WO2012132560A1 - Procédé de purification d'ammoniac et système de purification d'ammoniac - Google Patents

Procédé de purification d'ammoniac et système de purification d'ammoniac Download PDF

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WO2012132560A1
WO2012132560A1 PCT/JP2012/052779 JP2012052779W WO2012132560A1 WO 2012132560 A1 WO2012132560 A1 WO 2012132560A1 JP 2012052779 W JP2012052779 W JP 2012052779W WO 2012132560 A1 WO2012132560 A1 WO 2012132560A1
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ammonia
partial
phase component
impurities
partial reduction
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PCT/JP2012/052779
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English (en)
Japanese (ja)
Inventor
慎一 田井
啓之 畑
茂 森本
義則 吉田
修司 津野
豊仁 福島
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住友精化株式会社
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Priority to CN2012800041903A priority Critical patent/CN103269980A/zh
Priority to KR1020137013883A priority patent/KR20130140754A/ko
Publication of WO2012132560A1 publication Critical patent/WO2012132560A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/024—Purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/12—Separation of ammonia from gases and vapours
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia

Definitions

  • the present invention relates to a purification method and an ammonia purification system for purifying crude ammonia.
  • high-purity ammonia is used as a processing agent used for producing a nitride film.
  • Such high-purity ammonia can be obtained by purifying crude ammonia to remove impurities.
  • the crude ammonia contains hydrogen, nitrogen, oxygen, argon, nitrogen monoxide, carbon dioxide and other low-boiling gases, hydrocarbons, moisture and the like as impurities.
  • the purity of generally available crude ammonia is about 98 to 99% by weight.
  • hydrocarbons contained in crude ammonia are mainly those having 1 to 4 carbon atoms.
  • the oil content in the cracking gas is insufficiently separated.
  • hydrocarbons having a high boiling point and a large molecular weight may be mixed.
  • ammonia contains a large amount of moisture, the function of a semiconductor or the like manufactured using this ammonia may be greatly reduced, and the moisture in ammonia needs to be reduced as much as possible.
  • ammonia is used in the semiconductor manufacturing process and the liquid crystal manufacturing process
  • the manner in which the impurities in ammonia vary.
  • the purity of ammonia is required to be 99.9999% by weight or more (each impurity concentration of 100 ppb or less), more preferably about 99.99999% by weight.
  • a moisture concentration of less than 30 ppb has been demanded for the production of a light emitter such as gallium nitride.
  • high-purity ammonia is obtained by combining a moisture adsorption tower, a hydrocarbon adsorption tower, and a distillation tower.
  • impurities having a boiling point higher than the bottom of the distillation column are first removed using a rectification column, and ammonia derived from the top of the distillation column is passed through an adsorption column. Remove moisture. Thereafter, distillation is performed again in the rectification column to remove impurities having a lower boiling point than the top of the distillation column, and high-purity ammonia is obtained from the bottom of the distillation column.
  • the purification method disclosed in Patent Document 3 after removing impurities having a low boiling point with a distillation column, high-purity ammonia is obtained by removing moisture and oxygen with an adsorption column.
  • an object of the present invention is to provide an ammonia purification method and an ammonia purification system capable of purifying ammonia with high recovery, simple operation, short purification time, and low energy input even when impurities are contained in ammonia at a high concentration. Is to provide.
  • the present invention is a method for purifying crude ammonia containing impurities,
  • the method comprises a partial condensation step of separating and separating crude ammonia into a gas phase component and a liquid phase component, and separating and removing impurities contained in the crude ammonia as a gas phase component or a liquid phase component. It is a purification method of ammonia.
  • the partial reduction step comprises hydrogen, nitrogen, oxygen, argon, carbon monoxide, carbon dioxide, and hydrocarbons having 1 to 8 carbon atoms contained as impurities in the crude ammonia. It is preferable to include a first partial reduction step of separating and removing as a gas phase component.
  • the partial reduction step includes a second partial reduction step of separating and removing moisture and hydrocarbons having 9 or more carbon atoms as impurities in the crude ammonia as liquid phase components. It is preferable.
  • the first partial reduction step is preferably a step subsequent to the second partial reduction step.
  • the liquid phase component obtained by partial reduction of the crude ammonia in the first partial reduction step is vaporized, and the vaporized vaporized product is fractionated.
  • a third partial reduction step in which the gas phase component and the liquid phase component are separated, and impurities with respect to ammonia contained in the vaporized material are separated and removed as the gas phase component.
  • the first partial reduction step includes a plurality of partial reduction stages for partial reduction of the crude ammonia, and the crude ammonia is reduced at a lower temperature as the subsequent partial reduction stage is reached. It is preferable.
  • the crude ammonia is partial reduced at a temperature of ⁇ 77 to 50 ° C.
  • the crude ammonia is partial reduced under an absolute pressure of 0.007 to 2 MPa.
  • the ammonia purification method of the present invention preferably includes an adsorption removal step of adsorbing and removing impurities contained in the crude ammonia with an adsorbent.
  • the adsorption removal step includes a first adsorption removal step of adsorbing and removing moisture contained as impurities in the crude ammonia with an adsorbent.
  • the adsorption removal step includes a second adsorption removal step of adsorbing and removing hydrocarbons contained as impurities in the crude ammonia with an adsorbent.
  • the adsorption removal step is preferably a pre-step or a post-step of the partial reduction step.
  • the ammonia purification method of the present invention includes an adsorption removal step of adsorbing and removing impurities contained in the crude ammonia by an adsorbent,
  • the adsorption removal step is preferably a step between the second partial reduction step and the first partial reduction step.
  • the present invention also provides an ammonia purification system for purifying crude ammonia containing impurities, Crude ammonia is fractionated and separated into a gas phase component and a liquid phase component, and hydrogen, nitrogen, oxygen, argon, carbon monoxide, carbon dioxide, and carbon atoms of 1 to 8 contained as impurities in the crude ammonia.
  • an ammonia purification system characterized by comprising:
  • the ammonia purification system of the present invention further includes an adsorption removing unit that adsorbs and removes impurities contained in the crude ammonia by an adsorbent.
  • the second partial reduction unit, the first partial reduction unit, and the adsorption removal unit are connected in series in this order,
  • the first partial reduction unit performs partial reduction of the vapor phase component separated by the second partial reduction unit to separate into a vapor phase component and a liquid phase component, It is preferable that the adsorption removal unit adsorbs and removes impurities contained in the liquid phase component separated by the first partial reduction unit using an adsorbent.
  • the second partial reduction unit, the adsorption removal unit, and the first partial reduction unit are connected in series in this order,
  • the adsorption removal unit adsorbs and removes impurities contained in the gas phase component separated by the second partial reduction unit with an adsorbent, It is preferable that the first partial contraction unit contracts ammonia from which impurities have been adsorbed and removed by the adsorption removal unit.
  • the ammonia after the impurities are adsorbed and removed by the adsorption removing unit is divided to separate the gas phase component and the liquid phase component, and the impurities are separated and removed as the gas phase component. It is preferable to further include a three-fold reduced portion.
  • the adsorption removal unit and the first partial reduction unit are connected in series in this order, It is preferable that the first partial contraction unit contracts ammonia from which impurities have been adsorbed and removed by the adsorption removal unit.
  • the adsorption removal unit, the second partial reduction unit, and the first partial reduction unit are connected in series in this order,
  • the second partial reduction part reduces the ammonia from which impurities have been adsorbed and removed by the adsorption removal part,
  • the first partial reduction unit performs partial reduction of the gas phase component separated by the second partial reduction unit and separates it into a gas phase component and a liquid phase component.
  • the method for purifying ammonia is a method for purifying crude ammonia containing impurities, and includes a partial condensation step.
  • the partial contraction step the crude ammonia is partially contracted and separated into a gas phase component and a liquid phase component, whereby impurities contained in the crude ammonia are separated and removed as a gas phase component or a liquid phase component.
  • Partial contraction refers to liquefying a part of a gas that can be liquefied. Therefore, by the partial reduction operation in the partial reduction process, a part of the gaseous crude ammonia subjected to the partial reduction is liquefied by condensation to become a liquid phase component, and the uncondensed portion remains as a gas and remains as a gas phase component. It becomes.
  • the condensed liquid phase component or the gas phase component that remains uncondensed in the gaseous state contains a large amount of impurities originally present in the crude ammonia, and conversely The amount of impurities decreases in the gas phase component or liquid phase component forming a pair.
  • impurities that are less volatile in the crude ammonia are concentrated in the liquid phase components produced by the partial condensation by partial condensation of the gaseous crude ammonia, and volatile in the crude ammonia.
  • High impurities can be concentrated in the gas phase component that remains uncondensed.
  • purifying crude ammonia impurities contained in the crude ammonia can be separated and removed, and purified ammonia can be obtained. Therefore, it is possible to purify ammonia with high recovery rate, simple operation, short purification time, and low energy input even if impurities are contained in crude ammonia at a high concentration without going through a distillation step as in the prior art. Can do.
  • the partial reduction process includes a first partial reduction process.
  • gaseous crude ammonia is partially condensed and separated into a gas phase component and a liquid phase component, whereby impurities contained in the crude ammonia are separated and removed as a gas phase component.
  • impurities contained in the crude ammonia are separated and removed as a gas phase component.
  • hydrogen, nitrogen, oxygen, argon, carbon monoxide, carbon dioxide, and hydrocarbons having 1 to 8 carbon atoms which are highly volatile impurities in the crude ammonia, are condensed. It can be concentrated and concentrated in the uncondensed gas phase components that have not been present.
  • the partial reduction process includes a second partial reduction process.
  • gaseous crude ammonia is partially condensed and separated into a gas phase component and a liquid phase component, whereby impurities contained in the crude ammonia are separated and removed as a liquid phase component.
  • moisture and hydrocarbons having 9 or more carbon atoms which are low-volatility impurities in the crude ammonia, can be concentrated in the condensed liquid phase component and separated and removed. it can.
  • the first partial reduction process is a subsequent process of the second partial reduction process.
