CN103269980A - Method for purifying ammonia and ammonia purification system - Google Patents

Method for purifying ammonia and ammonia purification system Download PDF

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Publication number
CN103269980A
CN103269980A CN2012800041903A CN201280004190A CN103269980A CN 103269980 A CN103269980 A CN 103269980A CN 2012800041903 A CN2012800041903 A CN 2012800041903A CN 201280004190 A CN201280004190 A CN 201280004190A CN 103269980 A CN103269980 A CN 103269980A
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ammonia
condensation
impurity
condenser
absorption
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田井慎一
畑启之
森本茂
吉田义则
津野修司
福岛丰仁
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Sumitomo Seika Chemicals Co Ltd
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Seitetsu Kagaku Co Ltd
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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
    • C01C1/12—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
    • 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

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Abstract

The present invention is a method for purifying ammonia and an ammonia purification system with which ammonia can be purified at a high recovery rate by a simple procedure and in a short purification time under low energy consumption. A second partial condenser (3) of an ammonia purification system (100) partially condenses crude ammonia gasified by a first evaporator (2) and separates and removes, as a liquid-phase component, the impurities having low volatility from the crude ammonia. A first partial condenser (5) partially condenses the gas-phase component separated by the second partial condenser (3) and separates and removes, as a gas-phase component, the impurities having high volatility.

Description

The process for purification of ammonia and ammonia refining system
Technical field
The present invention relates to thick ammonia is made with extra care process for purification and the ammonia refining system of (purification).
Background technology
In semi-conductor manufacturing process and liquid crystal manufacturing process, as at nitride by the treatment agent that uses in the making of overlay film etc., use highly purified ammonia.Highly purified ammonia like this obtains by thick ammonia is made with extra care to remove impurity.
Contain low-boiling point gas such as hydrogen, nitrogen, oxygen, argon gas, nitrogen protoxide, carbonic acid gas, hydrocarbon, moisture etc. in the thick ammonia as impurity.Usually the purity of obtainable thick ammonia is about 98～99 weight %.
As the hydrocarbon that contains in the thick ammonia, usually mainly be that carbonatoms is 1～4 hydrocarbon, when making the hydrogen of the synthesis material that is used as ammonia, if the separation of the oil content in the reacted gas is insufficient or be subjected to the oil pollution that the pump oil of origin self-pumping class causes when making, then also can sneak into the big hydrocarbon of the high molecular weight of boiling point sometimes.In addition, when containing large quantity of moisture in the ammonia, use the function of semi-conductor that this ammonia makes etc. significantly to reduce sometimes, therefore need reduce the moisture in the ammonia as far as possible.
Different according to the kind of the operation of the use ammonia in semi-conductor manufacturing process and the liquid crystal manufacturing process, the influence mode of the impurity in the ammonia is also different.As the purity of ammonia, requirement is 99.9999 weight % above (each impurity concentration is that 100ppb is following), more preferably about 99.99999 weight %.In recent years, when sowing such twinkler manufacturing for nitrogenize, require moisture concentration to be lower than 30ppb.
As the process for purification of the ammonia of the highly purified ammonia that is met this specification, this mode of distillation was arranged in the past, the rectification method that special use can expect to have high impurity separating power.
For example, in the disclosed process for purification, obtain highly purified ammonia by the adsorption tower of combination moisture, adsorption tower and the distillation tower of hydrocarbon in the patent documentation 1.In addition, in the patent documentation 2 in the disclosed process for purification, use rectifying tower at first to remove the high impurity of boiling point from the tower bottom of distillation tower, will feed adsorption tower from the ammonia that the top of tower of this distillation tower is derived and moisture is removed., again in rectifying tower distilling, from the top of tower of distillation tower low-boiling impurity is being removed, obtaining highly purified ammonia from the tower bottom of distillation tower thereafter.In addition, in the disclosed process for purification, by in distillation tower, low-boiling impurity being removed, in adsorption tower, moisture and oxygen are removed then in the patent documentation 3, thereby obtained highly purified ammonia.
The prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Application Publication 2008-505830 communique
Patent documentation 2: No. 4605705 communique of Japanese Patent
Patent documentation 3: No. 4062710 communique of Japanese Patent
Summary of the invention
Invent problem to be solved
But, in the patent documentation 1～3 in the process for purification of disclosed ammonia, need high distillation hop count for the rectifying of removing trace impurity, and the reflux ratio in the time of need be with rectifying when impurity concentration is high is set greatlyyer, the result, building of rectifying tower established Charges with becoming great number, and simultaneously long-time distillation also needs to drop into lot of energy.In addition, when impurity concentration is high density, in order also to make the impurity concentration that contains in the ammonia reach below the aimed concn by this rectifying, need to reduce the yield rate of resulting ammonia, perhaps according to different situations, also can't remove impurity etc. fully even reduce yield rate sometimes.
In addition, the impurity that contains in the ammonia is adsorbed in adsorption tower when removing, when the concentration of impurity was high, it is saturated and leaked and (namely can't proceed to adsorb that sorbent material can reach absorption at short notice; English is " breakthrough "; Japanese is “ Po Over "), to need being shortened the problems such as situation that exist appearance to continue to produce efficiently the time that the adsorption tower of having filled sorbent material is regenerated.
Therefore, even the object of the present invention is to provide the impurity that in ammonia, contains high density, also can drop into process for purification and the ammonia refining system of the ammonia that ammonia is made with extra care with the high rate of recovery, simple operation, short refining time, low energy.
Be used for solving the means of problem
The present invention relates to a kind of process for purification of ammonia, it is the method that the thick ammonia that contains impurity is made with extra care, it is characterized in that, comprise the partial condensation operation, in this operation thick ammonia is carried out partial condensation (partial condensation) and is separated into gas phase composition and liquid composition, thereby the impurity that contains in the thick ammonia is removed as gas phase composition or liquid composition separation.
In addition, in the process for purification of ammonia of the present invention, described partial condensation operation preferably comprises part 1 condensation operation, in this operation is that 1～8 hydrocarbon separates as gas phase composition and removes with hydrogen, nitrogen, oxygen, argon gas, carbon monoxide, carbonic acid gas and the carbonatoms that contains as impurity in the thick ammonia.
In addition, in the process for purification of ammonia of the present invention, described partial condensation operation preferably comprises part 2 condensation operation, in this operation is that hydrocarbon more than 9 separates as liquid composition and removes with the moisture that contains as impurity in the thick ammonia and carbonatoms.
In addition, in the process for purification of ammonia of the present invention, in the described partial condensation operation, described part 1 condensation operation is preferably the subsequent handling of described part 2 condensation operation.
In addition, in the process for purification of ammonia of the present invention, described partial condensation operation preferably comprises the 3rd partial condensation operation, will be by in described part 1 condensation operation, thick ammonia being carried out the liquid composition gasification that partial condensation obtains in this operation, the vapour that this gasification is obtained carries out partial condensation and is separated into gas phase composition and liquid composition, the impurity for ammonia that contains in the vapour is separated as gas phase composition remove.
In addition, in the process for purification of ammonia of the present invention, described part 1 condensation operation preferably comprises a plurality ofly carries out partial condensation stage of partial condensation to thick ammonia, along with the partial condensation stage that enters back segment, at low temperatures thick ammonia is carried out partial condensation.
In addition, in the process for purification of ammonia of the present invention, in the described part 1 condensation operation, preferably under-77～50 ℃ temperature, thick ammonia is carried out partial condensation.
In addition, in the process for purification of ammonia of the present invention, in the described part 1 condensation operation, preferably under the absolute pressure of 0.007～2MPa, thick ammonia is carried out partial condensation.
In addition, the process for purification of ammonia of the present invention also preferably comprises the absorption that utilizes sorbent material that the impurity absorption that contains in the thick ammonia is removed and removes operation.
