JP2006206410A - Ammonia purification system and purification method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a highly efficient and highly reliable ammonia purification system and purification method which enables continuous supply of high-purity ammonia and reduces maintenance by using a simple function. <P>SOLUTION: The system for purifying crude ammonia into high-purity ammonia characteristically has a storing means 4 for storing crude liquid ammonia used as a raw material, two or more rectification means including a first rectification means 1 for removing mainly heavy impurities whose vapor pressure is lower than that of ammonia from the liquid ammonia and a second rectification means 2 for removing mainly light impurities whose vapor pressure is higher than that of ammonia from gaseous ammonia, and at least one adsorption means 3 for removing trace amounts of residues from the gaseous ammonia between the first rectification means 1 and the second rectification means 2. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

  The present invention relates to a system and a purification method for purifying crude ammonia, and more particularly, to an ammonia purification system and a purification method used in a high-purity ammonia purification process frequently used in a semiconductor manufacturing factory or a liquid crystal manufacturing factory. It is.

  Conventionally, high-purity ammonia has been used in semiconductor manufacturing factories, liquid crystal manufacturing factories, and the like as various processing agents such as the production of nitride films. Usually, such high-purity ammonia is supplied by a method in which crude ammonia is purified to remove impurities. Specifically, a method using a difference in boiling point between a substance to be purified and a substance to be removed, more specifically, a difference in vapor pressure under a predetermined pressure condition, and physical or A method using the difference in chemical adsorption capacity was used. Usually, the multi-stage treatment of the same method is common, but for the removal of a very small amount of impurities, several methods combining these are proposed, and some are put into practical use.

  For example, as a general high-purity chemical substance purification apparatus, as shown in FIG. 3, a storage tank 101 containing a liquid chemical substance and a liquid tank connected to receive the chemical substance from the storage tank 101, Therefore, in order to remove the column 109 in which the chemical substance is contaminated into the contaminated heavy liquid fraction and the purified light vapor fraction, and the purified light vapor fraction, the column 109 is removed. There has been proposed a system including a conduit 102 connected to (see, for example, Patent Document 1).

  Alternatively, as an apparatus for purifying crude ammonia into high-purity ammonia, for example, as shown in FIG. 4, crude ammonia gas is introduced into a dehydration tower (203) substantially at room temperature filled with a barium oxide-based moisture removing agent. Then, the water contained in the gas is removed by reaction, and the ammonia gas from which water has been removed by the process A is introduced into the central space reflux portion (242) of the distillation column (204) to introduce the upper condensing and cooling portion (241). While liquefying ammonia gas and separating low-boiling impurities, the liquefied product is allowed to flow down to the lower reservoir (243) to form substantially high-purity ammonia, and trace impurities contained in the stored liquid are further reduced. A method has been proposed in which the lower boiling heating unit (244) drives out by boiling (see, for example, Patent Document 2).

In addition, as shown in FIG. 5, the step of generating a first purified fluid by removing impurities from the liquid phase therein through the impure liquefied (ammonia) gas through the first absorption means (414), the first purified fluid Is passed through the evaporation means (422) to remove impurities therein to produce a second purified gas, and the second purified gas is passed through the second absorption means (426) to remove impurities from the vapor phase therein. There has been proposed a method having a constituent requirement that it includes a step of removing and producing a high purity gas (see, for example, Patent Document 3).
JP 2000-028264 A JP 2003-183021 A JP 2002-255542 A

  However, with the recent demand for higher density and higher accuracy of semiconductors, there is an increasing demand for higher purity or impurity treatment for ammonia. In the conventional method, it is difficult to sufficiently respond to such a request.

  Specifically, in the example shown in FIG. 4, the purpose is to further refine a relatively high-purity raw material to a higher purity, and when there are many impurities contained in the raw material, the final product is obtained only with the column. It is not possible to ensure sufficient purity. In addition, according to this method, since the light component is removed first and the heavy component is removed later, the product is limited to gas, so that it can be applied to the purification of ammonia where a liquefied product is required. There may be cases where a separate liquefaction device is installed.