  • the vapor phase component after the impurities contained in the crude ammonia in the second partial reduction step are separated and removed as the liquid phase component is subjected to partial reduction to obtain the vapor phase component and the liquid phase.
  • the remaining impurities contained in the crude ammonia can be separated and removed as gas phase components. Therefore, higher purity ammonia can be obtained.
  • the partial reduction process includes a third partial reduction process.
  • the liquid phase component obtained by partial reduction of the crude ammonia in the first partial reduction step is vaporized, and the vaporized vaporized product is partial condensed to obtain a gas phase component and a liquid phase component.
  • impurities with respect to ammonia contained in the vaporized material are separated and removed as gas phase components.
  • highly volatile impurities contained in the crude ammonia are separated and removed as gas phase components. That is, the liquid phase component obtained in the first partial condensation step is liquid ammonia in which the content of highly volatile impurities is reduced.
  • liquid ammonia is vaporized, and the vaporized vaporized product is separated and removed, so that impurities contained in the vaporized product are separated and removed as gas phase components. Liquid ammonia in which the content of high impurities is further reduced can be obtained.
  • the first partial reduction step includes a plurality of partial reduction stages for partial reduction of the crude ammonia, and the partial ammonia is reduced at a lower temperature as the subsequent partial reduction stage is reached.
  • impurities contained in the crude ammonia can be separated and removed efficiently as a gas phase component, and higher purity liquid ammonia can be obtained as a liquid phase component.
  • the crude ammonia is partial reduced at a temperature of ⁇ 77 to 50 ° C. Even when the temperature in the first partial contraction step is higher than 50 ° C., the effect of removing impurities by partial contraction can be obtained by increasing the pressure, but the ammonia pressure at that time becomes as high as 1.81 MPa, industrially. It is not a preferable condition for implementation. Further, even when the temperature in the first partial reduction step is lower than ⁇ 77 ° C., ammonia can be purified by lowering the pressure. However, since the temperature is low, high-purity ammonia is obtained as a liquid phase component. However, since the melting point of ammonia is ⁇ 78 ° C., it is necessary to periodically melt and solidify ammonia that solidifies at a low temperature. When considering a process, it is not an efficient method.
  • the crude ammonia in the first partial contraction step, is contracted under an absolute pressure of 0.007 to 2 MPa.
  • crude ammonia can be partially condensed at a temperature of ⁇ 77 to 50 ° C., so that high-purity ammonia can be obtained efficiently.
  • the method for purifying ammonia further includes an adsorption removal step.
  • impurities contained in the crude ammonia are removed by adsorption with an adsorbent.
  • the impurities that could not be removed in the partial condensation step can be adsorbed and removed by the adsorbent, so that higher purity ammonia can be obtained.
  • the adsorption removal step includes a first adsorption removal step.
  • moisture contained as impurities in the crude ammonia is adsorbed and removed by the adsorbent.
  • moisture impurities that cannot be removed in the partial condensation step can be adsorbed and removed by the adsorbent, so that higher purity ammonia can be obtained.
  • the adsorption removal step includes a second adsorption removal step.
  • this second adsorption removal step hydrocarbons contained as impurities in the crude ammonia are adsorbed and removed by the adsorbent.
  • hydrocarbon impurities that cannot be removed in the partial condensation step can be adsorbed and removed by the adsorbent, so that higher purity ammonia can be obtained.
  • the adsorption removal step is a pre-step or a post-step of the partial reduction step.
  • the adsorption removal step is a subsequent step of the partial reduction step, impurities that could not be removed in the partial reduction step can be adsorbed and removed by the adsorbent, so that higher purity ammonia can be obtained.
  • the adsorption removal step is a pre-step of the partial reduction step, the impurities contained in the crude ammonia can be effectively removed by the partial reduction after the impurities contained in the crude ammonia are removed by adsorption. Pure ammonia can be obtained.
  • the adsorption removal process is performed between the second partial reduction process and the first partial reduction process.
  • the ammonia purification system includes a first partial reduction unit and a second partial reduction unit.
  • the first partial reduction part separates and removes impurities contained in the crude ammonia as a gas phase component by partial condensation of the crude ammonia and separating it into a gas phase component and a liquid phase component.
  • the first partial contraction portion by partial contraction, hydrogen, nitrogen, oxygen, argon, carbon monoxide, carbon dioxide, and hydrocarbons having 1 to 8 carbon atoms, which are highly volatile impurities in the crude ammonia, It can be concentrated in an uncondensed uncondensed gas phase component and separated and removed.
  • the second partial reduction unit separates and removes impurities contained in the crude ammonia as a liquid phase component by partial condensation of the crude ammonia and separating it into a gas phase component and a liquid phase component.
  • the second partial contraction unit separates and removes moisture and hydrocarbons having 9 or more carbon atoms, which are low-volatile impurities in the crude ammonia, by concentration in the condensed liquid phase component. be able to.
  • the ammonia purification system further includes an adsorption removal unit.
  • the adsorption removal unit adsorbs and removes impurities contained in the crude ammonia with an adsorbent.
  • the impurities that could not be removed by the first partial contraction part and the second partial contraction part can be adsorbed and removed by the adsorbent, so that higher purity ammonia can be obtained.
  • the second partial reduction section, the first partial reduction section, and the adsorption removal section are connected in series in this order.
  • the first partial reduction unit performs partial reduction of the vapor phase component separated by the second partial reduction unit to separate the vapor phase component and the liquid phase component
  • the adsorption removal unit separates by the first partial reduction unit. Impurities contained in the liquid phase component thus formed are adsorbed and removed by an adsorbent. In this way, high purity ammonia can be obtained.
  • the second partial reduction section, the adsorption removal section, and the first partial reduction section are connected in series in this order.
  • the adsorption removal unit adsorbs and removes impurities contained in the gas phase component separated by the second partial reduction unit by the adsorbent, and the first partial reduction unit removes impurities by the adsorption removal unit. Shrink ammonia. In this way, high purity ammonia can be obtained.
  • the ammonia purification system in which the second partial reduction unit, the first partial reduction unit, and the adsorption removal unit are connected in series in this order further includes a third partial reduction unit.
  • the third partial reduction unit separates ammonia after impurities are removed by the second partial reduction unit, the first partial reduction unit, and the adsorption removal unit, and separates the ammonia into a vapor phase component and a liquid phase component. Are separated and removed as a gas phase component.
  • impurities that could not be removed by the second partial reduction unit, the first partial reduction unit, and the adsorption removal unit can be separated and removed as gas phase components, so that higher-purity ammonia can be obtained.
  • the adsorption removal unit and the first partial reduction unit are connected in series in this order. And a 1st partial reduction part carries out partial reduction of the ammonia from which the impurity was adsorbed and removed by the adsorption removal part. In this way, high purity ammonia can be obtained.
  • the adsorption removing unit, the second partial reduction unit, and the first partial reduction unit are connected in series in this order. Then, the second partial reduction unit reduces the ammonia from which the impurities have been adsorbed and removed by the adsorption removal unit, and the first partial reduction unit reduces the gas phase component separated by the second partial reduction unit to gas Separate into phase and liquid phase components. In this way, high purity ammonia can be obtained.
  • FIG. 3 is a diagram illustrating a configuration of a second divider 3.
  • FIG. 3 is a diagram showing a configuration of a first divider 5. It is a figure which shows the structure of the 1st frequency divider 5 by which the some partial reduction part was connected in series. It is a figure which shows the position which introduce
  • FIG. It is a figure which shows the connection structure between the 1st collection
  • FIG. It is a figure which shows the structure of the ammonia purification system 200 which concerns on 2nd Embodiment of this invention. It is a figure which shows the structure of the ammonia purification system 300 which concerns on 3rd Embodiment of this invention. It is a figure which shows the structure of the ammonia purification system 400 which concerns on 4th Embodiment of this invention. It is a figure which shows the structure of the ammonia purification system 500 which concerns on 5th Embodiment of this invention. It is a figure which shows the structure of the ammonia purification system 600 which concerns on 6th Embodiment of this invention.
  • FIG. 1 is a diagram showing a configuration of an ammonia purification system 100 according to the first embodiment of the present invention.
  • the ammonia purification system 100 of the present embodiment is a system that purifies crude ammonia containing impurities.
  • the ammonia purification system 100 includes a raw material storage tank 1, a first evaporator 2, a second divider 3 that is a second divider, a first divider 5 that is a first divider, 2 recovery tank 4, 1st recovery tank 6, 2nd evaporator 7, 1st adsorption tower 8 and 2nd adsorption tower 9 which are adsorption removal parts, full-condenser (liquefaction device) 10, and product tank 30.
  • the ammonia purification system 100 realizes the ammonia purification method according to the present invention, and the first divider 5 that is the first partial reduction unit executes the first partial reduction step and is the second partial reduction unit.
  • the second partial condenser 3 executes the second partial reduction process, the first adsorption tower 8 executes the first adsorption removal process, and the second adsorption tower 9 executes the second adsorption removal process.
  • a characteristic configuration in the ammonia purification system 100 of the present embodiment is the second divider 3 and the first divider 5.
  • the second partial condenser 3 separates gaseous crude ammonia into a gas phase component and a liquid phase component to separate low volatile impurities contained in the crude ammonia as a liquid phase component.
  • the first divider 5 separates gaseous volatile ammonia into a gas phase component and a liquid phase component, thereby separating a highly volatile impurity contained in the crude ammonia as a gas phase component. Remove.
  • Impurities contained in industrially produced ammonia are broadly classified into dissolved low boiling point gases such as hydrogen, nitrogen, oxygen, argon, carbon monoxide and carbon dioxide. , Hydrocarbons, moisture and the like.
  • hydrocarbons contained in the crude ammonia methane is the most abundant, but ethane, propane, ethylene and propylene are the next most abundant.
  • carbon number hydrocarbons having 1 to 3 carbon atoms constitute the main component of hydrocarbons.
  • crude ammonia contains hydrocarbons having 4 or more carbon atoms, and in many cases hydrocarbons having 4 to 6 carbon atoms, although the content thereof is small.