In addition, in the process for purification of ammonia of the present invention, described absorption is removed operation and is preferably also comprised the 1st absorption that utilizes sorbent material that the water adsorption that contains as impurity in the thick ammonia is removed and remove operation.
In addition, in the process for purification of ammonia of the present invention, described absorption is removed operation and is also preferably comprised the 2nd absorption that utilizes sorbent material that the absorption of the hydrocarbon that contains as impurity in the thick ammonia is removed and remove operation.
In addition, in the process for purification of ammonia of the present invention, preceding continuous operation or the subsequent handling that operation is preferably described partial condensation operation removed in described absorption.
In addition, in the process for purification of ammonia of the present invention preferably, comprise the absorption that utilizes sorbent material that the impurity absorption that contains in the thick ammonia is removed and remove operation, it is operation between described part 2 condensation operation and the described part 1 condensation operation that operation is removed in described absorption.
In addition, the invention still further relates to a kind of ammonia refining system, it is the ammonia refining system that the thick ammonia that contains impurity is made with extra care, and it is characterized in that possessing:
The part 1 condensation part, it carries out partial condensation and is separated into gas phase composition and liquid composition thick ammonia, is that 1～8 hydrocarbon separates as gas phase composition and removes with hydrogen, nitrogen, oxygen, argon gas, carbon monoxide, carbonic acid gas and the carbonatoms that contains as impurity in the thick ammonia; With
The part 2 condensation part, it carries out partial condensation and is separated into gas phase composition and liquid composition thick ammonia, is that hydrocarbon more than 9 separates as liquid composition and removes with moisture and the carbonatoms that contains as impurity in the thick ammonia.
In addition, ammonia refining system of the present invention preferably also possesses the absorption that utilizes sorbent material that the impurity absorption that contains in the thick ammonia is removed and removes portion.
In addition, in the ammonia refining system of the present invention preferably: described part 2 condensation part, described part 1 condensation part and the described absorption portion of removing are connected in series successively, described part 1 condensation part to utilize described part 2 condensation portion from gas phase composition carry out partial condensation and be separated into gas phase composition and liquid composition, the described absorption portion of removing utilize sorbent material will utilize described part 1 condensation portion from liquid composition in the impurity absorption that contains remove.
In addition, in the ammonia refining system of the present invention preferably: portion is removed in described part 2 condensation part, described absorption and described part 1 condensation part is connected in series successively, the described absorption portion of removing utilize sorbent material will utilize described part 2 condensation portion from gas phase composition in the impurity absorption that contains remove, partial condensation is carried out to the ammonia that utilizes the absorption of the described absorption portion of removing to remove impurity in described part 1 condensation part.
In addition, preferably also possess the 3rd partial condensation portion in the ammonia refining system of the present invention, it carries out partial condensation and is separated into gas phase composition and liquid composition utilizing the absorption of the described absorption portion of removing to remove the ammonia behind the impurity, impurity is separated as gas phase composition remove.
In addition, in the ammonia refining system of the present invention preferably: portion is removed in described absorption and described part 1 condensation part is connected in series successively, and partial condensation is carried out to the ammonia that utilizes the absorption of the described absorption portion of removing to remove impurity in described part 1 condensation part.
In addition, in the ammonia refining system of the present invention preferably, described absorption is removed portion, described part 2 condensation part and described part 1 condensation part and is connected in series successively, partial condensation is carried out to the ammonia that utilizes the absorption of the described absorption portion of removing to remove impurity in described part 2 condensation part, described part 1 condensation part to utilize described part 2 condensation portion from gas phase composition carry out partial condensation and be separated into gas phase composition and liquid composition.
The invention effect
According to the present invention, the process for purification of ammonia is the method that the thick ammonia that contains impurity is made with extra care, and it comprises the partial condensation operation.In the partial condensation operation, be separated into gas phase composition and liquid composition by thick ammonia is carried out partial condensation, thereby the impurity that contains in the thick ammonia is removed as gas phase composition or liquid composition separation.
Partial condensation refers to the part liquefaction with liquable gas.Therefore, the partial condensation operation by the partial condensation operation becomes liquid composition for the part in the thick ammonia of gas shape of partial condensation by condensation liquefaction, and uncooled part also left behind with the state of gas and becomes gas phase composition.Difference according to the kind of impurity, the liquid composition that condensation obtains or be not condensed and all contain a large amount of impurity that initially namely are present in the thick ammonia in any of the gas phase composition that left behind with gaseous phase, its impurity level reduces in the gas phase composition that constitutes another phase or liquid composition on the contrary.
Namely, in the process for purification of ammonia of the present invention, by the partial condensation of the thick ammonia of gas shape, the low impurity of volatility in the thick ammonia is concentrated in the liquid composition that generates by partial condensation, the high impurity of volatility in the thick ammonia is concentrated in the gas phase composition that is not condensed and left behind.So, by thick ammonia is carried out partial condensation, the impurity that contains in the thick ammonia can be separated and remove, the ammonia after obtaining making with extra care.Therefore, do not need to pass through as prior art distillation process, even contain the impurity of high density in the thick ammonia, yet can drop into ammonia is made with extra care with the high rate of recovery, simple operation, short refining time, low energy.
In addition, according to the present invention, the partial condensation operation comprises part 1 condensation operation.In this part 1 condensation operation, by being carried out partial condensation, the thick ammonia of gas shape is separated into gas phase composition and liquid composition, remove thereby the impurity that contains in the thick ammonia separated as gas phase composition.By the partial condensation of part 1 condensation operation, can make the high impurity of volatility in the thick ammonia is that hydrogen, nitrogen, oxygen, argon gas, carbon monoxide, carbonic acid gas and carbonatoms are that 1～8 hydrocarbon is concentrated in to separate in the uncooled gas phase composition that is not condensed and removes.
In addition, according to the present invention, the partial condensation operation also comprises part 2 condensation operation.In this part 2 condensation operation, be separated into gas phase composition and liquid composition by the thick ammonia of gas shape is carried out partial condensation, remove thereby the impurity that contains in the thick ammonia separated as liquid composition.By the partial condensation of part 2 condensation operation, can to make the low impurity of volatility in the thick ammonia be moisture with carbonatoms is that hydrocarbon more than 9 is concentrated in to separate in the liquid composition that condensation obtains and removes.
In addition, according to the present invention, part 1 condensation operation is the subsequent handling of part 2 condensation operation.Thus, in the part 1 condensation operation, can the impurity that contain in thick ammonia in part 2 condensation operation be carried out partial condensation and be separated into gas phase composition and liquid composition as the gas phase composition that liquid composition separates after removing, remove thereby the impurity of the remnants that contain in the thick ammonia separated as gas phase composition.Therefore, can access more highly purified ammonia.
In addition, according to the present invention, the partial condensation operation also comprises the 3rd partial condensation operation.In the 3rd partial condensation operation, by will be by in part 1 condensation operation, thick ammonia being carried out the liquid composition gasification that partial condensation obtains, the vapour that this gasification is obtained carries out partial condensation and is separated into gas phase composition and liquid composition, thereby contain in the vapour the impurity of ammonia is separated as gas phase composition removed.In the part 1 condensation operation, the impurity that the volatility that contains in the thick ammonia is high separates as gas phase composition to be removed.That is the ammonia liquor that reduced of the liquid composition that obtains in the part 1 condensation operation content that becomes the high impurity of volatility.In the 3rd partial condensation operation, by such ammonia liquor is gasified, the vapour that this gasification is obtained carries out partial condensation, removes thereby the impurity that contains in the vapour separated as gas phase composition, the ammonia liquor that the content that therefore can access the high impurity of volatility has further reduced.
In addition, according to the present invention, part 1 condensation operation comprises a plurality ofly carries out partial condensation stage of partial condensation to thick ammonia, along with the partial condensation stage that enters back segment, at low temperatures thick ammonia is carried out partial condensation.Thus, the impurity that contains in the thick ammonia can be separated efficiently as gas phase composition and remove, can access more highly purified ammonia liquor as liquid composition.
