar to the above-described ammonia purification system 100, and the same reference numerals will be given to the corresponding parts, and description thereof will be omitted. In the ammonia purification system 200, the configuration of the adsorption unit 201 is different from that of the adsorption unit 3 described above, and is the same as the ammonia purification system 100.

The adsorption unit 201 purifies and removes impurities contained in the gaseous ammonia derived from the gasifier 2 by adsorption. In the present embodiment, the adsorption unit 201 includes the first adsorption tower 2011, the second adsorption tower 2012, the third adsorption tower 2013, and the fourth adsorption tower 2014.

The first adsorption tower 2011 and the third adsorption tower 2013 are connected in parallel to the 20th piping 202. The 20th pipe 202 is provided with a 21st valve 2021 and a 22nd valve 2022 which open or close the flow path in the 20th pipe 202. In the 20th pipe 202, the 21st valve 2021 is disposed on the upstream side of the first adsorption tower 2011 (that is, on the top side of the first adsorption tower 2011), and the 22nd valve 2022 is disposed upstream of the third adsorption tower 2013. Side (ie, the top side of the tower of the third adsorption tower 2013). When the gaseous ammonia derived from the gasifier 2 is supplied to the first adsorption tower 2011, the 21st valve 2021 is opened, and the 22nd valve 2022 is closed, and the gaseous ammonia is passed through the gasifier 2 through the 20th. The inside of the pipe 202 flows into the first adsorption tower 2011. Moreover, when the gaseous ammonia derived from the gasifier 2 is supplied to the third adsorption tower 2013, When the 22nd valve 2022 is opened, the 21st valve 2021 is closed, and gaseous ammonia is flowed from the vaporizer 2 to the 3rd adsorption tower 2013 through the 20th piping 202.

In this way, the adsorption unit 201 has the first adsorption tower 2011 and the third adsorption tower 2013 that are connected in parallel, whereby the first adsorption tower 2011 and the third adsorption tower 2013 that are connected in parallel can be introduced into the gasifier in a state of being separated from each other. In the case where the ammonia is desorbed by the first adsorption tower 2011, the third adsorption tower 2013 that has been used can be regenerated so that the third adsorption tower 2013 can be used again. The adsorption removal operation is performed.

The second adsorption tower 2012 is connected in series to the first adsorption tower 2011 via the 21st pipe 203. In other words, one end of the 21st pipe 203 is connected to the bottom of the tower of the first adsorption tower 2011, and the other end is connected to the top of the tower of the second adsorption tower 2012. In this way, the gaseous ammonia introduced into the first adsorption tower 2011 after being led out from the gasifier 2 flows through the 21st pipe 203 and is introduced into the second adsorption tower 2012 while the 23rd valve 2031 is opened. In this way, the adsorption unit 201 has the first adsorption tower 2011 and the second adsorption tower 2012 connected in series, whereby the first adsorption tower 2011 and the second adsorption tower 2012 can be used to extract the gaseous ammonia derived from the gasifier 2. The impurities contained are adsorbed and removed, so that the adsorption and removal ability to impurities can be improved.

The gaseous ammonia derived from the second adsorption tower 2012 flows through the 22nd pipe 204 and is supplied to the condenser 4 in a state where the 24th valve 2041 is opened.

The fourth adsorption tower 2014 is connected in series to the third adsorption tower 2013 via the 23rd piping 205. In other words, one end of the 23rd pipe 205 is connected to the bottom of the third adsorption tower 2013, and the other end is connected to the top of the 4th adsorption tower 2014. unit. In this way, the gaseous ammonia introduced into the third adsorption tower 2013 after being led out from the gasifier 2 flows through the 23rd pipe 205 and is introduced into the fourth adsorption tower 2014 while the 25th valve 2051 is opened. In this way, the adsorption unit 201 has the third adsorption tower 2013 and the fourth adsorption tower 2014 connected in series, whereby the third adsorption tower 2013 and the fourth adsorption tower 2014 can be used to extract the gaseous ammonia derived from the gasifier 2. The impurities contained are adsorbed and removed, so that the adsorption and removal ability to impurities can be improved.

The gaseous ammonia derived from the fourth adsorption tower 2014 flows through the 24th pipe 206 and is supplied to the condenser 4 in a state where the 26th valve 2061 is opened.