  • an oil pump or the like is used for compression.
  • hydrocarbons having a large molecular weight such as oil components derived from pump oil mixed from an oil pump or the like are contained in the crude ammonia.
  • ammonia for the electronics industry, which is an ammonia purification system capable of removing hydrocarbons having a wide range of carbon atoms, which constitute these impurities.
  • the present inventors have found that a method using partial condensation is excellent as a method for removing impurities in crude ammonia in place of rectification.
  • Table 1 shows the boiling points of ammonia and saturated n-hydrocarbons having 1 to 8 carbon atoms, but hydrocarbons having 4 to 8 carbon atoms have a boiling point higher than that of ammonia when the hydrocarbon is present as a pure substance. However, in the rectification operation, it is discharged from the top of the distillation column as a highly volatile compound.
  • the boiling point of hydrocarbons having 1 to 8 carbon atoms is, for example, the boiling point of propane having 3 carbon atoms.
  • propane is put into a container and the temperature is changed, the pressure in the container is reduced. This is the temperature at 1 atm (0.1013 MPa).
  • the state of propane at this time is a state in which adjacent propane molecules are attracted to each other by van der Waals force or the like, and if the pulling force is strong, the boiling point appears high.
  • the concentration of propane present in ammonia is very low, which is now a problem, there is no propane molecule or other hydrocarbon molecule that can be attracted next to the propane molecule.
  • the concentration of hydrocarbons with 1 to 8 carbon atoms contained in trace amounts in ammonia shows the concentration distribution in the gas phase and liquid phase of liquefied ammonia by changing the temperature in various ways in ammonia.
  • Table 2 shows the measurement results when the concentration at the point where the gas-liquid equilibrium state was reached. The distribution ratio was measured after adjusting the initial concentration of each saturated n-hydrocarbon concentration in liquid ammonia to 5000 ppm, and then standing at a predetermined temperature for 2 days.
  • the gas-liquid distribution coefficient shown in Table 2 is an index of how much impurities can be separated by partial contraction, and is defined as follows.
  • Distribution coefficient (Kd) A 1 / A 2 (1)
  • a 1 represents an impurity concentration of gaseous ammonia after the gas-liquid equilibrium
  • a 2 represents an impurity concentration in liquid ammonia after gas-liquid equilibrium.
  • impurity concentrations A 1 and A 2 in the above formula (1) have mol-ppm as the unit, and are defined by the following formula (2).
  • Impurity concentration (A 1 , A 2 ) Impurity (mol) / (ammonia (mol) + impurity (mol)) ⁇ 10 6 ... (2)
  • an impurity having a larger gas-liquid partition coefficient is contained more in uncondensed gaseous ammonia that has not been condensed by partial condensation.
  • a hydrocarbon having a smaller carbon number has a higher ratio in the gas phase than in the liquid phase, and a hydrocarbon having a carbon number of up to 8 exists in a higher concentration in the gas phase. Furthermore, the lower the temperature, the higher the concentration of hydrocarbons in the ammonia gas phase.
  • Table 2 shows data for saturated straight-chain hydrocarbons. In the case of 4 or more carbon atoms, the corresponding various isomers, and in the case of hydrocarbons of 2 or more carbon atoms, unsaturated bonds are included in the molecule. There is also a tendency shown in Table 2.
  • the present inventors have confirmed that the behavior of hydrocarbons having 1 to 8 carbon atoms, which are dilute impurities in crude ammonia, is significantly different from the state considered conventionally. Taking this a step further, we thought that the difference in properties of this hydrocarbon having 1 to 8 carbon atoms in ammonia could be used for the purification of ammonia. Therefore, 95% of the gaseous crude ammonia containing methane, ethane and propane, respectively, 5000 ppm, 500 ppm and 500 ppm, the ammonia gas temperature is kept at -20 ° C, and the wall temperature in the first divider 5 is -30 ° C.
  • the purification method by fractionation in the first fractionator 5 not only provides high-purity ammonia in a short time but also has a great energy advantage. I understand that there is.
  • the present inventors use the first divider 5 to reduce the gaseous crude ammonia to about 90 to 99.5%.
  • the concentration of impurities contained in the liquid ammonia obtained as a liquid phase component is greatly reduced compared to the concentration of impurities contained in the first gaseous crude ammonia. Found the fact that.
  • the liquid ammonia obtained as a liquid phase component by the partial reduction is predicted from the gas-liquid distribution ratio as described above. Beyond that value, the concentration of impurity hydrocarbons is much lower. The reason for this is not clear, but it is presumed that in the partial reduction, the equilibrium relationship is lost and dynamic impurity separation occurs, and most of the impurity hydrocarbons remain in the vapor phase components that are not condensed.
  • the correctness of this inference is that the liquid ammonia obtained as a liquid phase component by the partial reduction in the first partial reducer 5 is not taken out from the first partial reducer 5 quickly, but in the liquid ammonia state, the first partial reduction. If it is kept inside the vessel 5, the concentration of impurity hydrocarbons in the liquid ammonia gradually increases with the passage of time, which is supported.
  • this gas-liquid distribution coefficient is affected by temperature, and a larger gas-liquid distribution coefficient can be obtained as the partial contraction temperature is lower.
  • the absolute temperature of ammonia supplied to the first partial condenser 5 is high when the set temperature of the partial condensation operation in the first partial condenser 5 is high, for example, when the temperature at which partial condensation of ammonia is 50 ° C.
  • the pressure is set to 1.81 MPa or more, ammonia can be partially condensed, which means that the separation efficiency of hydrocarbon impurities may be reduced as compared with the case where the set temperature of the partial operation is low. Yes.
  • the first partial reducer 5 reduces the crude ammonia so that the temperature of the gas phase component in the first partial reducer 5 is 50 ° C. or lower, more preferably ⁇ 77 ° C. to 30 ° C.
  • the crude ammonia may be partial reduced under an absolute pressure of 0.007 to 2 MPa.
  • the partial reduction temperature in the first partial condenser 5 is higher than 50 ° C., if the pressure is increased, the effect of removing impurity hydrocarbons by partial reduction can be obtained, but the absolute pressure of ammonia at that time is as high as 1.81 MPa. Therefore, it is not a preferable condition for industrial implementation.
  • the partial reduction temperature in the first partial condenser 5 is higher than 50 ° C., when the concentration of impurity hydrocarbons initially present in the crude ammonia becomes higher than expected, However, the possibility of impurities being contained in the liquefied ammonia increases, and the purification yield and the purification efficiency are lowered, for example, it is necessary to cope with the problem by lowering the partial contraction rate.
  • the partial temperature in the first partial condenser 5 is lower than ⁇ 77 ° C.
  • the melting point of ammonia is ⁇ 78 ° C.
  • the solidification of the liquid ammonia obtained by the condensation is caused when the wall temperature of the first divider 5 is reduced to a temperature lower than the melting point of ammonia. As the process proceeds, it is necessary to periodically melt and liquefy it, and when considering a continuous process, it is not an efficient method.
  • the partial reduction operation is performed at a temperature where the wall temperature of the first partial condenser 5 is below -77 ° C.
  • the wall of the first divider 5 was set to a low temperature for the partial reduction in the first divider 5, it was obtained as a liquid phase component present on the wall of the first divider 5.
  • the liquid film of liquid ammonia approaches its vessel wall temperature.
  • the lower the temperature the larger the ratio of impurity hydrocarbons present in the gas phase to the impurity hydrocarbons present in the liquid phase. It is done.
  • the liquid ammonia obtained as a liquid phase component by condensation due to partial condensation also suppresses the migration of impurity hydrocarbons from the gas phase component to the liquid ammonia into the liquid film.
  • the obtained liquid ammonia can be kept in high purity.
  • the impurity concentration in the crude ammonia is very high, it is effective to repeat the partial reduction in the first partial condenser 5 a plurality of times.
  • crude ammonia containing 30,000 ppm of methane and 10000 ppm of propane is subjected to partial reduction operation in the first partial condenser 5 at a partial reduction temperature of ⁇ 15 ° C. and a condensation rate of 95%.
  • the impurity concentration in liquid ammonia obtained as a liquid phase component by the first partial contraction is 9 ppm for methane and 57 ppm for propane.
  • this liquid ammonia is vaporized and fractionalization is performed again under the same conditions, the impurity concentration in the liquid ammonia obtained as the liquid phase component is not detected for both methane and propane.
  • the low boiling point gas such as hydrogen, nitrogen, oxygen, argon, carbon monoxide, carbon dioxide, etc. contained in the crude ammonia is far more than the above-mentioned impurity hydrocarbons due to the partial condensation in the first partial condenser 5. Can be easily separated and removed. Therefore, if the partial reduction conditions (temperature, pressure, time, etc.) in the first partial condenser 5 are set so that hydrocarbons can be separated and removed, the low-boiling point gas can also be separated and removed. That is, the low boiling point gas, which is an impurity contained in the crude ammonia, can be easily removed as an uncondensed gas phase component by partial condensation in the first partial condenser 5.
  • the concentration of carbon dioxide in the liquid ammonia obtained as the liquid phase component is about 400 minutes that of the concentration initially contained in the crude ammonia. 1 and can be reduced to a very low concentration. Further, as will be described in detail later, carbon dioxide can be adsorbed and removed with zeolite as an adsorbent.
  • the second partial condenser 3 separates gaseous crude ammonia into a gas phase component and a liquid phase component to separate low volatile impurities contained in the crude ammonia as a liquid phase component. Remove.
  • Examples of the low volatility impurities contained in the crude ammonia include moisture, hydrocarbons having a large number of carbon atoms, and trace metals.
  • the hydrocarbon having a large number of carbons refers to a hydrocarbon having 9 or more carbons.
  • Trace metals are components that are problematic in the semiconductor industry. Most of the trace metal contained in the crude ammonia is removed by remaining as a liquid phase component without being vaporized when the crude ammonia is vaporized in the first evaporator 2 described later.