In addition, according to the present invention, in the part 1 condensation operation, under-77～50 ℃ temperature, thick ammonia is carried out partial condensation.Even the temperature in part 1 condensation operation is higher than under 50 ℃ the situation, if improve the effect of removing that pressure then also can access the impurity that produced by partial condensation, but this moment, the pressure of ammonia became the high pressure of 1.81MPa, to being not preferred condition in industrial enforcement.In addition, even the temperature in part 1 condensation operation is lower than under-77 ℃ the situation, also can carry out the refining of ammonia by reducing pressure.But, because temperature is low, obtain highly purified ammonia as liquid composition, but because because the fusing point of ammonia be-78 ℃, therefore need the ammonia that will solidify at low temperatures termly fusion it is liquefied, considering under the situation of continuous processing the high-efficiency method of can not saying so.
In addition, according to the present invention, in the part 1 condensation operation, under the absolute pressure of 0.007～2MPa, thick ammonia is carried out partial condensation.Thus, can under above-mentioned-77～50 ℃ temperature, carry out partial condensation to thick ammonia, therefore can obtain highly purified ammonia efficiently.
In addition, according to the present invention, the process for purification of ammonia also further comprises absorption and removes operation.This absorption is removed in the operation, utilizes sorbent material that the impurity absorption that contains in the thick ammonia is removed.Thus, the impurity absorption that can utilize sorbent material not remove fully in the partial condensation operation is removed, and therefore can access more highly purified ammonia.
In addition, according to the present invention, absorption is removed operation and is also comprised the 1st absorption and remove operation.The 1st absorption is removed in the operation, utilizes sorbent material that the water adsorption that contains as impurity in the thick ammonia is removed.Thus, the moisture impurity absorption that can utilize sorbent material not remove fully in the partial condensation operation is removed, and therefore can access more highly purified ammonia.
In addition, according to the present invention, absorption is removed operation and is also comprised the 2nd absorption and remove operation.The 2nd absorption is removed in the operation, utilizes sorbent material that the hydrocarbon absorption that contains as impurity in the thick ammonia is removed.Thus, the hydrocarbon impurity absorption that can utilize sorbent material not remove fully in the partial condensation operation is removed, and therefore can access more highly purified ammonia.
In addition, according to the present invention, preceding continuous operation or the subsequent handling that operation is the partial condensation operation removed in absorption.When absorption being removed operation as the subsequent handling of partial condensation operation, the impurity absorption that can utilize sorbent material not remove fully in the partial condensation operation is removed, and therefore can access more highly purified ammonia.In addition, when absorption being removed operation as the preceding continuous operation of partial condensation operation, after the impurity absorption of utilizing sorbent material to contain in thick ammonia is removed, can effectively utilize partial condensation and remove impurity, therefore can access more highly purified ammonia.
In addition, according to the present invention, after part 2 condensation operation, implement in the process for purification of ammonia of part 1 condensation operation, between part 2 condensation operation and part 1 condensation operation, implement absorption and remove operation.Thus, the impurity that contain in will be in the part 2 condensation operation thick ammonia separates the impurity that contains in the gas phase composition after removing as liquid composition and utilizes adsorbents adsorb to remove, and then after, the impurity of the remnants that contain in the thick ammonia can be separated as gas phase composition and remove.
In addition, according to the present invention, the ammonia refining system possesses part 1 condensation part and part 2 condensation part.The part 1 condensation part is separated into gas phase composition and liquid composition by thick ammonia is carried out partial condensation, removes thereby the impurity that contains in the thick ammonia separated as gas phase composition.This part 1 condensation part is by partial condensation, is that hydrogen, nitrogen, oxygen, argon gas, carbon monoxide, carbonic acid gas and carbonatoms are that 1～8 hydrocarbon is concentrated to separate in the uncooled gas phase composition that is not condensed and removes thereby can make the high impurity of volatility in the thick ammonia.In addition, the part 2 condensation part is separated into gas phase composition and liquid composition by thick ammonia is carried out partial condensation, removes thereby the impurity that contains in the thick ammonia separated as liquid composition.This part 2 condensation part is by partial condensation, can be with the volatility in the thick ammonia low impurity be moisture with carbonatoms be that hydrocarbon more than 9 is concentrated to separate in the liquid composition that condensation obtains and removes.
In addition, according to the present invention, the ammonia refining system also further possesses absorption and removes portion.The absorption portion of removing utilizes sorbent material that the impurity absorption that contains in the thick ammonia is removed.Thus, the impurity absorption that can utilize sorbent material not remove fully in part 1 condensation part and part 2 condensation part is removed, and therefore can access more highly purified ammonia.
In addition, according to the present invention, part 2 condensation part, part 1 condensation part and the absorption portion of removing are connected in series successively.So, the part 1 condensation part to utilize the part 2 condensation portion from gas phase composition carry out partial condensation and be separated into gas phase composition and liquid composition, the absorption portion of removing utilize sorbent material will utilize the part 1 condensation portion from liquid composition in the impurity absorption that contains remove.So, can access highly purified ammonia.
In addition, according to the present invention, the part 2 condensation part, portion is removed in absorption and the part 1 condensation part is connected in series successively.So, the absorption portion of removing utilize sorbent material will utilize the part 2 condensation portion from gas phase composition in the impurity absorption that contains remove, partial condensation is carried out to the ammonia that utilizes the absorption of the absorption portion of removing to remove impurity in the part 1 condensation part.So, can access highly purified ammonia.
In the ammonia refining system that part 2 condensation part, part 1 condensation part and the absorption portion of removing are connected in series successively, also possesses the 3rd partial condensation portion.The 3rd partial condensation portion in the part 2 condensation part, part 1 condensation part and absorption removes and removed the ammonia behind the impurity in the portion and carry out partial condensation and be separated into gas phase composition and liquid composition, impurity is separated as gas phase composition removes.Thus, can with in the part 2 condensation part, part 1 condensation part and absorption removes the impurity of not removing fully in the portion and separates as gas phase composition and remove, and therefore can access more highly purified ammonia.
In addition, according to the present invention, portion is removed in absorption and the part 1 condensation part is connected in series successively.So partial condensation is carried out to the ammonia that utilizes the absorption of the absorption portion of removing to remove impurity in the part 1 condensation part.So, can access highly purified ammonia.
In addition, according to the present invention, absorption is removed portion, part 2 condensation part and part 1 condensation part and is connected in series successively.So partial condensation is carried out to the ammonia that utilizes the absorption of the absorption portion of removing to remove impurity in the part 2 condensation part, the part 1 condensation part to utilize the part 2 condensation portion from gas phase composition carry out partial condensation and be separated into gas phase composition and liquid composition.So, can access highly purified ammonia.
Description of drawings
Purpose of the present invention, characteristic and advantage become clearer and more definite by following detailed explanation and accompanying drawing.
Fig. 1 is the figure of the formation of the ammonia refining system 100 of expression the 1st embodiment of the present invention.
Fig. 2 is the figure of the formation of expression part 2 condenser 3.
Fig. 3 is the figure of the formation of expression part 1 condenser 5.
The figure of the formation of the part 1 condenser 5 that Fig. 4 is connected in series for a plurality of partial condensation of expression portion.
The vapour that Fig. 5 obtains gasification from the 1st withdrawing can 6 for expression imports the figure of the position of part 1 condenser 5.
Fig. 6 is the figure of the syndeton between expression the 1st withdrawing can 6 and the part 1 condenser 5.
Fig. 7 is the figure of the formation of the ammonia refining system 200 of expression the 2nd embodiment of the present invention.
Fig. 8 is the figure of the formation of the ammonia refining system 300 of expression the 3rd embodiment of the present invention.
Fig. 9 is the pie graph of the ammonia refining system 400 of expression the 4th embodiment of the present invention.
Figure 10 is the figure of the formation of the ammonia refining system 500 of expression the 5th embodiment of the present invention.