The first adsorption tower 2011 in the adsorption unit 201 of the ammonia purification system 200 has a column top adsorption layer 20111 and a first intermediate adsorption layer 20112 sequentially stacked from the top of the column to the bottom of the column (upstream side to the downstream side from the flow direction of ammonia). The laminated structure of the second intermediate adsorption layer 20113, the third intermediate adsorption layer 20114, and the bottom adsorption layer 20115.

The column top adsorption layer 20111 is a layer containing the first adsorbent and configured to be the same as the column top adsorption layer 311 of the first adsorption column 31 in the adsorption unit 3 described above, and has a function as a first adsorbent layer. The first intermediate adsorption layer 20112 has a second adsorbent-containing layer configured in the same manner as the first intermediate adsorption layer 312 of the first adsorption tower 31 described above, and has a function as a second adsorbent layer. The second intermediate adsorption layer 20113 is a layer containing the second adsorbent configured to be the same as the second intermediate adsorption layer 313 of the first adsorption tower 31 described above, and has a function as a second adsorbent layer. The third intermediate adsorption layer 20114 is a layer containing the second adsorbent, which is configured in the same manner as the first intermediate adsorption layer 312 and the second intermediate adsorption layer 313 of the first adsorption tower 31 described above, and has a second adsorption layer. The function of the sorbent layer. However, the first intermediate adsorption layer 20112, the second intermediate adsorption layer 20113, and the third intermediate adsorption layer 20114 are the same layers containing the second adsorbent, but different types of adsorbents are used. The bottom adsorption layer 20115 is a layer containing a third adsorbent which is configured in the same manner as the bottom adsorption layer 314 of the first adsorption tower 31 described above, and has a function as a third adsorbent layer.

The laminated structure in the first adsorption tower 2011 will be described with reference to specific examples. In the first specific example, the top adsorption layer 20111 contains activated carbon (GG, manufactured by Kuraray Chemical Co., Ltd.) as a layer of the first adsorbent, and the first intermediate adsorption layer 20112 contains tannin (Silbead N, Mizusawa Chemical Industry). The second intermediate adsorption layer 20113 is a layer containing a hydrophilic zeolite (MS-3A, manufactured by Tosoh Co., Ltd.) as a second adsorbent, and a third intermediate adsorption layer 20114 is a layer of the second adsorbent. Hydrophobic zeolite (HSZ-300, cerium oxide/alumina ratio = 10, manufactured by Tosoh Co., Ltd.) as a layer of the second adsorbent, and the bottom adsorbent layer 20115 contains activated carbon (GG, Kuraray Chemical Co., Ltd.) Manufactured as a layer of the third adsorbent.

In the second specific example, the column top adsorption layer 20111 contains activated carbon (GG, manufactured by Kuraray Chemical Co., Ltd.) as a layer of the first adsorbent, and the first intermediate adsorption layer 20112 contains a hydrophilic zeolite (MS-3A, As a layer of the second adsorbent, the second intermediate adsorption layer 20113 contains tantalum (Silbead N, manufactured by Mizusawa Chemical Co., Ltd.) as a layer of the second adsorbent, and the third intermediate adsorbent layer 20114 is a layer. Containing hydrophobic zeolite (HiSiv, manufactured by Union Showa Co., Ltd.) In the layer of the second adsorbent, the bottom adsorption layer 20115 contains MS-13X (manufactured by Tosoh Co., Ltd.) as a layer of the third adsorbent.

In the ammonia purification system 200 of the present embodiment configured as described above, the adsorbent layer having different adsorption capacities for water, an organic compound having a carbon number of less than 5, and an organic compound having a carbon number of 5 or more is laminated. The first adsorption tower 2011, the second adsorption tower 2012, the third adsorption tower 2013, and the fourth adsorption tower 2014 adsorb and remove impurities contained in the crude ammonia, so that impurities (mainly water) contained in the crude ammonia can be contained. And organic compounds) are efficiently adsorbed and removed. Further, the condenser 4 separates the ammonia derived from the second adsorption tower 2012 or the fourth adsorption tower 2014 into a gas phase component and a liquid phase component, so that hydrogen, nitrogen, oxygen, argon, carbon monoxide, carbon dioxide, or the like can be used. The highly volatile impurities are separated and removed in the form of a gas phase component, and the purified liquid ammonia is obtained as a liquid phase component. Therefore, in the ammonia purification system 200 of the present embodiment, it is not necessary to carry out distillation with reflux as in the prior art, and the ammonia can be purified by a simplified method, and ammonia can be efficiently purified by suppressing energy consumption.