  • the trace metal introduced into the second partial condenser 3 in a state of being contained in the gaseous crude ammonia without being removed in the first evaporator 2 is liquid phase component due to the partial condensation in the second partial condenser 3. Can be separated and removed.
  • the principle of separation or removal of water or hydrocarbons having a large number of carbon atoms contained in the crude ammonia by the partial condensation in the second partial condenser 3 is that the first partial condenser 5 described above is used for carbonization of 1 to 8 carbon atoms.
  • the principle is substantially the same as that in which hydrogen and low boiling point gas are separated and removed. The difference is that the impurities are concentrated on the gas phase side in the first divider 5 whereas the impurities are concentrated on the liquid phase side in the second divider 3.
  • the gaseous crude ammonia containing water is cooled by the second condenser 3 and part of it becomes liquid ammonia.
  • This liquid ammonia will contain a significant portion of the water initially present in the crude ammonia.
  • gaseous crude ammonia containing 3000 ppm of water is introduced into the second condenser 3 at 0 ° C. and 5% of the gas is condensed as liquid ammonia at a gas temperature of 0 ° C.
  • the moisture concentration in the condensed liquid ammonia Is 28 ppm, and 98.8% of the amount of water initially present in the crude ammonia will be contained in this liquid ammonia.
  • the moisture concentration in the gaseous ammonia remaining without being condensed is 38 ppm, which is reduced to about 1/80 compared with the moisture concentration initially present in the crude ammonia.
  • the partial moisture concentration in the gaseous ammonia that remains without being condensed is 13 ppm. Compared to, it is reduced to about 230 times, giving better results.
  • the partial reduction temperature is preferably ⁇ 75 to 50 ° C., more preferably ⁇ 75 to 30 ° C.
  • the partial compression temperature is lower than ⁇ 75 ° C.
  • a part of the mixture of ammonia and water obtained by condensation may be cooled to below the freezing point and solidify, and this solid is the wall of the second partial condenser 3.
  • the condensation rate of ammonia is reduced as a result of hindering heat removal from the pipe, or the piping is clogged with the generated solid, which is not preferable.
  • the ammonia condensation rate can be adjusted by lowering the pressure of gaseous ammonia and adjusting the temperature and heat transfer area of the wall of the second partial contractor 3. it can.
  • the partial reduction temperature is higher than 50 ° C.
  • the pressure of ammonia becomes high, and the equipment that can withstand the high pressure is expensive.
  • the amount of water removed in the condensed liquid ammonia tends to be smaller than when it is partially condensed at a low temperature, leading to a decrease in the yield and purity of purified ammonia.
  • the water concentration in the crude ammonia is very high, it is effective to repeat the partial reduction in the second partial condenser 3 a plurality of times.
  • This can be realized by connecting a plurality of second dividers 3 in series.
  • the partial temperature of the second partial condenser 3 in the first stage is solidified by a mixture of ammonia and water obtained as a liquid phase component by condensation.
  • the second partial reduction after the second stage where the gaseous ammonia, which is the gas phase component of the first stage second partial condenser 3 and has a reduced water concentration, is introduced.
  • the partial contraction temperature of the vessel 3 is lowered.
  • gaseous crude ammonia containing 3000 ppm of moisture is subjected to a partial reduction operation at a partial reduction temperature of ⁇ 10 ° C. and a condensation rate of 5% in the first stage second partial condenser 3
  • a gas obtained as a gas phase component The moisture concentration in ammonia is as low as 13 ppm or less.
  • this gas phase component is subjected to a partial reduction operation at a partial reduction temperature of -70 ° C. and a condensation rate of 5% in the second stage first partial condenser 5
  • the water concentration in the gaseous ammonia obtained as the vapor phase component is 1 ppm. The following is a low value.
  • the partial reduction temperature in the second partial condenser 3 As the partial reduction temperature in the second partial condenser 3 is lowered, more liquid is contained in the liquid phase component, so that the removal rate for separating and removing the water as the liquid phase component can be improved.
  • the melting point of ammonia having no impurities and a purity of 100% is ⁇ 78 ° C.
  • the melting point of 30% aqueous ammonia comprising 30% by weight of ammonia and 70% by weight of water is ⁇ 72 ° C. Therefore, even when the liquid ammonia condensed as a liquid phase component contains moisture at a high concentration due to the partial condensation in the second partial condenser 3, the temperature of the wall of the second partial condenser 3 is -70.
  • the liquid ammonia obtained as a liquid phase component by condensation will not solidify by solidification.
  • the moisture in the gaseous crude ammonia can be obtained by reducing the pressure of the gaseous crude ammonia in the adiabatic state to lower its temperature and condensing part of the gaseous crude ammonia. .
  • the second divider 3 and the first divider 5 are configured in the same manner except that the division conditions such as the partial temperature, pressure, and partial ratio are different.
  • the configurations of the second partial condenser 3 and the first partial condenser 5 for partial reduction of gaseous crude ammonia are roughly classified into a piston flow system and a complete mixing system.
  • gaseous crude ammonia is gradually liquefied by flowing through the second partial pressure reducing device 3 or the first partial pressure reducing device 5 while flowing in a fixed direction, and flows without being condensed.
  • Impurity concentration in gaseous ammonia gradually increases if the type of impurities is low boiling point gas or highly volatile hydrocarbons (hydrocarbons having 1 to 8 carbon atoms).
  • the piston flow method is included in liquid ammonia generated by partial contraction on the upstream side of the flow.
  • the impurity concentration in the liquid ammonia which is low in impurity concentration and shrunk toward the downstream side, gradually increases.
  • liquid ammonia containing impurities at the same concentration is obtained by the partial reduction operation regardless of the part of the partial condenser.
  • either the piston flow method or the complete mixing method may be adopted as the configuration of the second divider 3 and the first divider 5, but the piston flow method is more preferable.
  • FIG. 2 and 3 show the configurations of the second divider 3 and the first divider 5 that employ the piston flow method.
  • FIG. 2 is a diagram illustrating a configuration of the second divider 3.
  • FIG. 3 is a diagram illustrating a configuration of the first divider 5.
  • the second divider 3 and the first divider 5 are configured in the same manner except that the division conditions such as the partial temperature, pressure, and partial ratio are different.
  • the second divider 3 and the first divider 5 that employ the piston flow method penetrate through the divider main bodies 31 and 51 through which gaseous ammonia flows and the divider main bodies 31 and 51 in the axial direction.
  • the pipes 32 and 52 through which the refrigerant is provided are configured. A refrigerant that cools gaseous ammonia that flows in the main body 31, 51 flows through the pipes 32, 52.
  • the pressure reducer main bodies 31 and 51 are provided with gas introduction openings 33 and 53 penetrating in the thickness direction, gas discharge openings 34 and 54, and liquid discharge openings 35 and 55, respectively.
  • gaseous ammonia is introduced into the divider main bodies 31 and 51 from the gas introduction openings 33 and 53.
  • Gaseous ammonia introduced from the gas introduction openings 33 and 53 into the pressure reducer main bodies 31 and 51 is condensed by being cooled by the refrigerant flowing through the pipes 32 and 52, and partly condensed. Uncondensed ammonia that is an uncondensed gas phase component is discharged from the gas discharge openings 34 and 54, and condensed ammonia that is a condensed liquid phase component is discharged from the liquid discharge openings 35 and 55.
  • the flow direction of gaseous ammonia flowing through the main body 31 and 51 and the flow direction of refrigerant flowing through the pipes 32 and 52 are particularly limited as long as an efficient partial reduction effect is obtained. They may be in the same direction or in the opposite direction. Furthermore, the pipe lines 32 and 52 may be provided in the partial pressure body main bodies 31 and 51, or may be provided so as to cover the outer peripheral surfaces of the partial pressure body main bodies 31 and 51.
  • gas introduction openings 33 and 53 through which gaseous ammonia is introduced into the partial condenser bodies 31 and 51, and liquid discharge openings 35 and 55 through which condensed ammonia is exhausted from the partial condenser bodies 31 and 51 This position may be a position separated in the gaseous ammonia flow direction in the condenser main bodies 31 and 51, and the liquid discharge openings 35 and 55 are located immediately below the gas introduction openings 33 and 53. It may be.
  • the concentration of impurities contained in the condensed ammonia condensed by the division is the gas in the vicinity thereof.
  • the impurity concentration in the uncondensed ammonia is in a constant distribution ratio.
  • the hydrocarbons contained in the condensed ammonia condensed by partial reduction are much lower than the expected concentration. It is. Further, as described above, the condensed ammonia condensed by the partial condensation is quickly removed from the second partial condenser 3 and the first partial condenser 5.
  • the second and third dividers 3 and 5 are inclined so that the condensed ammonia easily flows toward the liquid discharge openings 35 and 55, or the second and third dividers 3 and 1 are separated.
  • the second divider 3 and the first divider 5 are set up in parallel to the vertical direction, the gas introduction openings 33 and 53 are arranged on the upper side in the vertical direction, and the liquid discharge opening 35. , 55 are arranged on the lower side in the vertical direction.
  • the flow of gaseous ammonia in the divider main bodies 31 and 51 becomes a laminar flow, and condensation occurs from a portion near the vessel wall.
  • the impurity concentration in the liquid condensed ammonia thus obtained is expected to be a high value.
  • a baffle plate or a bead-like obstacle that disturbs the flow of gaseous ammonia may be arranged in the main body 31 or 51 of the divider. As a result, the flow of gaseous ammonia in the divider main bodies 31 and 51 is disturbed, so that the impurity concentration in the central portion of the flow of gaseous ammonia and the vicinity of the vessel wall are the same.
  • the concentration of impurities composed of hydrocarbons having 1 to 8 carbon atoms in the condensed ammonia is in the vicinity of the gas introduction openings 33 and 53. It becomes low and becomes high as it goes to the liquid discharge openings 35 and 55.
  • the gaseous ammonia introduced into the partial condenser bodies 31 and 51 of the second partial condenser 3 and the first partial condenser 5 decreases in amount as the condensation by the partial condensation proceeds.