Figure 11 is the pie graph of the ammonia refining system 600 of expression the 6th embodiment of the present invention.
Embodiment
Fig. 1 is the figure of the formation of the ammonia refining system 100 of expression the 1st embodiment of the present invention.The system of ammonia refining system 100 for the thick ammonia that contains impurity is made with extra care of present embodiment.
Ammonia refining system 100 constitutes by comprising following apparatus: raw material store jar the 1, the 1st vaporizer 2, as the part 2 condenser 3 of part 2 condensation part, as the part 1 condensation part part 1 condenser 5, the 2nd withdrawing can 4, the 1st withdrawing can 6, the 2nd vaporizer 7, remove the 1st adsorption tower 8 and the 2nd adsorption tower 9, complete condenser (liquefying plant) 10 and the goods jar 30 of portion as absorption.In addition, ammonia refining system 100 is realized the process for purification of ammonia of the present invention, part 1 condenser 5 as the part 1 condensation part is implemented part 1 condensation operation, part 2 condenser 3 as the part 2 condensation part is implemented part 2 condensation operation, the 1st adsorption tower 8 is implemented the 1st absorption and is removed operation, and the 2nd adsorption tower 9 is implemented the 2nd absorption and removed operation.
Here, distinctive part 2 condenser 3 and the part 1 condenser 5 of constituting in the ammonia refining system 100 of present embodiment.Part 2 condenser 3 is separated into gas phase composition and liquid composition by the thick ammonia of gas shape is carried out partial condensation, removes thereby the impurity that the volatility that contains in the thick ammonia is low separates as liquid composition.Part 1 condenser 5 is separated into gas phase composition and liquid composition by the thick ammonia of gas shape is carried out partial condensation, removes thereby the impurity that the volatility that contains in the thick ammonia is high separates as gas phase composition.
At first, the partial condensation of utilizing 5 pairs of thick ammonia of gas shape of part 2 condenser 3 and part 1 condenser to carry out is illustrated.
If the kind of the impurity that contains in the ammonia (thick ammonia) to industrial manufacturing is carried out rough classification, then be generally dissolving low-boiling point gas, hydro carbons, moisture etc. such as hydrogen, nitrogen, oxygen, argon gas, carbon monoxide and carbonic acid gas.As the hydrocarbon that contains in the thick ammonia, containing maximum is methane, and next contains a large amount of ethane, propane, ethene and propylene etc.From carbonatoms, carbonatoms is the principal constituent that 1～3 hydrocarbon has constituted hydro carbons.
But, although the content in thick ammonia is few, but contain carbonatoms be more than 4 hydrocarbon, in most cases be 4～6 hydrocarbon for carbonatoms.In addition, when the ammonia with industrial manufacturing liquefies, for oil pump etc. is used in its compression.In the case, can contain the hydrocarbon that the oil content that comes from the pump oil of sneaking into from oil pump etc. etc. has macromolecule in the thick ammonia.
Make the refining system of the ammonia that can remove the hydro carbons of carbonatoms in wide region that constitutes these impurity, it is essential to have become towards the ammonia of electronic industry for manufacturing.
Present inventors find, the method for removing the impurity in the thick ammonia of rectifying instead, and it is excellent adopting the method for partial condensation.
For example, under the situation of hydrocarbon being separated by rectifying, 5～20 sections rectifying tower need be set usually and distill with 10～20 reflux ratio.In this distillation (rectifying), the carbonatoms that is mainly that contains in the ammonia is that 1～8 hydro carbons is removed from the top of tower of distillation tower as the high composition of volatility.Obtaining by this distillation operation under the situation of highly purified ammonia, need make from the discarded ammonia that contains the high impurity of volatility of the top of tower of distillation tower is a problem for the highly purified ammonia what kind of ratio just can obtain as target always.Even as under the situation of raw material, need be about 10% of the thick ammonia that is supplied to distillation tower so big ratio from the discarded ratio of the top of tower of distillation tower at the thick ammonia that foreign matter content is lower.
Table 1 shows the boiling point that ammonia and carbonatoms are 1～8 saturated positive hydrocarbon, it is 4～8 hydrocarbon about carbonatoms, when this hydrocarbon exists with the form of pure substance, although boiling point than ammonia height, also can be discharged from as the top of tower of the high compound of volatility from distillation tower by distillation operation.
Figure BDA00003361512800111
Though its reason is still uncertain, present inventors have carried out following supposition to this reason.That is, with carbonatoms be 1～8 hydrocarbon boiling point for example carbonatoms be that the boiling point of 3 propane is example, when propane being added container and temperature is changed, the temperature the when boiling point of propane reaches 1 normal atmosphere (0.1013MPa) for the pressure in this container.The state of propane of this moment is the state that adjacent propane molecule attracts each other under the effect of Van der Waals force etc. each other, and when this power that attracts each other was strong, boiling point showed highly.But, be to be in following state under the low-down situation of the concentration that is present in the propane in the ammonia as becoming problem now: propane molecule or other hydrocarbon molecules that can attract each other near the propane molecule do not exist, and only a propane molecule swims in the marine of ammonia liquor.
Usually, as hydrocarbon molecule each other or the amino molecule molecule that has similarity each other can produce big intermolecular forces each other.But this intermolecular forces that the molecule that nature difference is big as propane molecule and amino molecule produces each other is little.So, exist in ammonia under the situation of denier hydrocarbon impurity, it is nonsensical that the concept of existing distillation has become.In the ammonia liquor, amino molecule exerts an influence to the power that attracts each other each other, and on the other hand, even be 4～8 hydrocarbon as the boiling point of the pure substance carbonatoms higher than ammonia, the interaction of they and amino molecule is also little.Therefore, in the ammonia liquor, show as the boiling point compound lower than ammonia and also have nothing mysterious even the boiling point carbonatoms higher than ammonia is 4～8 hydrocarbon.In fact, from the result of rectifying as can be known, carbonatoms is that 1～8 hydrocarbon shows as the high compound of volatility with boiling point lower than ammonia.
It is 1～8 hydrocarbon for the carbonatoms that contains of trace in the ammonia, make temperature that various variations take place and when the concentration of these hydrocarbon in ammonia reaches the vapor liquid equilibrium state, be determined in the gas phase of liquefied ammonia and the liquid phase to present what kind of concentration distribution, the result of mensuration is shown in the table 2.Wherein, partition ratio is following mensuration: the starting point concentration of each saturated positive hydrocarbon concentration in ammonia liquor is adjusted to 5000ppm, measuring after the placement 2 round the clock under the temperature of regulation then.
[table 2]
Figure BDA00003361512800121
Need to prove that the gas-liquid partition coefficient shown in this table 2 is the index that impurity with which kind of degree can be separated by partial condensation, it is defined as follows.
Partition ratio (Kd)=A 1/ A 2(1)
In the formula, A 1Impurity concentration in the gaseous ammonia behind the expression vapor liquid equilibrium, A 2Impurity concentration in the ammonia liquor behind the expression vapor liquid equilibrium.］
Wherein, the impurity concentration A in the following formula (1) 1, A 2Be its unit with mol-ppm, be defined as follows formula (2).
Impurity concentration (A 1, A 2)=impurity (mol)/(ammonia (mol)+impurity (mol)) * 10 6
（2）
According to this definition, the impurity that gas-liquid partition coefficient is more big can contain more in large quantities by in the uncondensed gas ammonia of partial condensation condensation.The exist ratio of the more little hydrocarbon of carbonatoms in gas phase exists ratio more high in liquid phase, so long as carbonatoms is the hydrocarbon below 8, then exists with higher concentration in gas phase.In addition, temperature is more low, hydrocarbon more with higher concentration be present in ammonia mutually in.