  Further, in the example shown in FIG. 5, since ammonia is taken out from the crude ammonia liquid container (storage tank) by gas, moisture remains in the liquid phase, and the moisture in the gas phase is reduced. Since the water in the liquid container is concentrated while the remaining liquid is not left, the burden on the water removal tower increases. As a result, in the long term, there is a risk that the purity of the final product may be reduced due to the mixing of water into the distillation column. In addition, the moisture removal tower cannot be regenerated, and when a set amount of processing is performed, it is necessary to replace the removal agent, which complicates maintenance and costs.

  Furthermore, in the example shown in FIG. 6, since the purity of the final product depends on the characteristics of the vapor phase adsorption bed, a predetermined regeneration function is required, including a permanent moisture analyzer (FTIR), This will complicate maintenance and inspection and incur the cost of the equipment.

  The object of the present invention is to enable continuous supply of high-purity ammonia, and furthermore, continuous supply of high-purity ammonia frequently used in semiconductor manufacturing plants or liquid crystal manufacturing plants, etc., and reduce maintenance by using simple functions. A high-performance and highly reliable ammonia purification system and purification method are provided.

  As a result of intensive studies, the present inventors have found that the above object can be achieved by the ammonia purification system and purification method described below, and have completed the present invention.

  The present invention is a system for purifying high-purity ammonia from crude ammonia, (1) first rectification means for removing heavy impurities mainly having a vapor pressure lower than ammonia from crude ammonia as a raw material, A plurality of rectifying means that mainly remove light impurities having a vapor pressure higher than that of ammonia from ammonia; and (2) intermediate between the first rectifying means and the second rectifying means, And at least one fixed bed adsorbing means for removing trace residue from gaseous ammonia.

  Further, the present invention is a method for purifying crude ammonia containing heavy impurities having a vapor pressure lower than that of ammonia and light impurities having a vapor pressure higher than that of ammonia, and introducing crude ammonia as a raw material into the first rectification means. After removing most of the heavy impurities, the ammonia gas from which heavy impurities have been removed is introduced into the fixed bed adsorption means to remove trace residues, and then introduced into the second rectification means to remove the light impurities. By removing, high-purity ammonia is obtained.

  The removal of a trace amount of impurities in the purification system or the purification method according to the present invention is composed of a plurality of rectification means and one or more adsorption means, and sequentially from impurities having a low vapor pressure (hereinafter referred to as “heavy impurities”). It is a refinement to impurities with high vapor pressure (hereinafter referred to as “light impurities”), and it has excellent features that it can function independently and complement each other. .

Specifically, the purification of ammonia (NH ₃ ), which is very difficult to separate because there are many kinds of impurities and various impurities that are difficult to remove, is (1) removes heavy impurities. A combination of three (or more) means: (1) a first rectification separation, (2) an adsorption separation for removing heavy and light impurities, and (3) a second rectification separation for removing light impurities. Separation is effectively achieved by controlling conditions such as properties, temperature, and pressure of the sample introduced into the means.

  For example, by introducing crude ammonia in liquid form into the first purification means, it is possible to eliminate instability factors of the purification capacity of the system due to concentration of moisture in the storage means. That is, since the raw material is collected from the liquid phase of the storage means and most of the water is removed by the first rectifying means, the operation can be stably performed. In addition, a slight amount of water that could not be removed by the first rectifying means can be removed by the fixed bed adsorbing means (adsorber), and further, maintainability is improved by using a reusable adsorber. be able to.

  As described above, according to the present invention, it is possible to continuously supply high-purity ammonia, reduce maintenance by using a simple function, and provide a high-performance and high-reliability ammonia purification system and purification method. It becomes possible.

  The present invention is the above ammonia purification system, characterized in that crude liquid ammonia as a raw material is supplied from a storage tank or a bulk transport tank.