Fig. 4 is a view showing the configuration of an ammonia purification system 300 according to a fourth embodiment of the present invention. The ammonia purification system 300 of the present embodiment is similar to the above-described ammonia purification system 100, and the same reference numerals will be given to the corresponding parts, and the description thereof will be omitted. In the ammonia purification system 300, the configuration of the raw material storage tank 1A is the same as that of the above-described raw material storage tank 1, and is the same as the ammonia purification system 100.

The raw material storage tank 1A included in the ammonia purification system 300 stores crude ammonia in the form of liquid ammonia and is controlled to a specific temperature and pressure. raw material The storage tank 1A has a cylindrical internal space, and in a state in which liquid ammonia is stored in the internal space thereof, a gas phase is formed in the upper portion of the raw material storage tank 1A, and a liquid phase is formed in the lower portion.

In the present embodiment, the raw material storage tank 1A discharges the stored crude ammonia to the adsorption unit 3. Further, the vaporizer 2 described above is not provided in the ammonia purification system 300. When the crude ammonia is led out from the raw material storage tank 1A to the adsorption unit 3, most of the impurities having low volatility (for example, water, hydrocarbons having more than 6 carbon atoms) remain in the liquid phase, from the raw material storage tank 1A. The formed gas phase is derived in the form of gaseous crude ammonia. In order to vaporize a part of the liquid crude ammonia stored in the raw material storage tank 1A to increase the ammonia concentration in the gas phase, the raw material storage tank 1A is provided with a heating device 302 for heating the liquid crude ammonia. .

A gas-like ammonia outlet pipe 301 is connected to the upper portion of the raw material storage tank 1A (the portion where the gas phase is formed). A flow rate adjuster 71 is connected to an end of the gaseous ammonia-derived piping 301 on the side opposite to the side connected to the raw material storage tank 1A. Further, the gas-like ammonia outlet pipe 301 is provided with an opening and closing valve 3011 that opens or closes the flow path in the gaseous ammonia-outflow pipe 301.

The crude ammonia stored in the raw material storage tank 1A is taken out from the gas phase formed in the raw material storage tank 1A in the form of gaseous crude ammonia in a state where the opening and closing valve 3011 is opened. The gaseous crude ammonia derived from the raw material storage tank 1A flows through the gaseous ammonia-extracting pipe 301 and is supplied to the flow rate adjuster 71. Then, the gaseous crude ammonia is supplied to the adsorption unit 3 including the first adsorption tower 31 and the second adsorption tower 32 by the flow rate adjuster 71. The gaseous crude ammonia supplied to the adsorption unit 3 is contaminated by the first adsorption tower 31 and the second adsorption tower 32. Purified by adsorption removal. Further, the purified gaseous ammonia in the first adsorption tower 31 and the second adsorption tower 32 is segregated in the condenser 4, and impurities having higher volatility are separated and removed.

In the ammonia purification system 300 of the present embodiment configured as described above, the adsorbent layer having different adsorption capacities for water, an organic compound having less than 5 carbon atoms, and an organic compound having 5 or more carbon atoms is laminated. Since the first adsorption tower 31 and the second adsorption tower 32 adsorb and remove impurities contained in the gaseous crude ammonia, impurities (mainly water and organic compounds) contained in the crude ammonia can be efficiently adsorbed and removed. Further, the condenser 4 separates the ammonia derived from the first adsorption tower 31 or the second adsorption tower 32 into a gas phase component and a liquid phase component, so that hydrogen, nitrogen, oxygen, argon, carbon monoxide, carbon dioxide, or the like can be used. The highly volatile impurities are separated and removed in the form of a gas phase component, and the purified liquid ammonia is obtained as a liquid phase component. Therefore, in the ammonia purification system 300 of the present embodiment, it is not necessary to carry out distillation with reflux as in the prior art, and the ammonia can be purified by a simplified method, and ammonia can be efficiently purified by suppressing energy consumption.

Fig. 5 is a view showing the configuration of an ammonia purification system 400 according to a fifth embodiment of the present invention. The ammonia purification system 400 of the present embodiment is similar to the above-described ammonia purification system 100, and the same reference numerals will be given to the corresponding parts, and the description thereof will be omitted. In the ammonia purification system 400, the configuration of the raw material storage tank 1B is the same as that of the above-described raw material storage tank 1, and is the same as the ammonia purification system 100.