In addition as can be known, the time when reaching the balance shown in this table 2 is elongated along with the hydrocarbon concentration step-down that contains in the ammonia, in the concentration of the ppm level shown in, needs time a few days when reaching its balance here.This is illustrated in by in the operation of rectifying except the impurity in the deammoniation, in the gas-liquid contact time of the weak point that each distilling period of rectifying tower takes place, moves as the material of the hydrocarbon of impurity and fully not to carry out.Consider that from this result the method that rectifying is used for the high purityization of ammonia stresses results lower from industry.Need to prove that table 2 is the data about saturated straight chain shape hydrocarbon, is that 4 to comprise corresponding various isomer or carbonatoms when above be that intramolecularly comprises under the situation of unsaturated link(age) in the hydrocarbon more than 2 at carbonatoms, also has the tendency shown in the table 2.
As implied above, present inventors have confirmed that the thin impurity in the thick ammonia is that carbonatoms is that the performance of 1～8 hydrocarbon has a great difference with the state of thinking in the past.Further thinking, can be that 1～8 the nature difference of hydrocarbon in ammonia is used for the refining of ammonia with this carbonatoms.Therefore, trial remains on the ammonia temperature-20 ℃, makes the wall temperature in the part 1 condenser 5 be-30 ℃, 95% liquefaction of the thick ammonia of gas shape of the about 5000ppm of methane, ethane and propane, about 500ppm and about 500ppm will be contained by condensation respectively, do not detect these hydrocarbon in the ammonia liquor that the result obtains, the major part of impurity remains in the uncooled gaseous ammonia as can be known.Partition ratio according to table 2, operating in-20 ℃ by partial condensation issues in the ammonia liquor that raw food coagulates, calculating methane, ethane and propane can exist with 54ppm, 24ppm and 56ppm respectively, but be unexpectedly, partial condensation by part 1 condenser 5, its value becomes very little, thick ammonia can be made with extra care at short notice as can be known to be very high purity.
When the impurity that contains in thick ammonia by rectifying separates when removing, owing to be the distillation that refluxes simultaneously, thereby therefore in distillation tower, make the ammonia liquor heating evaporation form gaseous ammonia, on the other hand, repeat following operation: utilize the condenser of the top of tower of distillation tower to make from the gaseous ammonia condensation of rectifying tower and make ammonia liquor.Therefore, the energy that need in this operation, have high input in the distillation operation.
Relative therewith, the impurity that contains in thick ammonia when the partial condensation by part 1 condenser 5 separates when removing, owing to only gaseous ammonia is carried out 1 condensation, so it needs energy seldom to finish.So as can be known, compare with the process for purification of the ammonia that is undertaken by rectifying, the process for purification that is undertaken by the partial condensation of part 1 condenser 5 not only can obtain highly purified ammonia at short notice, and very big advantage is also arranged aspect energy.
In addition, present inventors also find the following fact: when the impurity that contains in the thick ammonia is that carbonatoms is when being 1～8 hydrocarbon, if utilize part 1 condenser 5 to be accompanied by to reach the partial condensation operation of about 90～99.5% liquefaction of the thick ammonia of gas shape, then the impurity concentration that contains in the concentration of the impurity that contains in the ammonia liquor that obtains as liquid composition and the initial thick ammonia of gas shape is compared greatly and is reduced.
The impurity that contains in thick ammonia in the partial condensation by part 1 condenser 5 separates in the process for purification of removing, the ammonia liquor that obtains as liquid composition by partial condensation surpasses the value of being predicted by the gas-liquid partition ratio as previously mentioned, and the concentration of impurity hydrocarbon reduces greatly.Though its reason is also uncertain, equilibrium relationship is broken when inferring partial condensation, dynamic impurity takes place separate, and nearly all impurity hydrocarbon remains in the uncooled gas phase composition.It is supported that the exactness of this supposition can obtain following item: when the ammonia liquor that will obtain as liquid composition by the partial condensation of part 1 condenser 5 is not taken out but when making its state with ammonia liquor be trapped in the inside of part 1 condenser 5 fast from part 1 condenser 5, along with time lapse, the impurity hydrocarbon concentration in the ammonia liquor rises gradually.
This is inferred and the result shows, for obtain high purity ammonia essential be: the ammonia liquor that will obtain as liquid composition by the partial condensation of part 1 condenser 5 derives fast and only exists the mode of uncooled gas phase composition that part 1 condenser 5 is turned round according to the inside of part 1 condenser 5 from part 1 condenser 5.
In addition, it is believed that in order to improve the purification efficiency of ammonia, though only be standard roughly, gas-liquid partition coefficient is more big more preferred.As indicated above, this gas-liquid partition coefficient is subjected to Temperature Influence, and the partial condensation temperature is more low more to access big gas-liquid partition coefficient.This means, when the design temperature of the partial condensation of part 1 condenser 5 operation is high, for example when the temperature that will the partial condensation of ammonia take place is set at 50 ℃, if to make the pressure of the ammonia that is supplied to part 1 condenser 5 be more than the 1.81MPa, then the partial condensation of ammonia becomes possibility, compare with the situation that the design temperature of partial condensation operation is low, the separation efficiency of its hydrocarbon impurity might reduce.
Part 1 condenser 5 preferably according to the temperature of the gas phase composition in the part 1 condenser 5 reach below 50 ℃, the mode that more preferably reaches-77 ℃～30 ℃ carries out partial condensation to thick ammonia.For the partial condensation temperature that makes part 1 condenser 5 in-77～50 ℃ scope, under the absolute pressure of 0.007～2MPa, thick ammonia is carried out partial condensation and gets final product.
Even be higher than in the partial condensation temperature of part 1 condenser 5 under 50 ℃ the situation, if improve the effect of removing that pressure then also can access impurity that partial condensation produces, but this moment, the pressure of ammonia became the high pressure of 1.81MPa, to being not preferred condition in industrial enforcement.In addition, be higher than in the partial condensation temperature of part 1 condenser 5 under 50 ℃ the situation, when the concentration of the initial impurity hydrocarbon that exists is the high density that has surpassed imagination in thick ammonia, even pass through partial condensation, the possibility that contains impurity in the liquefied ammonia also becomes big, need be by reducing that the partial condensation rate is dealt with etc., thus refining yield or purification efficiency reduce.
In addition, even be lower than in the partial condensation temperature of part 1 condenser 5 under-77 ℃ the situation, also can carry out the refining of ammonia by the pressure that reduces gaseous ammonia, because temperature is low, highly purified ammonia obtains as liquid composition (ammonia liquor).But, because the fusing point of ammonia is-78 ℃, when carrying out partial condensation under the temperature below the wall temperature at part 1 condenser 5 drops to the fusing point of ammonia, solidifying of the ammonia liquor that obtains in the condensation advanced, therefore need fusion termly to make its liquefaction, consider continuous processing, the high-efficiency method of can not saying so.But, owing to confirm by partial condensation and obtained being on the quality ammonia of ultra-high purity, therefore even drop to partial condensation operation under the temperature below-77 ℃ in the wall temperature of part 1 condenser 5, for the purpose that obtains highly purified ammonia with high yield, also be a kind of good method.
In addition, when for the partial condensation of part 1 condenser 5 wall of part 1 condenser 5 being set at low temperature, liquid film and this wall temperature of the ammonia liquor that obtains as the liquid composition on the wall that is present in part 1 condenser 5 approach.Therefore as shown in table 2, temperature is more low, and it is big that the ratio of the impurity hydrocarbon that exists in the impurity hydrocarbon that exists in the gas phase and the liquid phase becomes, and in addition, the motion of molecule is inhibited under the low temperature.Consequently, for the ammonia liquor that obtains as liquid composition by the condensation of being undertaken by partial condensation, the gas phase composition of its impurity hydrocarbon from liquid film also is inhibited to the movement of ammonia liquor, therefore can keep the ammonia liquor that obtains as liquid composition by condensation under highly purified state.