  As described above, for high-purity ammonia in recent years, there has been a growing demand for a system that can supply a large amount of ammonia with high purity as well as high purity due to the increasing trend of short-term mass production. Therefore, a conventional supply system using a plurality of cylinders cannot sufficiently cope with it, and a bulk transport tank having a capacity several times or several tens of these is preferable. In addition, the bulk transport tank is preferable from the viewpoint of installation location and necessity of replacement. Since this system has a configuration that can meet such demands, it is possible to continuously supply a large amount of high-purity ammonia, reduce maintenance, and provide a high-performance and highly reliable ammonia purification system. In addition, as described above, by introducing crude ammonia in liquid form into the first purification means, it is possible to eliminate instability factors of the purification capacity of the system due to concentration of water in the storage means. Since the raw material is collected from the liquid phase of the means and most of the water is removed by the first rectification means, stable operation is possible.

  The present invention is the above ammonia purification system, characterized in that crude ammonia as a raw material is supplied from an ammonia production plant.

  As described above, for high-purity ammonia in recent years, due to the increasing trend of short-term mass production, high purity and a system that can supply ammonia several tens of times the conventional supply amount or continuous in quantity. The demand for is getting stronger. Since this system can supply high-purity ammonia using relatively low-purity ammonia as a raw material, it has a configuration that can sufficiently meet these requirements. Specifically, it is supplied from an ammonia production plant. High-purity ammonia can be continuously supplied from a large amount of crude ammonia. It is possible to form a highly versatile system such as combining with existing facilities, reducing maintenance, and providing a high-performance and highly reliable ammonia purification system. Moreover, since crude ammonia can be continuously introduced into the first purification means, unstable factors such as concentration of water in the storage means can be eliminated, and stable operation is possible.

  The present invention is the above ammonia purification system, wherein the adsorption means is filled with synthetic zeolite 3A.

  In this system, the adsorption means removes residual heavy impurities from the first rectification means and plays a complementary role for the first rectification means, and also plays a complementary role for removal of light impurities in the second rectification means. Yes. Therefore, while the purity of the purified ammonia largely depends on the adsorption means, it is practically difficult to identify and remove the target impurities by various restrictions on the system configuration. As a result of analyzing the behavior of various impurities and their mixed components in the first rectification means and the second rectification means, the present inventor made a selection based on the size of ammonia molecules while utilizing physical adsorption. It has been found that the synthetic zeolite 3A is the optimum adsorbent in this system. As a result, it was possible to have a function of effectively supplementing the rectifying means constituting the system, and a large amount of high-purity ammonia could be continuously supplied.

  The present invention is the above ammonia purification method, characterized in that the crude ammonia is industrial ammonia having a purity of about 99.9 wt%.

  As described above, an object of the present invention is to stably supply a large amount of very high-purity ammonia, while as the required purity is increased, the purification technique is accompanied by a great difficulty. . Further, the higher the purity of ammonia as a raw material, the more easily it can be purified. On the other hand, the cost and the availability of the raw material vary greatly depending on the purity of the raw material. Therefore, if industrial ammonia having a purity that is generally widely used can be used, a large amount of a raw material having a stable composition can be used, and its practical value is very high.

  Here, the ammonia purification method according to the present invention combines three or more means of the first rectification separation, the adsorption separation, and the second rectification separation, and the properties, temperature, pressure, etc. of the sample introduced into each means. By controlling the conditions, the mutual functions are complemented and effective separation of impurities is achieved, so the allowable range of impurities is wider than other methods, and even industrial ammonia can be sufficiently purified. I found out. Therefore, it has become possible to continuously supply a large amount of high-purity ammonia using a relatively inexpensive and stably available raw material.

  The present invention is the above ammonia purification method, wherein the high purity ammonia has a purity of 99.999 wt% or more.

  As described above, in the present invention, the ammonia purification method combining three or more means of the first rectification separation, the adsorption separation, and the second rectification separation is used, and the functions of each means are complemented. As a result, a large amount of high-purity ammonia can be continuously supplied. Specifically, when industrial ammonia having a purity of about 99.9 wt% is used as a raw material, high purity ammonia having a purity of 99.999 wt% or more can be continuously and efficiently supplied as a product. It became.