  • the cross-sectional area of the cross section perpendicular to the axial direction of the contractor bodies 31 and 51 is made smaller as the gaseous ammonia condenses.
  • Examples of the piston flow type dividers constituting the second divider 3 and the first divider 5 include, for example, a spiral heat exchanger, a plate heat exchanger, a double tube heat exchanger, and a multi-tube.
  • a cylindrical heat exchanger (shell and tube heat exchanger), a multi-tube heat exchanger, a swirl tube heat exchanger, a swirl plate heat exchanger, and the like can be given.
  • a double tube heat exchanger, a multi-tube cylindrical heat exchanger (shell and tube heat exchanger), a multi-tube heat exchanger, and the like are particularly preferable.
  • suitable results can be obtained both in the case of flowing gaseous ammonia on the tube side and in the case of flowing gaseous ammonia in the barrel. .
  • the ammonia purification system 100 includes the raw material storage tank 1, the first evaporator 2, the second partial condenser 3, the first partial condenser 5, the second recovery tank 4, and the first recovery tank.
  • the tank 6 is configured to include a second evaporator 7, a first adsorption tower 8 and a second adsorption tower 9, a full condenser 10, and a product tank 30.
  • the raw material storage tank 1 stores crude ammonia.
  • the raw material storage tank 1 is not particularly limited as long as it is a heat insulating container having pressure resistance and corrosion resistance.
  • the raw material storage tank 1 stores crude ammonia as liquid ammonia and is controlled so that the temperature and pressure are constant.
  • crude ammonia is extracted from the raw material storage tank 1 as a gas, or crude ammonia extracted as a liquid is vaporized and supplied to the second partial condenser 3.
  • the raw material storage tank 1 must be pressurized to extract crude ammonia, and as a general method, a heat source such as a heat transfer pipe is disposed in the raw material storage tank 1, or There is a method in which liquid crude ammonia led to an external reboiler is heated and the raw material storage tank 1 is pressurized with the pressure of the generated gaseous crude ammonia.
  • crude ammonia is extracted from the raw material storage tank 1 as a liquid, and the liquid crude ammonia is vaporized by passing it through the first evaporator 2 to form gaseous crude ammonia. Ammonia is sent to the second divider 3 and the first divider 5.
  • a first pipe 11 is connected between the raw material storage tank 1 and the first evaporator 2, and the liquid crude ammonia led out from the raw material storage tank 1 passes through the first pipe 11 to the first. It is supplied to the evaporator 2.
  • the first pipe 11 is provided with a first valve 11 a that opens or closes the flow path in the first pipe 11.
  • a first valve 11 a that opens or closes the flow path in the first pipe 11.
  • the liquid crude ammonia supplied from the raw material storage tank 1 to the first evaporator 2 is vaporized by the first evaporator 2.
  • the gaseous crude ammonia vaporized in the first evaporator 2 is supplied to the second partial condenser 3.
  • a second pipe 12 is connected between the first evaporator 2 and the second partial condenser 3, and gaseous crude ammonia derived from the first evaporator 2 passes through the second pipe 12.
  • the second pipe 12 is provided with a second valve 12a that opens or closes the flow path in the second pipe 12.
  • the second valve 12 a When supplying gaseous crude ammonia derived from the first evaporator 2 to the second partial condenser 3, the second valve 12 a is opened, and the first evaporator 2 toward the second partial condenser 3 is opened. Gaseous crude ammonia flows in the second pipe 12.
  • the second partial condenser 3 fractionates the gaseous crude ammonia vaporized by the first evaporator 2 and separates it into a gas phase component and a liquid phase component, so that the volatility contained in the crude ammonia is obtained. Impurities (water and hydrocarbons having 9 or more carbon atoms) are separated and removed as liquid phase components.
  • the liquid phase component separated by the second divider 3, that is, the liquid phase component in which impurities having low volatility are concentrated, is connected to the second divider 3 and is provided with a fourth valve 14 a. It is stored in the second recovery tank 4 through the four pipes 14. The liquid phase component stored in the second recovery tank 4 can be returned to the raw material storage tank 1 and used again as raw material ammonia.
  • gas phase component separated by the second divider 3 that is, gaseous ammonia in which the content of impurities having low volatility is reduced, is supplied to the first divider 5.
  • a third pipe 13 is connected between the second divider 3 and the first divider 5, and gaseous ammonia derived from the second divider 3 passes through the third pipe 13. And is supplied to the first divider 5.
  • the third pipe 13 is provided with a third valve 13a that opens or closes the flow path in the third pipe 13.
  • the third valve 13 a When supplying gaseous ammonia derived from the second divider 3 to the first divider 5, the third valve 13 a is opened, and the second divider 3 is directed to the first divider 5. Then, gaseous ammonia flows in the third pipe 13.
  • the first frequency divider 5 is configured to reduce the gaseous ammonia from which the low-volatile impurities have been separated and removed by the second voltage divider 3 and separate the gaseous ammonia into a gas phase component and a liquid phase component. Highly volatile impurities (low boiling point gas and hydrocarbons having 1 to 8 carbon atoms) contained in are separated and removed as gas phase components.
  • the vapor phase component separated by the first divider 5, that is, the vapor phase component in which highly volatile impurities are concentrated, is connected to the first divider 5 and is provided with a sixth valve 16 a. It is discharged outside the system through 6 pipes 16.
  • the liquid phase component separated by the first divider 5, that is, condensed ammonia (liquid ammonia) with a reduced content of highly volatile impurities is connected to the first divider 5. It is stored in the first recovery tank 6 through the fifth pipe 15 provided with the 5 valve 15a. The liquid ammonia separated by the first divider 5 flows through the fifth pipe 15 from the first divider 5 toward the first recovery tank 6 by opening the fifth valve 15a.
  • the first partial condenser 5 when the first partial condenser 5 is set to the piston flow method, when the introduction of new gaseous ammonia from the gas introduction opening 53 starts, the internal state of the partial condenser main body 51 becomes steady. It takes less time to become. Further, the vapor phase component separated by the first divider 5 is discharged through the sixth pipe 16 from the gas discharge opening 54 when the sixth valve 16a is opened.
  • the discharge ratio can be determined by the discharge amount at the gas discharge opening 54, and even when the discharge ratio is changed, the time until the first divider 5 is in a steady state can be shortened.
  • the first divider 5 may have a configuration in which a plurality of dividers 5a, 5b, 5c as shown in FIG. 4 are connected in series.
  • FIG. 4 is a diagram illustrating a configuration of the first divider 5 in which a plurality of dividers are connected in series. In this way, by configuring the first divider 5 to have a plurality of partial reduction sections 5a, 5b, 5c connected in series, a plurality of ammonias having different degrees of purity in the respective partial reduction sections 5a, 5b, 5c. Can be made separately.
  • the partial reduction part 5a, 5b, 5c arrange
  • the concentration temperature of the impurity hydrocarbons contained in the liquid ammonia obtained as the liquid phase component can be reduced by lowering the partial condensation temperature.
  • FIG. 5 is a view showing a position where the vaporized material vaporized from the first recovery tank 6 is introduced into the first partial condenser 5. What is necessary is just to set suitably the position which introduces the vaporization material vaporized from the 1st collection tank 6 to the 1st partial condenser 5 according to the purity of the target liquid ammonia.
  • the multiple partial reduction portions 5a, 5b, 5c shown in FIG. The present invention can also be applied to the connected first dividers 5.
  • FIG. 6 is a view showing a connection structure between the first recovery tank 6 and the first divider 5.
  • the pressure equalizing pipe 6a equalizes the pressure of the first divider 5 and the pressure of the first recovery tank 6. In this way, by providing the pressure equalizing pipe 6 a between the first divider 5 and the first recovery tank 6, while the vaporized material evaporated from the first recovery tank 6 is controlled by the first divider 5. Can be introduced. In addition, the pressure of liquid ammonia at low temperatures varies greatly only with a temperature difference of several degrees.
  • the pressure in the first recovery tank 6 is changed to the pressure in the divider main body 51 of the first divider 5. Even if it becomes lower than that, the flow of the gas phase component (concentrated with high volatility impurities) from the first partial condenser 5 to the first recovery tank 6 can be prevented.
  • the gas phase component separated by the partial reduction in the second partial reducer 3 is supplied to the first partial reducer 5, and the first partial reducer 5 further performs the partial reduction.
  • the continuous partial reduction operation in the 1st partial reducer 5 was demonstrated.
  • the ammonia purification system 100 of the present embodiment is not limited to such a continuous partial reduction operation, and the partial reduction operation in the second partial reducer 3 and the first partial reducer 5 is performed as a batch. You may make it implement by a system. In the batch system, the vapor phase component separated by the partial reduction in the second partial condenser 3 is temporarily stored in a recovery container, and then the vapor phase component is supplied from the recovery container to the first partial condenser 5. It is a structured method.
  • the second divider 3 and the first divider 5 are connected in series in this order, and the low-volatile impurities due to the division in the second divider 3 are separated and removed as liquid phase components.
  • the configuration in which the highly volatile impurities are separated and removed as gas phase components by the partial condensation in the first partial condenser 5 has been described.
  • the first divider 5 and the second divider 3 are connected in series in this order, and impurities that are highly volatile due to the division in the first divider 5 are removed.
  • it may be configured to separate and remove impurities having low volatility due to partial condensation in the second partial condenser 3 as liquid phase components.
  • the liquid ammonia stored in the first recovery tank 6 is led out toward the second evaporator 7.
  • a seventh pipe 17 is connected between the first recovery tank 6 and the second evaporator 7, and the liquid ammonia led out from the first recovery tank 6 passes through the seventh pipe 17 to perform the second evaporation. Is supplied to the vessel 7.
  • the seventh pipe 17 is provided with a seventh valve 17a that opens or closes the flow path in the seventh pipe 17.
  • the seventh valve 17 a When supplying liquid ammonia derived from the first recovery tank 6 to the second evaporator 7, the seventh valve 17 a is opened, and the inside of the seventh pipe 17 is directed from the first recovery tank 6 toward the second evaporator 7. The liquid ammonia flows.