The raw material storage tank 1B included in the ammonia purification system 400 stores crude ammonia in the form of liquid ammonia and is controlled to a specific temperature and pressure. raw material The storage tank 1B has a cylindrical internal space, and in a state in which liquid ammonia is stored in the internal space thereof, a gas phase is formed in the upper portion of the raw material storage tank 1B, and a liquid phase is formed in the lower portion. In addition, in order to vaporize a part of the liquid crude ammonia stored in the raw material storage tank 1B, the ammonia concentration in the gas phase is increased, and a heating device for heating the liquid crude ammonia is provided in the raw material storage tank 1B. 403.

In the present embodiment, the raw material storage tank 1B is configured to be capable of deriving the stored crude ammonia from any of the gas phase and the liquid phase.

The concentration of impurities (especially impurities having a higher volatility) in the gas phase formed in the raw material storage tank 1B is different depending on the filling amount (storage amount) of the liquid crude ammonia in the raw material storage tank 1B. The higher the filling amount of the liquid crude ammonia in the raw material storage tank 1B, the higher the concentration of impurities having higher volatility in the gas phase formed in the raw material storage tank 1B. Further, the smaller the filling amount of the liquid crude ammonia in the raw material storage tank 1B, the less volatile impurities (for example, water and organic compounds having a large carbon number) in the liquid phase formed in the raw material storage tank 1B. The higher the concentration. In other words, when liquid ammonia is derived from the liquid phase formed in the raw material storage tank 1B, the amount of liquid ammonia in the raw material storage tank 1B is reduced, and the volatility is gradually lowered. The crude ammonia having a higher impurity concentration is derived from the liquid phase of the raw material storage tank 1B.

Therefore, the ammonia purification system 400 of the present embodiment is configured to switch the export state of the crude ammonia according to the filling amount of the liquid crude ammonia in the raw material storage tank 1B (which phase of the crude gas is derived from the gas phase and the liquid phase) Export action control). The ammonia purification system 400 is configured to calculate a volume ratio of a ratio of a volume of a liquid phase to a volume of an internal space in the raw material storage tank 1B, when the volume is When the ratio is equal to or greater than a predetermined threshold, the liquid ammonia is derived from the liquid phase formed in the raw material storage tank 1B, and when the above threshold is not reached, the gas phase formed in the raw material storage tank 1B is derived. Crude ammonia in the form of a gas.

Specifically, in the ammonia purification system 400, the liquid level of the liquid-like crude ammonia stored in the raw material storage tank 1B in the internal space is detected. If the size of the internal space is known in advance, the volume ratio can be calculated using the liquid level. In particular, in the internal space in which the cross section parallel to the bottom surface is fixed, the ratio of the height of the liquid surface to the height of the internal space is the same as the volume ratio described above, so that the volume ratio can be easily calculated.

In the present embodiment, since the internal space formed in the raw material storage tank 1B has a columnar shape, the cross section parallel to the bottom surface of the circular shape is a fixed internal space. Therefore, the ratio of the liquid level to the height of the internal space is the same as the above volume ratio. Therefore, the ammonia purification system 400 calculates the ratio of the liquid level height to the height of the internal space (the liquid level height / the height of the internal space) using the value of the height of the internal space of the raw material storage tank 1B and the value of the liquid level height. Hereinafter, it is referred to as "height ratio" as a value corresponding to the above volume ratio.

Further, in the ammonia purification system 400, when the height ratio is equal to or greater than a predetermined threshold (in the present embodiment, the threshold value is 1/2), the liquid phase is derived from the liquid phase formed in the raw material storage tank 1B. The method of crude ammonia controls the derivation of crude ammonia in the raw material storage tank 1B. Further, in the ammonia purification system 400, when the height ratio is less than a predetermined threshold value, the crude ammonia of the raw material storage tank 1B is controlled so that the gaseous ammonia is derived from the gas phase formed in the raw material storage tank 1B. The export action.