  As described above, according to the present invention, it is possible to continuously supply high-purity ammonia, reduce maintenance by using a simple function, and provide a high-performance and high-reliability ammonia purification system and purification method. It becomes possible.

  In particular, since high-purity ammonia can be continuously supplied as a product, this system can be installed near the point of use and high-purity ammonia can be delivered by piping.

  In addition, since the industrial ammonia can be supplied using a general lorry or a bulk transport tank, a highly versatile usage method is possible.

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

<Example of basic form of high-purity ammonia purifier>
FIG. 1 shows a flow sheet of an example of a high-purity ammonia purifying apparatus based on the present invention.
1 represents a first rectification column as a first purification means, 2 represents a second rectification column as a second purification means, 3 represents a fixed bed adsorber as an adsorption means, and 4 represents a storage tank as a storage means, The case where the lorry 5 is used as a crude ammonia supply means is illustrated. In order to ensure stable operation of the system, measuring means such as thermometers T ₁ ... Tn, pressure gauges G _1. Pressure regulators D ₁ ... Dn are disposed as appropriate, and their outputs and functions are managed and controlled by control means (not shown). Furthermore, when a resorbable adsorbent is used as the adsorbing means 3, a regenerating purge fluid supply means R is provided to manage and control the operation periodically or according to the operating time of the system. At this time, it is preferable that the members constituting the sample channel such as the above-mentioned means and the accompanying pipes and valves form a heat insulating structure and are maintained at a predetermined temperature.

The flow from raw materials to products and waste liquid or waste gas generation is outlined.
(1) The liquid crude ammonia supplied from the lorry 5 is accumulated in the storage tank 4, and the accumulated crude ammonia is introduced from the bottom of the storage tank 4 into the central space M <b> 1 of the first fractionator 1. .
(2) In the first rectification column 1, the primary purified gaseous ammonia is supplied from the tower top, and the concentrated and liquefied impurities are supplied from the tower bottom as waste liquid. The primary purified ammonia is introduced into the bottom of the fixed bed adsorber 3.
(3) In the fixed bed adsorber 3, impurities are adsorbed by the adsorbent disposed therein, and secondarily purified gaseous ammonia is supplied from the upper part. The secondary purified ammonia is introduced into the central space M2 of the second rectification column 2.
(4) In the second rectifying column 2, the tertiary purified liquid ammonia is supplied from the tower bottom, and the concentrated impurities are supplied as waste gas from the tower top. The tertiary purified liquid high purity ammonia is delivered as a product.

<Functions and overview of each means that is the basis of this system>
(1) Storage means The storage tank 4 is not particularly limited as long as it is a pressure-resistant and corrosion-resistant heat retaining container having a capacity that can basically correspond to the supply amount. For example, it is possible to use various types of containers such as tanks made of stainless steel and having a heat insulating layer inside, and bulk transport tanks. However, continuous supply of raw materials is possible and replacement is easy without taking place. In view of this, a bulk transport tank is preferable. Specifically, a container having a capacity of about 5 to ³⁰ m ³ is preferable.
In the storage tank 4, the temperature and pressure of the liquid ammonia are controlled so as to be substantially constant, and the level of the liquid level is managed and controlled by the level gauge L so as to always ensure the supply of the necessary amount. Is preferred.

  Further, as shown in FIG. 1, it is preferable that a part of the internal liquid in the storage tank 4 is taken out and returned to the storage tank 1 via the pressure evaporator 6. By setting the temperature and pressure of the liquid ammonia in the storage tank 4 to substantially constant conditions, the liquid ammonia can be stably supplied.

(2) First rectification means The first rectification column 1 forms a bottom space U1, a lower rectification section A1, a central space section M1, an upper rectification section B1, and an upper space section T1 in this order from the bottom. The reboiler E1 is installed in the part U1, and the capacitor C1 is installed in the upper space part T1. The reboiler E1 is supplied with a heating medium such as heated water from the outside to support the reboiling of the sample, and the condenser C1 is supplied with a refrigerant such as cooling water from the outside to support the condensation of the sample.