  • the liquid ammonia supplied from the first recovery tank 6 to the second evaporator 7 is vaporized by the second evaporator 7.
  • Gaseous ammonia vaporized by the second evaporator 7 is supplied to the first adsorption tower 8.
  • An eighth pipe 18 is connected between the second evaporator 7 and the first adsorption tower 8, and gaseous ammonia derived from the second evaporator 7 passes through the eighth pipe 18 to the second. 1 is supplied to the adsorption tower 8.
  • the eighth pipe 18 is provided with an eighth valve 18a that opens or closes the flow path in the eighth pipe 18.
  • the eighth valve 18 a When supplying gaseous ammonia derived from the second evaporator 7 to the first adsorption tower 8, the eighth valve 18 a is opened, and the eighth pipe is directed from the second evaporator 7 to the first adsorption tower 8. Gaseous ammonia flows through 18. That is, the second divider 3, the first divider 5, and the first adsorption tower 8 are connected in series via the second evaporator 7.
  • the first adsorption tower 8 adsorbs and removes a very small amount of water contained in gaseous ammonia vaporized by the second evaporator 7 with an adsorbent.
  • the adsorbent filled in the first adsorption tower 8 include silica gel, alumina, zeolite 3A, zeolite 4A, zeolite 5A, and zeolite 13X.
  • a very small amount of carbon dioxide contained in gaseous ammonia can also be adsorbed and removed.
  • a ninth pipe 19 is connected between the first adsorption tower 8 and the second adsorption tower 9, and gaseous ammonia derived from the first adsorption tower 8 passes through the ninth pipe 19 to 2 is supplied to the adsorption tower 9.
  • the ninth pipe 19 is provided with a ninth valve 19a that opens or closes the flow path in the ninth pipe 19.
  • the ninth valve 19 a When supplying gaseous ammonia derived from the first adsorption tower 8 to the second adsorption tower 9, the ninth valve 19 a is opened, and the ninth pipe is directed from the first adsorption tower 8 to the second adsorption tower 9. Gaseous ammonia flows through 19.
  • the second adsorption tower 9 adsorbs and removes a very small amount of hydrocarbons contained in gaseous ammonia derived from the first adsorption tower 8 with an adsorbent.
  • Examples of the adsorbent filled in the second adsorption tower 9 include activated carbon.
  • the configuration of the ammonia purification system 100 is the first adsorption.
  • the used adsorbent in the first adsorption tower 8 and the second adsorption tower 9 can be reused by heat treatment.
  • the second partial condenser 3, the first partial condenser 5, the first adsorption tower 8, and the second adsorption tower 9 are connected in series in this order, and in the second partial condenser 3 and the first partial condenser 5
  • the structure in which impurities are removed by adsorption in the first adsorption tower 8 and the second adsorption tower 9 after separating and removing impurities by partial condensation has been described.
  • the first adsorption tower 8, the second adsorption tower 9, the second partial condenser 3, and the first partial condenser 5 are connected in series in this order, and the first adsorption tower 8.
  • the impurities may be separated and removed by the partial condensation in the second divider 3 and the first divider 5.
  • the gaseous ammonia after the hydrocarbons are adsorbed and removed in the second adsorption tower 9 is led out toward the total condenser 10.
  • a tenth pipe 20 is connected between the second adsorption tower 9 and the full contractor 10, and gaseous ammonia derived from the second adsorption tower 9 passes through the tenth pipe 20 and is fully reduced. Supplied to the vessel 10.
  • the tenth pipe 20 is provided with a tenth valve 20a that opens or closes the flow path in the tenth pipe 20.
  • a tenth valve 20a that opens or closes the flow path in the tenth pipe 20.
  • the tenth valve 20 a is opened, and the inside of the tenth pipe 20 is directed from the second adsorption tower 9 to the full condenser 10. Gaseous ammonia flows.
  • the total condenser 10 liquefies gaseous ammonia derived from the second adsorption tower 9. Ammonia liquefied by the total condenser 10 is led out toward the product tank 30.
  • An eleventh pipe 21 is connected between the full contractor 10 and the product tank 30, and the liquid ammonia derived from the full contractor 10 is supplied to the product tank 30 through the eleventh pipe 21. Is done.
  • the eleventh pipe 21 is provided with an eleventh valve 21a that opens or closes the flow path in the eleventh pipe 21.
  • the eleventh valve 21 a is opened, and the inside of the eleventh pipe 21 is liquefied from the total contractor 10 toward the product tank 30. Ammonia flows. In this way, the highly purified ammonia is stored in the product tank 30.
  • FIG. 7 is a diagram showing a configuration of an ammonia purification system 200 according to the second embodiment of the present invention.
  • the ammonia purification system 200 of the present embodiment is similar to the ammonia purification system 100 described above, and corresponding portions are denoted by the same reference numerals and description thereof is omitted.
  • the ammonia purification system 200 includes a second partial condenser 3, a first partial condenser 5, a first adsorption tower 8, a second adsorption tower 9, and a third partial condenser 201 which is a third partial condenser in this order. Are connected in series.
  • ammonia from which impurities have been removed by the second partial condenser 3, the first partial condenser 5, the first adsorption tower 8, and the second adsorption tower 9 has the twelfth valve 202a opened. Then, the second adsorption tower 9 passes through the twelfth pipe 202 and is supplied to the third divider 201.
  • the third partial pressure device 201 performs partial condensation of the gaseous ammonia derived from the second adsorption tower 9 and separates it into a gas phase component and a liquid phase component, so that a very small amount of volatilization contained in the ammonia is obtained.
  • High-impurity impurities low boiling point gas and hydrocarbons having 1 to 8 carbon atoms
  • the vapor phase component separated by the third divider 201 that is, the vapor phase component in which highly volatile impurities are concentrated, is connected to the third divider 201 and is provided with a thirteenth valve 203a. It is discharged outside the system through 13 pipes 203.
  • liquid phase component separated by the third divider 201 that is, condensed ammonia (liquid ammonia) in which the content of highly volatile impurities is reduced, is connected to the third divider 201.
  • the product is stored in the product tank 30 through a fourteenth pipe 204 provided with a 14 valve 204a.
  • impurities that could not be removed by the second partial condenser 3, the first partial condenser 5, the first adsorption tower 8, and the second adsorption tower 9 are used as gas phase components. Since it can be separated and removed, higher purity ammonia can be obtained.
  • FIG. 8 is a diagram showing a configuration of an ammonia purification system 300 according to the third embodiment of the present invention.
  • the ammonia purification system 300 of the present embodiment is similar to the ammonia purification system 100 described above, and corresponding portions are denoted by the same reference numerals and description thereof is omitted.
  • the ammonia purification system 300 is configured by connecting the second partial condenser 3, the first adsorption tower 8, the second adsorption tower 9, and the first partial condenser 5 in this order in series.
  • gaseous ammonia from which impurities have been removed by the second divider 3 is supplied to the first adsorption tower 8 through the fifteenth pipe 301 by opening the fifteenth valve 301a, After that, it is supplied to the second adsorption tower 9 through the ninth pipe 19 and the adsorbent removes impurities by adsorption.
  • the gaseous ammonia led out from the second adsorption tower 9 is supplied to the first partial condenser 5 through the sixteenth pipe 302 by opening the sixteenth valve 302a.
  • the first divider 5 fractionates the gaseous ammonia derived from the second adsorption tower 9 and separates it into a gas phase component and a liquid phase component, so that a very small amount contained in the ammonia can be obtained.
  • Highly volatile impurities low boiling point gases and hydrocarbons having 1 to 8 carbon atoms
  • the vapor phase component separated by the first divider 5, that is, the vapor phase component in which highly volatile impurities are concentrated is connected to the first divider 5 and is provided with an 18th valve 304 a. It is discharged outside the system through 18 pipes 304.
  • the liquid phase component separated by the first divider 5, that is, condensed ammonia (liquid ammonia) with a reduced content of highly volatile impurities is connected to the first divider 5.
  • the product is stored in the product tank 30 through a seventeenth pipe 303 provided with a 17 valve 303a.
  • the liquid ammonia separated by the first divider 5 flows through the seventeenth pipe 303 from the first divider 5 toward the product tank 30 by opening the seventeenth valve 303a.
  • FIG. 9 is a diagram showing a configuration of an ammonia purification system 400 according to the fourth embodiment of the present invention.
  • the ammonia purification system 400 of this embodiment is similar to the ammonia purification system 100 described above, and corresponding portions are denoted by the same reference numerals and description thereof is omitted.
  • the ammonia purification system 400 includes a first adsorption tower 8, a second adsorption tower 9, and a first divider 5 connected in series in this order.
  • the ammonia purification system 400 is configured to be able to extract crude ammonia from the raw material storage tank 1 in both a gas and a liquid state.
  • a 19th pipe 401 provided with a 19th valve 401a and a 20th valve 401b is connected between the raw material storage tank 1 and the first adsorption tower 8, and the gaseous state led out from the raw material storage tank 1 is connected.
  • the crude ammonia is supplied to the first adsorption tower 8 through the 19th pipe 401 with the 19th valve 401a and the 20th valve 401b being opened.
  • a first pipe 11 provided with a first valve 11 a is connected between the raw material storage tank 1 and the first evaporator 2, and liquid crude ammonia led out from the raw material storage tank 1 is In the state where the first valve 11 a is opened, the first valve 11 is supplied to the first evaporator 2.
  • the liquid crude ammonia supplied to the first evaporator 2 is vaporized by the first evaporator 2.
  • a twentieth pipe 402 provided with a twenty-first valve 402a, which is a flow path through which gaseous crude ammonia vaporized in the first evaporator 2 flows toward the nineteenth pipe 401. Has been.
  • the 20th pipe 402 is connected between the 19th valve 401a and the 20th valve 401b in the 19th pipe 401.
  • the gaseous crude ammonia derived from the first evaporator 2 passes through the 20th pipe 402 and the 19th pipe 401 with the 19th valve 401a closed and the 20th valve 401b and 21st valve 402a opened. It is supplied to the first adsorption tower 8 through.