In addition, when the impurity concentration in the thick ammonia was very high, the partial condensation that repeatedly repeats part 1 condenser 5 was effective.For example, thick ammonia condensation rate under the partial condensation temperature is-15 ℃, with 95% in part 1 condenser 5 that will contain methane 30000ppm, propane 10000ppm carries out 2 partial condensations operations.About the impurity concentration in the ammonia liquor that obtains by the 1st partial condensation and as liquid composition, methane is that 9ppm, propane are 57ppm.Again when the same terms carries out the partial condensation operation, about the impurity concentration in the ammonia liquor that obtains as liquid composition, these two does not all detect methane and propane when making the gasification of this ammonia liquor.
In addition, by the partial condensation of part 1 condenser 5, much can be than impurity hydrocarbon mentioned above simple ground separates low-boiling point gas such as the hydrogen that contains in the thick ammonia, nitrogen, oxygen, argon gas, carbon monoxide, carbonic acid gas to be removed.Therefore, if the partial condensation condition (temperature, pressure, time etc.) of part 1 condenser 5 is set at the condition that can separate except dealkylation, then also can separates and remove above-mentioned low-boiling point gas.That is by the partial condensation of part 1 condenser 5, can easily be that low-boiling point gas is removed as uncooled gas phase composition with the impurity that contains in the thick ammonia.
Even the carbonic acid gas among the low-boiling point gas also can with thick ammonia in ammonia interact, its part is with volatile salt ((NH 4) 2CO 3) or ammonium carbamate (H 2NCOONH 4: form Ammonium Carbamate) exists.Thick ammonia condensation rate under the partial condensation temperature is-15 ℃, with 95% in part 1 condenser 5 that will contain such carbonic acid gas with the concentration of 1000ppm carries out 2 partial condensations operations.Concentration of carbon dioxide about in the ammonia liquor that obtains by the 1st partial condensation and as liquid composition is about 50ppm, is about 1/20th of the concentration that contains in the initial thick ammonia.When making this ammonia liquor gasification and under identical condition, carrying out the partial condensation operation again, concentration of carbon dioxide in the ammonia liquor that obtains as liquid composition can be for the concentration that contains in the initial thick ammonia about 1/400th, it is reduced to the low-down concentration that contains.In addition, details as described later, but carbonic acid gas can also utilize as the zeolite adsorption of sorbent material and removes.
Part 2 condenser 3 is separated into gas phase composition and liquid composition by the thick ammonia of gas shape is carried out partial condensation, removes thereby the impurity that the volatility that contains in the thick ammonia is low separates as liquid composition.As the low impurity of the volatility that contains in the thick ammonia, can list moisture, carbonatoms hydrocarbon how and trace metal etc.Here, the hydrocarbon that carbonatoms is many refers to that carbonatoms is the hydrocarbon more than 9.
Trace metal is the composition that becomes problem in the semiconductor industry.When making thick ammonia in the 1st vaporizer 2 described later, thereby the trace metal that contains in the thick ammonia is not vaporized, left behind major part as liquid composition and be removed.In the 1st vaporizer 2, be not removed and be imported into the trace metal of part 2 condenser 3 with the state that in the thick ammonia of gas shape, contains and can be by the partial condensation of part 2 condenser 3 separate as liquid composition and remove.
It is that separate the principle of removing with low-boiling point gas be identical basically for 1～8 hydrocarbon with carbonatoms with the part 1 condenser 5 that passes through mentioned above that partial condensation by part 2 condenser 3 is separated the water that contains in the thick ammonia or the many hydrocarbon of carbonatoms the principle of removing.Difference is that impurity is concentrated to gas phase side in the part 1 condenser 5, and impurity is concentrated to liquid side in the part 2 condenser 3.
About the partial condensation by part 2 condenser 3 water or the many hydrocarbon of carbonatoms being separated and to remove, is that example describes with the situation of water, but the situation of the many hydrocarbon of carbonatoms can be separated too and removed.
The thick ammonia of gas shape that contains moisture is cooled in part 2 condenser 3, and its part becomes ammonia liquor.Contain quite a few of the moisture that is present at first in the thick ammonia in this ammonia liquor.For example, in the part 2 condenser 3 of 0 ℃ of the thick ammonia importing of the gas shape that will contain 3000ppm moisture, it is 0 ℃ when making its 5% be condensed into ammonia liquor with gas temperature, moisture concentration in the ammonia liquor that condensation obtains is 28ppm, and 98.8% quilt that is present in the amount of moisture in the thick ammonia is at first contained in this ammonia liquor.Be not condensed and moisture concentration in the residual gaseous ammonia is 38ppm, compare and be reduced to about 1/80th with the moisture concentration in being present in thick ammonia at first.When only the partial condensation temperature being reduced to-10 ℃ and other conditions when carrying out partial condensation in the same manner, be not condensed and moisture concentration in the residual gaseous ammonia is 13ppm, compare and be reduced to approximately 1/230th with the moisture concentration in being present in thick ammonia at first, show better result.
For the partial condensation by part 2 condenser 3 is removed the moisture in the thick ammonia, the partial condensation temperature be preferably-75～50 ℃, more preferably-75～30 ℃.When the partial condensation temperature is lower than-75 ℃, sometimes the part of the mixture of the ammonia that obtains by condensation and water is cooled to below the zero pour and solidifies, this solid can hinder from the wall of part 2 condenser 3 except reducing phlegm and internal heat, the condensing rate of ammonia diminishes as a result, perhaps the solid of Sheng Chenging causes the pipe arrangement obturation, and is therefore not preferred.In addition, when the partial condensation temperature is low, by the pressure that reduces gaseous ammonia, temperature and the heat-conducting area of regulating the wall of part 2 condenser 3, can regulate the condensing rate of ammonia.On the other hand, when the partial condensation temperature was higher than 50 ℃, the increased pressure of ammonia was needing expense aspect the equipment of tolerance high pressure.In addition, carry out the situation of partial condensation under the amount of moisture that in the ammonia liquor that condensation obtains, is removed and the low temperature and compare, also have the tendency that reduces, therefore can cause the yield of refining ammonia to reduce or purity drop.
In addition, when the moisture concentration in the thick ammonia was very high, the partial condensation that repeatedly repeats part 2 condenser 3 was effective.This can be by being connected in series more than 3 of part 2 condensers to realize.When being set to more than 3 formations that are connected in series of part 2 condenser, the partial condensation temperature of the 1st section part 2 condenser 3 is set at can the high slightly temperature of state of cure than the mixture of the ammonia that obtains as liquid composition by condensation and water, and the gas phase composition of the 1st section part 2 condenser 3 is that the gaseous ammonia that moisture concentration has reduced reduces the partial condensation temperature of the part 2 condenser 3 after the 2nd section that imports.
For example, when the thick ammonia of gas shape that will contain 3000ppm moisture in the 1st section part 2 condenser 3 when the partial condensation temperature is carried out the partial condensation operation for the condensation rate under-10 ℃, with 5%, the moisture concentration in the gaseous ammonia that obtains as gas phase composition is the low value below the 13ppm.When to this gas phase composition in the 2nd section part 1 condenser 5 when the partial condensation temperature is carried out the partial condensation operation for the condensation rate under-70 ℃, with 5%, the moisture concentration in the gaseous ammonia that obtains as gas phase composition is the low value below the 1ppm.
Fall the partial condensation temperature of part 2 condenser 3 more low, owing to contain a large amount of moisture in the liquid composition, therefore more can improve moisture is separated the rate of removing of removing as liquid composition.The fusing point that does not contain impurity and its purity and be 100% ammonia is-78 ℃, and the fusing point of 30% ammoniacal liquor that is made of ammonia 30 weight % and water 70 weight % is-72 ℃.Therefore, partial condensation by part 2 condenser 3, even in the ammonia liquor that the condensation as liquid composition obtains, contain under the situation of moisture with high density, if the temperature of the wall of part 2 condenser 3 then can not solidified curing by condensation as the ammonia liquor that liquid composition obtains yet near-70 ℃.In addition, even the moisture in the thick ammonia of gas shape reduces the pressure of the thick ammonia of gas shape under state of thermal isolation and make its temperature reduce, make a part of condensation of the thick ammonia of gas shape, also can access identical effect.