  The crude ammonia liquid introduced into the central space part M1 of the first rectifying column 1 moves to the bottom space part U1 while making gas-liquid contact with the ammonia gas rising in the lower rectifying part A1. Then, the ammonia gas which has been reboiled and vaporized is purified via the lower rectifying part A1, the central space part M1 and the upper rectifying part B1 while making gas-liquid contact with the flowing solution.

  At this time, the ammonia gas containing light impurities and a small amount of heavy impurities reaches the upper space T1, is cooled by the capacitor C1, and is delivered from the top. On the other hand, heavy impurities are separated from the sample in the two rectifying sections, flow down to the bottom space U1 to become a concentrated liquid, and are discharged from the bottom of the tower as waste liquid periodically or continuously.

(3) Adsorbing means The adsorbing means (fixed bed adsorber) 3 is not particularly limited as long as it has a small amount of adsorption of ammonia and can uniformly adsorb purified substances such as impurities having a boiling point lower than that of ammonia, such as a very small amount of water. Is not to be done. In general, it is preferable to use physical adsorption capable of regeneration, and for example, an adsorbent such as alumina, silica gel, or synthetic zeolite is preferably used. In particular, synthetic zeolite has a uniform pore size, low ammonia adsorption, stable adsorption capacity for other components, reproducible, chemically and mechanically resistant, molded and available Therefore, application to this system is preferable. In addition, in this system, it was found that the ability to adsorb moisture, which makes it difficult to remove trace components by rectification means, and that synthetic zeolite 3A is optimal experimentally.

  Impurities can be evenly adsorbed by introducing the sample from the bottom using the fixed bed adsorber 3 in which such an adsorbent is disposed.

  In order to regenerate the adsorbent, it is preferable to purge using, for example, nitrogen. Specifically, as shown in FIG. 1, a high-pressure gas supply line as a nitrogen supply means R and a part of the line are used. A regeneration effect is enhanced by providing a means for heating the gas and heating the nitrogen gas for use in purging.

  Also, as illustrated in FIG. 3, two fixed bed adsorbers 3 are arranged in parallel, one (A side) is used for sample adsorption, the other (B side) is regenerated, and its operation It is preferable to manage and control the system periodically or according to the operating time of the system. A large amount of ammonia can be treated continuously by securing an adsorption means having a high adsorption capacity at all times. For example, in the case of the configuration shown in FIG. 2, by controlling the operation of the valves V1 to V8 as shown in Table 1, one of the two fixed bed adsorbers 3A and B is operated and the other is simultaneously operated. It can be purged. The fixed bed adsorber 3 is not necessarily two, and three or more means can be arranged in parallel and switched.

(4) Second rectification tower 2
The second rectifying column 2 has the same structure as the first rectifying column 1, and forms a bottom space U2, a lower rectifying portion A2, a central space M2, an upper rectifying portion B2, and an upper space T2. A reboiler E2 and a capacitor C2 are installed.

  The ammonia gas introduced into the central space part M2 of the second rectification tower 2 rises in the upper rectification part B2, and is rectified by gas-liquid contact with the reflux liquid flowing down. That is, ammonia contained in the rising gas phase is dissolved and liquefied in the reflux liquid, and nitrogen, oxygen and the like having a lower boiling point than ammonia dissolved in the reflux liquid are vaporized.

  At this time, the high-purity ammonia condensed and purified by removing light impurities flows down into the bottom space U2, and then periodically or continuously from the bottom of the tower except for a part returned to the upper part of the upper rectification part B. To be delivered as a final product. On the other hand, the light impurities are separated from the sample in the two rectification sections and rise to the upper space T2 to become concentrated gas, which is cooled by the condenser C1 and continuously discharged as waste gas.

<Purification process of high purity ammonia>
Hereinafter, based on the conditions illustrated in Table 2, for example, an example of a high-purity ammonia purification process using a system having the above-described means as constituent elements will be described. Hereinafter, the temperature is expressed as temperature (° C.) / Pressure (MPa) as the fluid condition.