  • the gaseous ammonia supplied to the first adsorption tower 8 is then supplied to the second adsorption tower 9 through the ninth pipe 19, and the first adsorption tower 8 and the second adsorption tower are supplied. 9, the adsorbent removes impurities by the adsorbent.
  • the gaseous ammonia led out from the second adsorption tower 9 is supplied to the first divider 5 through the 21st pipe 403 by opening the 22nd valve 403a.
  • the first divider 5 fractionates the gaseous ammonia derived from the second adsorption tower 9 and separates it into a gas phase component and a liquid phase component, so that a very small amount contained in the ammonia can be obtained.
  • Highly volatile impurities low boiling point gases and hydrocarbons having 1 to 8 carbon atoms
  • the vapor phase component separated by the first divider 5, that is, the vapor phase component in which highly volatile impurities are concentrated is connected to the first divider 5 and is provided with a sixth valve 16 a. It is discharged outside the system through 6 pipes 16.
  • the liquid phase component separated by the first divider 5, that is, condensed ammonia (liquid ammonia) with a reduced content of highly volatile impurities is connected to the first divider 5.
  • the product is stored in the product tank 30 through a 22nd pipe 404 provided with a 23 valve 404a.
  • the liquid ammonia separated by the first divider 5 flows in the 22nd pipe 404 from the first divider 5 toward the product tank 30 by opening the 23rd valve 404a. In this way, the highly purified ammonia is stored in the product tank 30.
  • FIG. 10 is a diagram showing a configuration of an ammonia purification system 500 according to the fifth embodiment of the present invention.
  • the ammonia purification system 500 of the present embodiment is similar to the ammonia purification system 100 described above, and corresponding portions are denoted by the same reference numerals and description thereof is omitted.
  • the first adsorption tower 8, the second adsorption tower 9, the second partial condenser 3, and the first partial condenser 5 are connected in series in this order.
  • the liquid crude ammonia led out from the raw material storage tank 1 is supplied to the first evaporator 2 through the first pipe 11 with the first valve 11a being opened.
  • the liquid crude ammonia supplied to the first evaporator 2 is vaporized by the first evaporator 2.
  • the first evaporator 2 has a 23rd pipe 501 provided with a 24th valve 501a that serves as a flow path for the gaseous crude ammonia vaporized in the first evaporator 2 to flow toward the first adsorption tower 8. It is connected.
  • the gaseous crude ammonia derived from the first evaporator 2 is supplied to the first adsorption tower 8 through the 23rd pipe 501 with the 24th valve 501a being opened.
  • the gaseous ammonia supplied to the first adsorption tower 8 is then supplied to the second adsorption tower 9 through the ninth pipe 19, and the first adsorption tower 8 and the second adsorption tower are supplied. 9, the adsorbent removes impurities by the adsorbent. Then, gaseous ammonia led out from the second adsorption tower 9 is supplied to the second divider 3 through the 24th pipe 502 by opening the 25th valve 502a.
  • the second partial condenser 3 degenerates gaseous ammonia from which impurities have been adsorbed and removed by the first adsorption tower 8 and the second adsorption tower 9 and separates it into a gas phase component and a liquid phase component.
  • Low volatility impurities water and hydrocarbons having 9 or more carbon atoms contained therein are separated and removed as liquid phase components.
  • the liquid phase component separated by the second divider 3, that is, the liquid phase component in which impurities having low volatility are concentrated, is connected to the second divider 3 and is provided with a fourth valve 14 a. It is stored in the second recovery tank 4 through the four pipes 14.
  • the liquid phase component stored in the second recovery tank 4 can be returned to the raw material storage tank 1 and used again as raw material ammonia.
  • gaseous component separated by the second divider 3 that is, gaseous ammonia having a reduced content of low-volatility impurities, is removed from the third pipe with the third valve 13 a opened. 13 is supplied to the first divider 5.
  • the first divider 5 is configured to partially separate gaseous ammonia from which low-volatile impurities are separated and removed by the second divider 3 and separate the gaseous ammonia into a vapor phase component and a liquid phase component.
  • a very small amount of highly volatile impurities (low boiling point gas and hydrocarbon having 1 to 8 carbon atoms) contained therein are separated and removed as gas phase components.
  • the vapor phase component separated by the first divider 5, that is, the vapor phase component in which highly volatile impurities are concentrated, is connected to the first divider 5 and is provided with a sixth valve 16 a. It is discharged outside the system through 6 pipes 16.
  • the liquid phase component separated by the first divider 5, that is, condensed ammonia (liquid ammonia) with a reduced content of highly volatile impurities is connected to the first divider 5.
  • the product is stored in the product tank 30 through a 25th pipe 503 provided with a 26 valve 503a.
  • the liquid ammonia separated by the first divider 5 flows in the 25th pipe 503 from the first divider 5 toward the product tank 30 by opening the 26th valve 503a. In this way, the highly purified ammonia is stored in the product tank 30.
  • FIG. 11 is a diagram showing a configuration of an ammonia purification system 600 according to the sixth embodiment of the present invention.
  • the ammonia purification system 600 of the present embodiment is similar to the ammonia purification system 100 described above, and corresponding portions are denoted by the same reference numerals and description thereof is omitted.
  • the ammonia purification system 600 is configured by connecting the first divider 5 and the first adsorption tower 8 in series in this order. In addition, the ammonia purification system 600 is configured to be able to extract crude ammonia from the raw material storage tank 1 in both gas and liquid states.
  • a 26th pipe 601 provided with a 27th valve 601a and a 28th valve 601b is connected between the raw material storage tank 1 and the first divider 5, and the gaseous state led out from the raw material storage tank 1 is connected.
  • the crude ammonia is supplied to the first divider 5 through the 26th pipe 601 with the 27th valve 601a and the 28th valve 601b being opened.
  • a first pipe 11 provided with a first valve 11 a is connected between the raw material storage tank 1 and the first evaporator 2, and liquid crude ammonia led out from the raw material storage tank 1 is In the state where the first valve 11 a is opened, the first valve 11 is supplied to the first evaporator 2.
  • the liquid crude ammonia supplied to the first evaporator 2 is vaporized by the first evaporator 2.
  • a 27th pipe 602 provided with a 29th valve 602a which is a flow path through which gaseous crude ammonia vaporized in the first evaporator 2 flows toward the 26th pipe 601. Has been.
  • the 27th pipe 602 is connected between the 27th valve 601a and the 28th valve 601b in the 26th pipe 601.
  • the gaseous crude ammonia derived from the first evaporator 2 passes through the 27th pipe 602 and the 26th pipe 601 with the 27th valve 601a closed and the 28th valve 601b and the 29th valve 602a opened. And is supplied to the first divider 5.
  • the first fractionator 5 fractionates the supplied gaseous crude ammonia and separates it into a gas phase component and a liquid phase component, so that a highly volatile impurity (low boiling point) contained in the crude ammonia is obtained. Gas and hydrocarbons having 1 to 8 carbon atoms) are separated and removed as gas phase components.
  • the vapor phase component separated by the first divider 5, that is, the vapor phase component in which highly volatile impurities are concentrated, is connected to the first divider 5 and is provided with a sixth valve 16 a. It is discharged outside the system through 6 pipes 16.
  • the liquid phase component separated by the first divider 5, that is, condensed ammonia (liquid ammonia) with a reduced content of highly volatile impurities is connected to the first divider 5. It is stored in the first recovery tank 6 through the fifth pipe 15 provided with the 5 valve 15a. The liquid ammonia separated by the first divider 5 flows through the fifth pipe 15 from the first divider 5 toward the first recovery tank 6 by opening the fifth valve 15a.
  • the liquid ammonia stored in the first recovery tank 6 is supplied to the second evaporator 7 through the seventh pipe 17 with the seventh valve 17a being opened.
  • the liquid ammonia supplied from the first recovery tank 6 to the second evaporator 7 is vaporized by the second evaporator 7.
  • the gaseous ammonia vaporized by the second evaporator 7 is supplied to the first adsorption tower 8 through the eighth pipe 18 with the eighth valve 18a being opened.
  • the first adsorption tower 8 adsorbs and removes impurities contained in gaseous ammonia vaporized by the second evaporator 7, that is, impurities that could not be separated and removed by the first divider 5 with an adsorbent.
  • the first adsorption tower 8 has an adsorbent having a high adsorption capacity for moisture (for example, silica gel, alumina, zeolite 3A, zeolite 4A, zeolite 5A, zeolite 13X, etc.) and high adsorption to hydrocarbons.
  • An adsorbent having a function (for example, activated carbon or the like) is filled in a laminated state.
  • a 28th pipe 603 provided with a 30th valve 603a is connected between the first adsorption tower 8 and the total condenser 10, and gaseous ammonia led out from the first adsorption tower 8 It is supplied to the full contractor 10 through the 28 pipe 603.
  • the total condenser 10 liquefies gaseous ammonia derived from the first adsorption tower 8. Ammonia liquefied by the total condenser 10 is led out toward the product tank 30.
  • An eleventh pipe 21 provided with an eleventh valve 21a is connected between the full contractor 10 and the product tank 30, and the liquid ammonia led out from the full contractor 10 is connected to the eleventh pipe 21. And is supplied to the product tank 30. In this way, the highly purified ammonia is stored in the product tank 30.
  • ammonia purification system 100, 200, 300, 400, 500 has been described as a configuration including the first adsorption tower 8 that adsorbs and removes moisture and the second adsorption tower 9 that adsorbs and removes hydrocarbons.
  • the first adsorption tower 8 For the purpose of removing a very small amount of water remaining in ammonia, it is often necessary to provide the first adsorption tower 8 for adsorbing and removing moisture, but it is necessary to provide the second adsorption tower 9 for adsorbing and removing hydrocarbons. Often there is no. For example, when the initial concentration of hydrocarbons contained in the crude ammonia is low, the hydrocarbons can be sufficiently removed by the separation and removal by the second partial condenser 3 and the first partial condenser 5. In this case, it is not necessary to provide the second adsorption tower 9.