In other words, the ammonia purification system 400 of the present embodiment is configured to be inspected. When it is measured that the liquid ammonia in the raw material storage tank 1B is filled to a height position of 1/2 or more (corresponding to the above-mentioned threshold value) of the raw material storage tank 1B, the liquid phase formed from the raw material storage tank 1B is derived. Crude ammonia in liquid form. Further, the ammonia purification system 400 is configured to detect that the liquid-like crude ammonia in the raw material storage tank 1B is filled to a height position that is less than 1/2 of the height of the raw material storage tank 1B (corresponding to the above-described threshold value). The gaseous ammonia is derived from the gas phase formed in the raw material storage tank 1B.

In this manner, the crude ammonia is switched in accordance with the filling amount of the liquid crude ammonia in the raw material storage tank 1B, whereby the crude ammonia can be led out from the raw material storage tank 1B in a state where the variation in the impurity concentration is small. Thereby, it is possible to prevent a large deviation in the purity of the ammonia obtained by the final purification.

A liquid ammonia-extracting pipe 401 is connected to a lower portion of the raw material storage tank 1B (a portion where a liquid phase is formed). The end of the liquid ammonia-derived piping 401 opposite to the side connected to the raw material storage tank 1B is connected to the vaporizer 2. Further, the liquid ammonia-derived piping 401 is provided with an opening and closing valve 4011 that opens or closes the flow path in the liquid ammonia-extracting pipe 401. The crude ammonia stored in the raw material storage tank 1B is taken out from the liquid phase formed in the raw material storage tank 1B in the form of liquid crude ammonia in a state where the opening and closing valve 4011 is opened. The liquid crude ammonia derived from the raw material storage tank 1B flows through the liquid ammonia-extracting pipe 401 and is supplied to the vaporizer 2 . The liquid crude ammonia derived from the raw material storage tank 1B is vaporized by the vaporizer 2, and then supplied to the flow rate adjuster 71 in the form of gaseous ammonia. The gaseous ammonia obtained by vaporization of the vaporizer 2 is adjusted in flow rate by the flow rate adjuster 71, and then supplied to the adsorption unit 3 including the first adsorption tower 31 and the second adsorption tower 32.

Further, a gaseous ammonia outlet pipe 402 is connected to the upper portion of the raw material storage tank 1B (the portion where the gas phase is formed). An end portion of the gaseous ammonia-derived piping 402 opposite to the side connected to the raw material storage tank 1B is connected to the flow rate adjuster 71. Further, the gas-like ammonia outlet pipe 402 is provided with an opening and closing valve 4021 that opens or closes the flow path in the gaseous ammonia-outlet pipe 402.

The crude ammonia stored in the raw material storage tank 1B is taken out from the gas phase formed in the raw material storage tank 1B in the form of gaseous crude ammonia in a state where the opening and closing valve 4021 is opened. The gaseous crude ammonia derived from the raw material storage tank 1B flows through the gaseous ammonia-extracting pipe 402 and is supplied to the flow rate adjuster 71. Then, the gaseous crude ammonia is supplied to the adsorption unit 3 including the first adsorption tower 31 and the second adsorption tower 32 by the flow rate adjuster 71.

In the ammonia purification system 400 of the present embodiment, the gaseous ammonia supplied to the adsorption unit 3 is purified by adsorbing and removing impurities from the first adsorption tower 31 and the second adsorption tower 32. Further, the purified gaseous ammonia in the first adsorption tower 31 and the second adsorption tower 32 is segregated in the condenser 4, and impurities having higher volatility are separated and removed.

In the ammonia purification system 400 of the present embodiment configured as described above, the adsorbent layer having different adsorption capacities for water, an organic compound having less than 5 carbon atoms, and an organic compound having 5 or more carbon atoms is laminated. Since the first adsorption tower 31 and the second adsorption tower 32 adsorb and remove impurities contained in the gaseous crude ammonia, impurities (mainly water and organic compounds) contained in the crude ammonia can be efficiently adsorbed and removed. Further, the condenser 4 separates the ammonia derived from the first adsorption tower 31 or the second adsorption tower 32 into a gas phase component and a liquid phase component, so that hydrogen, nitrogen, oxygen, argon, carbon monoxide, or the like can be used. The highly volatile impurities such as carbon dioxide are separated and removed in the form of a gas phase component, and the purified liquid ammonia is obtained in the form of a liquid phase component. Therefore, in the ammonia purification system 400 of the present embodiment, it is not necessary to carry out distillation with reflux as in the prior art, and the ammonia can be purified by a simplified method, and ammonia can be efficiently purified by suppressing energy consumption.