(1) First, the raw crude ammonia is stored in the storage tank 4 as a normal temperature liquid from the lorry 5 using industrial ammonia which is usually easily available. It is preferable that the storage amount corresponds to the amount of high purity liquefied ammonia to be used. Long-term storage of unused raw materials is not preferable because concentration at the bottom of impurities such as moisture tends to occur. It contains about 99.9 wt% ammonia as a main component, and moisture (H ₂ O), hydrogen (H ₂ ), oxygen (O ₂ ), nitrogen (N ₂ ), argon (Ar), carbon dioxide (CO) as impurities ₂ ), carbon monoxide (CO), methane (CH ₄ ), ethane (C ₂ H ₆ ), oil and the like. The case where each component becomes a composition like Table 1 can be mentioned. Among these, moisture, oil, and the like are heavy impurities as described above, and hydrogen, oxygen, nitrogen, and the like correspond to light impurities.

  (2) In a state in which the process is operated, liquid crude ammonia is adjusted from the tank bottom of the storage tank 4 to a predetermined pressure condition using a liquid pressure evaporator, and the first rectification tank 1 is used as a purification raw material. (About 10 ° C./about 0.6 MPa). The amount to be introduced depends on the amount of high purity liquefied ammonia to be used, but usually about 10 to 200 Kg / hr is processed. In the first rectification tank 1, the pressure condition and temperature condition of the rectification tower are set for the purpose of separating heavy impurities and ammonia.

  That is, the crude ammonia liquid introduced into the central space part M1 of the first rectifying column 1 is mixed with the reflux liquid descending from the upper rectifying part B1, and comes into gas-liquid contact with the air stream rising in the lower rectifying part A1. In addition to vaporizing ammonia and light impurities, the ammonia moves to the bottom space U1 while absorbing heavy impurities. The gas phase that has been reboiled and raised to about 10 to 15 ° C. in the bottom space U1 is the crude ammonia solution introduced into the central space M1 and the upper rectification B1 in the lower rectification section A1 of about 10 to 15 ° C. The impurities are dissolved in the solution by contact with the condensate from the gas, and purified by bringing the condensate into contact with the condensate in the upper rectifying section B1 at about 9 to 10 ° C. That is, the heavy impurities that are components having a vapor pressure lower than that of ammonia (that is, having a high boiling point) are separated from the sample in the two rectification portions and concentrated into the liquid in the bottom space portion U1. The concentrated waste liquid is discharged periodically or continuously.

  At this time, for example, the ammonia gas delivered from the top of the first rectification column 1 is about 9.5 ° C./about 0.6 MPa, the flow rate is about 120 Kg / hr, and impurities are as shown in Table 2. About 0.1 wtppm or less of moisture remains as a part of light impurities and heavy impurities. The waste liquid discharged from the bottom of the tower is, for example, about 14 ° C./about 0.6 MPa, the flow rate is about 1 to 10 kg / hr, and the heavy impurities such as water and oil are concentrated about several dozen times to one hundred times. Has been.

  (3) The ammonia gas supplied from the first rectifying column 1 is introduced into the fixed bed adsorber 3. In the fixed bed adsorber 3, the heavy impurities such as moisture can be efficiently removed by allowing gas to flow evenly through an adsorbent such as synthetic zeolite disposed in the fixed bed. it can. When synthetic zeolite 3A is used as the adsorbent, not only heavy impurities but also light impurities according to the pore diameter can be removed.

  For example, when ammonia gas containing impurities is processed using the fixed bed adsorber 3, the impurities of ammonia gas delivered from the outlet of the fixed bed adsorber 3 include light impurities as shown in Table 2. The heavy impurities such as water and oil are removed to a non-measurable level (for example, 0.1 wtppm or less).