  • the concentration of hydrocarbon in ammonia can be lowered by performing partial contraction a plurality of times. There is no need to provide the adsorption tower 9. However, if the partial reduction operation is performed once and hydrocarbons still remain as impurities in the liquid ammonia obtained after partial reduction, the ammonia is recovered by adsorbing and removing hydrocarbons in the second adsorption tower 9. High purity ammonia can be obtained without reducing the rate.
  • the order is not subject to any restrictions.
  • ammonia purification systems 100, 200, and 600 after liquid ammonia led out from the first recovery tank 6 is vaporized by the second evaporator 7, gaseous ammonia is introduced into the first adsorption tower 8. I did it. However, in the ammonia purification system 100, 200, 600 of the present embodiment, the liquid ammonia stored in the first recovery tank 6 is introduced into the first adsorption tower 8 in a liquid ammonia state without vaporizing. Good.
  • Example 1 ⁇ Raw crude ammonia> Hydrogen, nitrogen, oxygen, argon, carbon monoxide and carbon dioxide as low boiling point gases, methane, ethane, propane, n-butane, n-pentane, n-hexane, n-heptane, n as highly volatile hydrocarbons
  • n-decane as octane, a low-volatility hydrocarbon, and ammonia containing water in the concentrations shown in Table 3 as raw crude ammonia.
  • n-hexane, n-heptane, n-octane and n-decane were added to the raw materials to adjust the concentration.
  • the ammonia purification system 100 shown in FIG. 1 was used.
  • the second divider 3 is a shell-and-tube condenser in which the divider main body 31 has a diameter of 100 mm and a length of 500 mm, and 14 pipes 32 having a diameter of 10 mm through which the refrigerant passes are arranged.
  • the second voltage divider 3 was tilted by 5 degrees from the horizontal so that the liquid discharge opening 35 was disposed on the lower side in the vertical direction than the gas introduction opening 33.
  • the first divider 5 is a shell-and-tube condenser in which the divider main body 51 has a diameter of 100 mm and a length of 500 mm, and 14 pipes 52 having a diameter of 10 mm through which the refrigerant passes are arranged. . Further, the first voltage divider 5 was tilted by 5 degrees from the horizontal so that the liquid discharge opening 55 was disposed on the lower side in the vertical direction than the gas introduction opening 53.
  • the first adsorption tower 8 is a tower having a diameter of 30 mm and a length of 1000 mm.
  • the upstream side is zeolite 13X (F-9, manufactured by Tosoh Corporation), and the downstream side is zeolite 3A (A-3, manufactured by Tosoh Corporation). What was filled so that it might become a volume was used.
  • the liquid crude ammonia stored in the raw material storage tank 1 was vaporized by introducing it into the first evaporator 2 heated to 150 ° C.
  • the gaseous crude ammonia vaporized in this manner was introduced into the second condenser 3 at a rate of 100 mL per minute in the standard state.
  • the absolute pressure in the second divider 3 was set to 0.30 MPa.
  • chiller water at ⁇ 15 ° C. was circulated through the pipe line 32 in the second partial condenser 3.
  • 5% of the ammonia was condensed, and the condensed ammonia thus condensed was quickly discharged from the liquid discharge opening 35.
  • the absolute pressure in the first divider 5 was 0.20 MPa. Further, chiller water at ⁇ 30 ° C. was circulated through the pipe line 52 in the first condenser 5. In the first divider 5 configured as described above, 95% of ammonia was condensed, and the condensed ammonia thus condensed was quickly led out from the liquid discharge opening 35.
  • the condensed ammonia obtained as a liquid phase component by the partial condensation in the first partial condenser 5 was vaporized by introducing it into the second evaporator 7 heated to 150 ° C.
  • the gaseous ammonia thus vaporized was guided to the first adsorption tower 8 and the second adsorption tower 9 at an absolute pressure of 0.6 MPa.
  • the aeration rate was 90 mL per minute under standard conditions.
  • the concentration of hydrogen, nitrogen, oxygen, argon, carbon monoxide, carbon dioxide, and hydrocarbons having 1 to 8 carbon atoms in the condensate derived from the first condenser 5 is higher than the raw crude ammonia. Has been reduced. From this, it is understood that the low-boiling gas and the hydrocarbon having 1 to 8 carbon atoms can be separated and removed as gas phase components by the partial reduction in the first partial condenser 5.
  • the impurity concentration at the outlets of the first adsorption tower 8 and the second adsorption tower 9 is sufficiently reduced as compared with the raw crude ammonia. From this, it can be seen that higher purity ammonia can be obtained by adopting a configuration including the first adsorption tower 8 and the second adsorption tower 9.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Separation By Low-Temperature Treatments (AREA)
  • Separation Of Gases By Adsorption (AREA)
  • Industrial Gases (AREA)

Abstract

Cette invention concerne un procédé de purification d'ammoniac et un système de purification d'ammoniac qui permettent de purifier l'ammoniac à un taux de récupération élevé par un procédé simple et un court temps de purification ne nécessitant qu'une faible consommation d'énergie. Un second condenseur partiel (3) d'un système de purification d'ammoniac (100) condense partiellement l'ammoniac brut gazéifié par un premier évaporateur (2) et sépare et élimine, sous forme de composant de phase liquide, les impuretés de basse volatilité contenues dans l'ammoniac brut. Un premier condenseur partiel (5) condense partiellement le composant en phase gazeuse séparé par le second condenseur partiel (3) et sépare et élimine, sous forme de composant de phase gazeuse, les impuretés de volatilité élevée.
PCT/JP2012/052779 2011-03-31 2012-02-07 Procédé de purification d'ammoniac et système de purification d'ammoniac WO2012132560A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5988285B1 (ja) * 2015-10-21 2016-09-07 株式会社島川製作所 アンモニアを含む排ガスの処理装置および処理方法
CN111960436A (zh) * 2020-09-03 2020-11-20 福建省宜品生物科技有限公司 一种超纯氨生产装置及生产方法

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* Cited by examiner, † Cited by third party
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WO2015134778A1 (fr) 2014-03-05 2015-09-11 Bechtel Hydrocarbon Technology Solutions, Inc. Systèmes et procédés d'épuration d'ammoniac

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD159259A3 (de) * 1979-10-16 1983-03-02 Wolfgang Renker Verfahren zur herstellung hochreinen ammoniaks
JPH0462710B2 (fr) * 1988-04-08 1992-10-07 Naoaki Ono
DE4239021A1 (de) * 1992-11-19 1994-05-26 Linde Kca Dresden Gmbh Verfahren zur Abtrennung gasförmiger Komponenten aus wasserstoffhaltigen Synthesepurgegasen
JPH07240407A (ja) * 1993-08-31 1995-09-12 L'air Liquide 部分凝縮による半導体プロセス用薬品の精製方法及び装置
JPH10120415A (ja) * 1996-10-21 1998-05-12 英正 ▲鶴▼田 液安を水溶液より回収する方法
US6065306A (en) * 1998-05-19 2000-05-23 The Boc Group, Inc. Method and apparatus for purifying ammonia
JP2004536011A (ja) * 2001-07-24 2004-12-02 ディーエスエム アイピー アセッツ ビー．ブイ． Ｎｈ３、ｈ２ｏ及びｃｏ２を含む気体混合物からアンモニウムカルバメート溶液を得る方法
JP2006516527A (ja) * 2003-01-30 2006-07-06 デーエスエム アイピー アセッツ ベー． ヴェー． Ｎｈ３、ｃｏ２およびｈ２ｏを含有する混合物からｎｈ３ならびに場合によりｃｏ２およびｈ２ｏを分離するための方法
JP2008505830A (ja) * 2004-07-07 2008-02-28 レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード アンモニアの精製および移送充填
JP4605705B2 (ja) * 2005-01-31 2011-01-05 日本エア・リキード株式会社 アンモニア精製システムおよび精製方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4062710B2 (ja) * 2003-12-03 2008-03-19 大陽日酸株式会社 アンモニアの精製方法及び精製装置

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD159259A3 (de) * 1979-10-16 1983-03-02 Wolfgang Renker Verfahren zur herstellung hochreinen ammoniaks
JPH0462710B2 (fr) * 1988-04-08 1992-10-07 Naoaki Ono
DE4239021A1 (de) * 1992-11-19 1994-05-26 Linde Kca Dresden Gmbh Verfahren zur Abtrennung gasförmiger Komponenten aus wasserstoffhaltigen Synthesepurgegasen
JPH07240407A (ja) * 1993-08-31 1995-09-12 L'air Liquide 部分凝縮による半導体プロセス用薬品の精製方法及び装置
JPH10120415A (ja) * 1996-10-21 1998-05-12 英正 ▲鶴▼田 液安を水溶液より回収する方法
US6065306A (en) * 1998-05-19 2000-05-23 The Boc Group, Inc. Method and apparatus for purifying ammonia
JP2004536011A (ja) * 2001-07-24 2004-12-02 ディーエスエム アイピー アセッツ ビー．ブイ． Ｎｈ３、ｈ２ｏ及びｃｏ２を含む気体混合物からアンモニウムカルバメート溶液を得る方法
JP2006516527A (ja) * 2003-01-30 2006-07-06 デーエスエム アイピー アセッツ ベー． ヴェー． Ｎｈ３、ｃｏ２およびｈ２ｏを含有する混合物からｎｈ３ならびに場合によりｃｏ２およびｈ２ｏを分離するための方法
JP2008505830A (ja) * 2004-07-07 2008-02-28 レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード アンモニアの精製および移送充填
JP4605705B2 (ja) * 2005-01-31 2011-01-05 日本エア・リキード株式会社 アンモニア精製システムおよび精製方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5988285B1 (ja) * 2015-10-21 2016-09-07 株式会社島川製作所 アンモニアを含む排ガスの処理装置および処理方法
CN111960436A (zh) * 2020-09-03 2020-11-20 福建省宜品生物科技有限公司 一种超纯氨生产装置及生产方法

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