The present invention may be embodied in other various forms without departing from the spirit or essential characteristics thereof. Therefore, the above-described embodiments are merely illustrative in all aspects, and the scope of the present invention is not limited by the scope of the specification. Further, all modifications or alterations belonging to the scope of the claims are within the scope of the invention.

1‧‧‧Material storage tank

1A‧‧‧Material storage tank

1B‧‧‧Material storage tank

2‧‧‧ gasifier

3‧‧‧Adsorption unit

4‧‧‧Condenser

5‧‧‧Recycling tank

6‧‧‧Filling device

31‧‧‧1st adsorption tower

32‧‧‧2nd adsorption tower

71‧‧‧Flow Regulator

72‧‧‧Cooling liquid feeding device

80‧‧‧Exhaust piping

80A‧‧‧ discharge piping

81‧‧‧1st piping

82‧‧‧2nd piping

83‧‧‧3rd piping

84‧‧‧4th piping

85‧‧‧5th piping

86‧‧‧6th piping

87‧‧‧7th piping

88‧‧‧8th piping

89‧‧‧9th piping

90‧‧‧10th piping

91‧‧‧11th piping

92‧‧‧12th piping

93‧‧‧13th piping

94‧‧‧14th piping

95‧‧‧15th piping

100‧‧‧Ammonia Purification System

150‧‧‧Ammonia Purification System

151‧‧‧Adsorption unit

200‧‧‧Ammonia Purification System

201‧‧‧Adsorption unit

300‧‧‧Ammonia Purification System

311‧‧‧ top adsorption layer

312‧‧‧1st intermediate adsorption layer

313‧‧‧2nd intermediate adsorption layer

314‧‧‧ bottom adsorption layer

321‧‧‧ top adsorption layer

322‧‧‧1st intermediate adsorption layer

323‧‧‧2nd intermediate adsorption layer

324‧‧‧ bottom adsorption layer

400‧‧‧Ammonia Purification System

801‧‧‧Exhaust valve

801A‧‧‧ discharge valve

811‧‧‧1st valve

821‧‧‧2nd valve

841‧‧‧4th valve

851‧‧‧5th valve

871‧‧‧7th valve

881‧‧‧8th valve

891‧‧‧9th valve

901‧‧‧10th valve

911‧‧‧11th valve

921‧‧‧12th valve

931‧‧‧13th valve

951‧‧‧15th valve

1511‧‧‧1st adsorption tower

1512‧‧‧2nd adsorption tower

1513‧‧‧3rd adsorption tower

2011‧‧‧1st adsorption tower

2012‧‧‧Second adsorption tower

2013‧‧‧3rd adsorption tower

2014‧‧‧4th adsorption tower

15111‧‧‧ top adsorption layer

15112‧‧‧1st intermediate adsorption layer

15113‧‧‧2nd intermediate adsorption layer

15114‧‧‧ bottom adsorption layer

15121‧‧‧ top adsorption layer

15122‧‧‧1st intermediate adsorption layer

15123‧‧‧2nd intermediate adsorption layer

15124‧‧‧ bottom adsorption layer

15131‧‧‧ top adsorption layer

15132‧‧‧1st intermediate adsorption layer

15133‧‧‧2nd intermediate adsorption layer

15134‧‧‧ bottom adsorption layer

20111‧‧‧ top adsorption layer

20112‧‧‧1st intermediate adsorption layer

20113‧‧‧2nd intermediate adsorption layer

20114‧‧‧3rd intermediate adsorption layer

20115‧‧‧ bottom adsorption layer

20121‧‧ ‧ top adsorption layer

20122‧‧‧1st intermediate adsorption layer

20123‧‧‧2nd intermediate adsorption layer

20124‧‧‧3rd intermediate adsorption layer

20125‧‧‧ bottom adsorption layer

20131‧‧‧ top adsorption layer

20132‧‧‧1st intermediate adsorption layer

20133‧‧‧2nd intermediate adsorption layer

20134‧‧‧3rd intermediate adsorption layer

20135‧‧‧ bottom adsorption layer

20141‧‧ ‧ top adsorption layer

20142‧‧‧1st intermediate adsorption layer

20143‧‧‧2nd intermediate adsorption layer

20144‧‧‧3rd intermediate adsorption layer

20145‧‧‧ bottom adsorption layer

Fig. 1 is a view showing the configuration of an ammonia purification system 100 according to a first embodiment of the present invention.