  (4) Next, the ammonia gas delivered from the fixed bed adsorber 3 is adjusted to a predetermined pressure or flow rate condition and introduced into the second fractionator 2 (about 9 ° C./about 0.6 MPa, flow rate About 120 Kg / hr). In the second rectification column 2, the pressure condition and temperature condition of the rectification column are set for the purpose of separating light impurities and ammonia.

  That is, the gaseous sample introduced into the central space part M2 of the second rectifying column 2 rises to the upper rectifying part B2 at about 4-9 ° C. and is cooled to about 4-5 ° C. there, By making gas-liquid contact with refluxing liquefied ammonia with high purity flowing down, the ammonia component in the sample is dissolved in the refluxing solution and flows down together. The ammonia component that has flowed down further moves to the lower space U2 via the lower rectification part A2 at about 9 to 10 ° C. and is purified. In the lower rectification part A2, the remaining light impurities are brought into gas-liquid contact with a gas containing a trace amount of light impurities reboiled in the lower space part U2, thereby further increasing the purity of ammonia and moving to the lower space part U2. The concentrated high-purity ammonia solution is delivered from the bottom of the column periodically or continuously.

  On the other hand, the light impurities pass through the upper rectification part B2 together with the components rising from the lower rectification part A2, move to the upper space part T2, and further cooled to about 0 to 2 ° C. and move to the upper space part T2. To do. That is, light impurities, which are components having a higher vapor pressure (that is, lower boiling point) than ammonia, are separated from the sample in the two rectifying portions and are concentrated in the gas in the upper space T2, and from the top of the column Continuously discharged.

  At this time, for example, the liquefied ammonia delivered from the bottom of the second rectification column 2 has a concentration of 99.999 wt%, about 9 ° C./about 0.6 MPa, and a flow rate of about 115 to 117 kg / hr. As shown in Table 2, almost no detection is possible. The waste gas discharged from the top is, for example, about 2 ° C./about 0.6 MPa, the flow rate is about 5 to 3 kg / hr, and air components, methane, carbon dioxide, which are light impurities as shown in Table 2. , Carbon monoxide, etc. are concentrated and discharged several tens of times.

(5) As described above, in the present invention,
(A) removal of heavy impurities and vaporization of ammonia in the first rectification column 1 (b) removal of heavy impurities and some light impurities in the fixed bed adsorber (c) second rectification In the tower 2, mainly by removing light impurities and liquefying ammonia,
The treatment of heavy impurities that could not be sufficiently treated only by the first rectification means and the treatment of light impurities that could not be sufficiently treated only by the second rectification means can be supplemented by the adsorption means. At the same time, by setting the conditions of both rectification means within a specific range, it is possible to treat ammonia with a strong adsorption force under conditions with little adsorption loss in the adsorption means. That is, both rectification means play a role of complementing the adsorption means.

  In general, the adsorption is performed at a high pressure because the capacity is improved as the pressure is increased, and the pressure condition is ensured by arranging the adsorption between the two rectification means. Also in the rectification means, the separation efficiency is improved by changing the pressure along with the temperature. By using the separation means corresponding to the boiling point of the impurities in sequence, the pressure treatment load of each means can be greatly reduced, and the removal efficiency is very high. The technical effect of becoming higher can be obtained.

Further, the present invention is characterized in that an adsorption means is independently provided between two rectification means. That means
(A) Compared with the case where it is introduced into the adsorbing means at normal pressure, when it is introduced into the adsorbing means in a pressurized state after the first rectifying column, a large adsorption function can be exhibited.
(B) Regeneration can be easily performed by flowing nitrogen through the heating unit separately to the adsorption means, and a member necessary to maintain the purge cooling or heating function is not necessary.
(C) The efficiency of the adsorbing means mainly responsible for removing heavy impurities because the first rectification column buffers heavy impurities even when there are fluctuations in the composition of impurities in the raw material that is the removal component. Will not be damaged.
(D) Even when a small amount of oil or the like is contained in the raw material, since most of the oil is removed by the first rectification column, the capacity of the adsorbent of the adsorption means is hardly lowered.