Part 2 condenser 3 and part 1 condenser 5 are different aspect the partial condensation conditions such as partial condensation temperature, pressure, partial condensation rate, and in addition, other side all similarly constitutes.As the formation of the thick ammonia of gas shape being carried out part 2 condenser 3 and the part 1 condenser 5 of partial condensation, be broadly divided into piston flow (Piston flow) mode and complete hybrid mode.Piston stream mode refers to following mode: the thick ammonia of gas shape flows along constant direction in part 2 condenser 3 or part 1 condenser 5, liquefied by partial condensation gradually simultaneously, not by partial condensation and the impurity concentration in the mobile gaseous ammonia if the kind of impurity to be the situation of the high hydrocarbon of low-boiling point gas or volatility (carbonatoms is 1～8 hydrocarbon) etc. next increases gradually, if reduce gradually in that the situation of the low hydrocarbon (carbonatoms is the hydrocarbon more than 9) of moisture or volatility etc. is next.On the other hand, hybrid mode refers to following mode fully: when the thick ammonia of gas shape is directed to part 2 condenser 3 or part 1 condenser 5, immediately with part 2 condenser 3 or part 1 condenser 5 in the gaseous ammonia that contains impurity evenly mix, cause partial condensation by this mixed uniformly gaseous ammonia.
The big difference of this two mode is as follows: for example, when the kind of impurity was the high hydrocarbon of low-boiling point gas or volatility etc., the impurity concentration that piston stream mode contains in the ammonia liquor that the upstream side of air-flow generates by partial condensation was low, increase gradually along with flowing to the impurity concentration of carrying out in the ammonia liquor of partial condensation in the downstream side.Relative therewith, fully in the hybrid mode, which part of no matter getting fractional distillating tube all can obtain containing the ammonia liquor of the impurity of same concentrations by the partial condensation operation.
In the present embodiment, as the formation of part 2 condenser 3 and part 1 condenser 5, can adopt piston stream mode and the complete arbitrary mode in the hybrid mode, but more preferably piston stream mode.
Adopted the formation of the part 2 condenser 3 of piston stream mode and part 1 condenser 5 shown in Fig. 2,3.Fig. 2 is the figure of the formation of expression part 2 condenser 3.Fig. 3 is the figure of the formation of expression part 1 condenser 5.As indicated above, part 2 condenser 3 and part 1 condenser 5 are different aspect the partial condensation conditions such as partial condensation temperature, pressure, partial condensation rate, and in addition, other side all similarly constitutes.Adopted part 2 condenser 3 and the part 1 condenser 5 of piston stream mode to constitute by comprising following apparatus: the fractional distillating tube body 31 that gas shape ammonia flows through, 51 and fractional distillating tube body 31,51 connected the pipeline that flows through refrigeration agent 32,52 arrange at axis direction.The refrigeration agent of the gas shape ammonia cooling of flowing through in the fractional distillating tube body 31,51 is flow through.
Be respectively arranged with the gas inlet opening part 33,53, gas outlet opening portion 34,54 and the liquid outlet opening portion 35,55 that connect along thickness direction on the fractional distillating tube body 31,51.By part 2 condenser 3 and part 1 condenser 5 gas shape ammonia is directed in the fractional distillating tube body 31,51 from gas inlet opening part 33,53.The refrigeration agent that gas shape ammonia utilization in gas inlet opening part 33,53 is directed into fractional distillating tube body 31,51 is flow through from pipeline 32,52 cools off, carry out partial condensation thus and a part is condensed, uncooled gas phase composition is that uncooled ammonia is that condensation ammonia is discharged from from liquid outlet opening portion 35,55 from the liquid composition that gas outlet opening portion 34,54 is discharged from, condensation obtains.
In addition, as long as the flow direction of the flow direction of the gas shape ammonia that flows through in the fractional distillating tube body 31,51 and the refrigeration agent that flows through in the pipeline 32,52 can access partial condensation effect efficiently, be not particularly limited, can be equidirectional, also can be in the other direction.In addition, pipeline 32,52 can be arranged in the fractional distillating tube body 31,51, also can arrange according to the mode of the periphery of cover part condenser body 31,51.
In addition, with the gas inlet opening part 33 in the gas shape ammonia lead-in portion condenser body 31,51,53 and condensation ammonia can be positioned at the position of the flow direction that departs from fractional distillating tube body 31,51 gas shape ammonia from the position of fractional distillating tube body 31, the 51 liquid outlet opening portions 35,55 that discharge, also can so that liquid outlet opening portion 35,55 be positioned at gas inlet opening part 33,53 under.
In the part 2 condenser 3 and part 1 condenser 5 of piston stream mode, no matter in which part of fractional distillating tube, the concentration of the impurity that contains in the condensation ammonia that obtains by the partial condensation condensation and the impurity concentration near the gasiform uncooled ammonia it exist with constant partition ratio.As mentioned above, practical situation are to infer to cause dynamic separation by partial condensation, and the hydrocarbon that contains in the condensation ammonia that obtains by the partial condensation condensation is more much lower than the concentration of prediction.In addition, as mentioned above, remove rapidly from part 2 condenser 3 and part 1 condenser 5 by the condensation ammonia that the partial condensation condensation obtains.For this reason, for being become, condensation ammonia is easy to flow towards liquid outlet opening portion 35,55, part 2 condenser 3 and part 1 condenser 5 are tilted, perhaps different according to the structure of part 2 condenser 3 and part 1 condenser 5, make part 2 condenser 3 and part 1 condenser 5 parallel setting vertically, gas inlet opening part 33,53 is configured in the upper side of vertical direction, and liquid outlet opening portion 35,55 is configured in the lower side of vertical direction.
In the part 2 condenser 3 and part 1 condenser 5 of piston stream mode, flowing of gaseous ammonia in the fractional distillating tube body 31,51 is laminar flow, begin to take place condensation from the part near wall, although therefore the centre portions at air-flow is the impurity concentration near thick ammonia composition, but be concentrated in the partial impurities near wall, can access the condensation ammonia that forms from this concentrating part condensation sometimes.Impurity concentration in the liquid condensation ammonia that so obtains can be contemplated for high value.In order to prevent the generation of this phenomenon, can dispose in the fractional distillating tube body 31,51 and upset the interference plate that flows of gaseous ammonia or the obstacle of bead.Thus, the movement disorder of fractional distillating tube body 31, the gaseous ammonia in 51, so near the impurity concentration of the central part of the air-flow of gaseous ammonia and wall portion is identical.
In addition, in the part 2 condenser 3 and part 1 condenser 5 of piston stream mode, by the carbonatoms in the condensation ammonia be the impurity that constitutes of 1～8 hydrocarbon concentration gas inlet opening part 33,53 near low, increase along with flowing to liquid outlet opening portion 35,55.
In addition, be directed into the fractional distillating tube body 31 of part 2 condenser 3 and part 1 condenser 5, the gas shape ammonia in 51 along with the progress of the condensation of being undertaken by partial condensation, its gas volume reduces, and therefore the sectional area with fractional distillating tube body 31, cross section that 51 axis direction is vertical reduces along with the progress of the condensation of gas shape ammonia.Thus, gas shape ammonia and fractional distillating tube body 31,51 wall contact well, therefore obtain high refining effect.Such effect also can realize by being set to following formation: a plurality of part 2 condensers 3 or part 1 condenser 5 are connected in series respectively, little equipment as the fractional distillating tube in the downstream side of the flow direction that is disposed at gas shape ammonia is set.