Fig. 2 is a view showing the configuration of an ammonia purification system 150 according to a second embodiment of the present invention.

Fig. 3 is a view showing the configuration of an ammonia purification system 200 according to a third embodiment of the present invention.

Fig. 4 is a view showing the configuration of an ammonia purification system 300 according to a fourth embodiment of the present invention.

Fig. 5 is a view showing the configuration of an ammonia purification system 400 according to a fifth embodiment of the present invention.

1‧‧‧Material storage tank

2‧‧‧ gasifier

3‧‧‧Adsorption unit

4‧‧‧Condenser

5‧‧‧Recycling tank

6‧‧‧Filling device

31‧‧‧1st adsorption tower

32‧‧‧2nd adsorption tower

71‧‧‧Flow Regulator

72‧‧‧Cooling liquid feeding device

80‧‧‧Exhaust piping

80A‧‧‧ discharge piping

81‧‧‧1st piping

82‧‧‧2nd piping

83‧‧‧3rd piping

84‧‧‧4th piping

85‧‧‧5th piping

86‧‧‧6th piping

87‧‧‧7th piping

88‧‧‧8th piping

89‧‧‧9th piping

90‧‧‧10th piping

91‧‧‧11th piping

92‧‧‧12th piping

93‧‧‧13th piping

94‧‧‧14th piping

95‧‧‧15th piping

100‧‧‧Ammonia Purification System

311‧‧‧ top adsorption layer

312‧‧‧1st intermediate adsorption layer

313‧‧‧2nd intermediate adsorption layer

314‧‧‧ bottom adsorption layer

321‧‧‧ top adsorption layer

322‧‧‧1st intermediate adsorption layer

323‧‧‧2nd intermediate adsorption layer

324‧‧‧ bottom adsorption layer

801‧‧‧Exhaust valve

801A‧‧‧ discharge valve

811‧‧‧1st valve

821‧‧‧2nd valve

841‧‧‧4th valve

851‧‧‧5th valve

871‧‧‧7th valve

881‧‧‧8th valve

891‧‧‧9th valve

901‧‧‧10th valve

911‧‧‧11th valve

921‧‧‧12th valve

931‧‧‧13th valve

951‧‧‧15th valve

Claims (5)

An ammonia purification system for purifying crude ammonia containing impurities, comprising: a storage portion for storing crude ammonia and discharging the stored crude ammonia; and an adsorption portion selected from activated carbon, The adsorbent in the hydrophilic zeolite, the hydrophobic zeolite, the tannin extract, and the activated alumina is purified by adsorbing and removing impurities contained in the crude ammonia derived from the storage portion, and purifying the purified ammonia, and the adsorption portion includes a Or a plurality of adsorption portions, wherein the adsorption portion is laminated along the flow direction of the crude ammonia: a first adsorbent layer containing a first adsorbent, and a plurality of second adsorbent layers having a different species than the first adsorbent a second adsorbent and a third adsorbent layer containing a third adsorbent different in type from the second adsorbent; and a partial condensation unit that separates and purifies the purified ammonia derived from the adsorption unit It is a gas phase component and a liquid phase component, whereby impurities with higher volatility are separated and removed in the form of a gas phase component, and purified liquid ammonia is obtained in the form of a liquid phase component. The ammonia purification system of claim 1, further comprising a gasification portion that vaporizes a portion of the liquid crude ammonia derived from the storage portion, and derives gaseous ammonia, and the adsorption portion passes through the adsorption portion The impurities contained in the gaseous ammonia derived from the vaporization section are adsorbed and removed. An ammonia purification system as claimed in claim 1, wherein The first adsorbent is an adsorbent having a high adsorption capacity for water, and the second adsorbent is an adsorbent having a high adsorption capacity for an organic compound having a carbon number of less than 5, and the third adsorbent is a pair. An organic compound having a carbon number of 5 or more and an adsorbent having a high adsorption capacity with water. The ammonia purification system according to claim 1, wherein the adsorption portion sequentially deposits the first adsorbent layer, the plurality of second adsorbent layers, and the third adsorbent from the upstream side to the downstream side in the flow direction of the crude ammonia. Agent layer. The ammonia purification system of claim 1, wherein the adsorption portion comprises a plurality of the adsorption portions, and the plurality of adsorption portions are connected in series or in parallel.