  Thus, each means complemented each other, and it was possible to continuously supply high-purity ammonia from crude ammonia, which was difficult in the past.

<Other embodiments of the invention>
(1) In the above embodiment, the case where the raw ammonia, which is the raw material, is supplied from the storage means to the rectification means has been mainly described. However, from the aspect of continuous supply of the crude ammonia, the raw ammonia is supplied from the ammonia production plant. It is preferable. According to the ammonia purification system or the purification method of the present invention, since the raw material supply from the ammonia production plant has a high purity because it has a structure that can sufficiently purify even a large amount of relatively low purity ammonia as a raw material. It is also useful in that ammonia can be continuously supplied. In particular, it can be combined with existing equipment, making it possible to use an ammonia production plant to form a highly versatile system. In addition, maintenance such as management of the storage amount becomes unnecessary, and the system can be simplified. Furthermore, since crude ammonia can be continuously introduced into the first purification means, instability factors such as moisture concentration can be eliminated, and stable operation becomes possible. As described above, it is possible to provide a high-performance and highly reliable ammonia purification system having excellent technical effects including continuous supply of high-purity ammonia.

  (2) The case where cooling water is used as a refrigerant for introducing cold heat into the upper condensing condensers C1 and C2 of the rectifying column has been described, but liquefied ammonia, liquefied carbon dioxide, freon, liquefied ethane, liquefied propane, etc. May be. In the above description, the capacitors C1 and C2 or the reboilers E1 and E2 are installed inside the rectifying columns 1 and 2, but can also be installed outside the rectifying columns 1 and 2. It is also possible to use steam or an electric heater for heating the reboiler.

Explanatory drawing which shows the structural example of the high purity ammonia refiner | purifier which concerns on this invention. Explanatory drawing which shows the structural example of the adsorption | suction means based on this invention. Explanatory drawing which shows the structural example of the ammonia refiner | purifier which concerns on a prior art. Explanatory drawing which shows 1 of the other structural example of the ammonia refiner | purifier which concerns on a prior art. Explanatory drawing which shows 2 of the other structural examples of the ammonia refiner | purifier which concerns on a prior art.

Explanation of symbols

1 First rectification means (first rectification tower)
2 Second rectification means (second rectification tower)
3 Adsorption means (fixed bed adsorber)
4 storage means (storage tank)
5 Lorries A1, A2 Lower rectification part B1, B2 Upper rectification part C1, C2 Capacitor E1, E2 Reboiler M1, M2 Central space part T1, T2 Upper space part U1, U2 Bottom space part

Claims (7)

A system for purifying crude ammonia,
A first rectifying means for mainly removing heavy impurities having a lower vapor pressure than ammonia from the raw crude ammonia; and a second rectifying means for removing light impurities having a higher vapor pressure than ammonia from gaseous ammonia. A plurality of rectification means including
Between the first rectification means and the second rectification means, at least one adsorption means for removing trace residue from gaseous ammonia;
An ammonia purification system characterized by comprising:   2. The ammonia purification system according to claim 1, wherein crude liquid ammonia as a raw material is supplied from a storage tank or a bulk transport tank.   2. The ammonia refining system according to claim 1, wherein crude ammonia as a raw material is supplied from an ammonia production plant.   The ammonia purification system according to any one of claims 1 to 3, wherein the adsorption means is filled with synthetic zeolite 3A. A method for purifying crude ammonia containing heavy impurities having a vapor pressure lower than that of ammonia and light impurities having a vapor pressure higher than that of ammonia,
Crude ammonia as a raw material is introduced into the first rectification means to remove most of heavy impurities, ammonia gas from which heavy impurities have been removed is introduced into the adsorption means to remove trace residues, A method for purifying ammonia, characterized in that high purity ammonia is obtained by removing light impurities by introducing into a double rectification means.   The ammonia purification method according to claim 5, wherein the crude ammonia is industrial ammonia having a purity of about 99.9 wt%. The ammonia purification method according to claim 5 or 6, wherein the high-purity ammonia has a purity of 99.999 wt% or more.

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