Fractional distillating tube as the piston stream mode that constitutes part 2 condenser 3 and part 1 condenser 5 can list for example votator, plate-fin heat exchanger, dual-tubes heat exchanger, multitube drum type brake interchanger (shell-and-tube (shell and tube) interchanger), multi-layer tube formula interchanger, vortex tubular heat exchanger, vortex plate-fin heat exchanger etc.Wherein, preferred especially dual-tubes heat exchanger, multitube drum type brake interchanger (tube and shell heat exchanger), multi-layer tube formula interchanger etc.In tube and shell heat exchanger, flow at gas shape ammonia under the situation of pipe (tube) side, perhaps under gas shape ammonia flows to situation in the trunk portion, all can obtain suitable result under arbitrary situation.
Get back to Fig. 1, the formation of the ammonia refining system 100 of present embodiment is described.As indicated above, ammonia refining system 100 constitutes by comprising following apparatus: raw material stores jar the 1, the 1st vaporizer 2, part 2 condenser 3, part 1 condenser 5, the 2nd withdrawing can 4, the 1st withdrawing can 6, the 2nd vaporizer 7, the 1st adsorption tower 8 and the 2nd adsorption tower 9, complete condenser 10 and goods jar 30.
Raw material stores jar 1 and is used for storing thick ammonia.Raw material store jar 1 so long as the insulating container with resistance to pressure and erosion resistance just, be not particularly limited.This raw material stores jar 1 the form of thick ammonia with ammonia liquor is stored, and is that the mode of controlled condition is controlled according to temperature and pressure.
In the ammonia refining system 100, store jar 1 from raw material thick ammonia extracted out with gas form, perhaps make the thick ammoniaization of extracting out with liquid form and be supplied to part 2 condenser 3.In either case, raw material stores jar 1 needs all to keep-up pressure that thick ammonia is extracted out, as its usual method, following method etc. is arranged: thermals source such as heat pipe are configured in raw material store in the jar 1, perhaps will import to the liquid thick ammonia heating in the outer reboiler of installing, pressurize thereby with the pressure of the thick ammonia of gas shape that generates raw material is stored jar 1.In the present embodiment, store jar 1 from raw material thick ammonia extracted out with liquid form, feed the 1st vaporizer 2 thick ammonia of formation gas shape that gasify by making this liquid thick ammonia, the thick ammonia of this gas shape is delivered to part 2 condenser 3 and part 1 condenser 5.
The 1st pipe arrangement 11 is connected raw material and stores between jar the 1 and the 1st vaporizer 2, from raw material store jar 1 liquid thick ammonia of deriving from the 1st pipe arrangement 11 by being supplied to the 1st vaporizer 2.
The 1st pipe arrangement 11 is provided with the 1st valve 11a for the stream of the 1st pipe arrangement 11 is open or sealing.When storing jar 1 liquid thick ammonia of deriving from raw material when being supplied to the 1st vaporizer 2, the 1st valve 11a is open, and liquid thick ammonia stores jar 1 from raw material and flows through in the 1st pipe arrangement 11 towards the 1st vaporizer 2.
Storing jar 1 liquid thick ammonia that is supplied to the 1st vaporizer 2 from raw material is vaporized the 1st vaporizer 2.The thick ammonia of gas shape that gasification obtains in the 1st vaporizer 2 is supplied to part 2 condenser 3.The 2nd pipe arrangement 12 is connected between the 1st vaporizer 2 and the part 2 condenser 3, the thick ammonia of gas shape of deriving from the 1st vaporizer 2 from the 2nd pipe arrangement 12 by being supplied to part 2 condenser 3.
The 2nd pipe arrangement 12 is provided with the 2nd valve 12a for the stream of the 2nd pipe arrangement 12 is open or sealing.When the thick ammonia of gas shape of deriving from the 1st vaporizer 2 was supplied to part 2 condenser 3, the 2nd valve 12a was open, and the thick ammonia of gas shape flows through in the 2nd pipe arrangement 12 from the 1st vaporizer 2 towards part 2 condenser 3.
Part 2 condenser 3 is separated into gas phase composition and liquid composition by the thick ammonia of gas shape that obtains of gasification in the 1st vaporizer 2 is carried out partial condensation, thereby the impurity that the volatility that contains in the thick ammonia is low (moisture and carbonatoms are the hydrocarbon more than 9) separates as liquid composition and removes.Utilize liquid composition that part 2 condenser 3 separates, be that the liquid composition that the low impurity of volatility has concentrated passes through from the 4th pipe arrangement 14 that is provided with the 4th valve 14a that is connected with part 2 condenser 3, store in the 2nd withdrawing can 4.Storing liquid composition at the 2nd withdrawing can 4 can also be back to raw material and store jar 1 and again as the raw material ammonia utilization.
In addition, utilize gas phase composition that part 2 condenser 3 separates, be that the gas shape ammonia that the content of the low impurity of volatility has reduced is supplied to part 1 condenser 5.The 3rd pipe arrangement 13 is connected between part 2 condenser 3 and the part 1 condenser 5, the gas shape ammonia of deriving from part 2 condenser 3 from the 3rd pipe arrangement 13 by being supplied to part 1 condenser 5.
The 3rd pipe arrangement 13 is provided with the 3rd valve 13a for the stream of the 3rd pipe arrangement 13 is open or sealing.When the gas shape ammonia of deriving from part 2 condenser 3 was supplied to part 1 condenser 5, the 3rd valve 13a was open, and gas shape ammonia flows through in the 3rd pipe arrangement 13 from part 2 condenser 3 towards part 1 condenser 5.
Part 1 condenser 5 is by carrying out partial condensation and be separated into gas phase composition and liquid composition separate the gas shape ammonia removed the low impurity of volatility in part 2 condenser 3, thereby the impurity that the volatility that contains in the ammonia is high (low-boiling point gas and carbonatoms are 1～8 hydrocarbon) separates as gas phase composition and removes.Utilize gas phase composition that part 1 condenser 5 separates, be the gas phase composition that concentrated of the high impurity of volatility from the 6th pipe arrangement 16 that is provided with the 6th valve 16a that is connected with part 1 condenser 5 by being disposed to the system outside.
In addition, utilize liquid composition that part 1 condenser 5 separates, be that the condensation ammonia (ammonia liquor) that the content of the high impurity of volatility has reduced passes through from the 5th pipe arrangement 15 that is provided with the 5th valve 15a that is connected with part 1 condenser 5, store in the 1st withdrawing can 6.Wherein, open by the 5th valve 15a, the ammonia liquor of utilizing part 1 condenser 5 to separate flows through in the 5th pipe arrangement 15 from part 1 condenser 5 towards the 1st withdrawing can 6.
Here, be piston stream mode by making part 1 condenser 5, when beginning to import new gas shape ammonia from gas inlet opening part 53, the state of the inside of fractional distillating tube body 51 reaches stable needs the short time to finish.In addition, open by the 6th valve 16a, utilize gas phase composition that part 1 condenser 5 separates by gas outlet opening portion 54 from the 6th pipe arrangement 16 by being discharged from, the discharge ratio of this gas phase composition can be determined by the output in the gas outlet opening portion 54, even its discharge ratio is changed, part 1 condenser 5 reaches steady state also only needs the short time to finish.
In addition, part 1 condenser 5 can be a plurality of partial condensation 5a of portion as shown in Figure 4, the formation that 5b, 5c are connected in series.The figure of the formation of the part 1 condenser 5 that Fig. 4 is connected in series for a plurality of partial condensation of expression portion.So, by part 1 condenser 5 being arranged to the formation that a plurality of partial condensation 5a of portion, 5b, 5c are connected in series, can in each several part condensation part 5a, 5b, 5c, make the different multiple ammonia of degree of purity respectively.
In addition, a plurality of partial condensation 5a of portion, 5b, 5c are connected in series and in the part 1 condenser 5 that constitutes, be configured in the 5a of partial condensation portion, 5b, the 5c in the downstream side of the mobile direction of gas shape ammonia along with arrival, the partial condensation temperature is reduced, the concentration of the impurity hydrocarbon that contains in the ammonia liquor that obtains as liquid composition is reduced.
In addition, can also be with the ammonia liquor of in part 1 condenser 5, the separating gasification that stores in the 1st withdrawing can 6, the vapour that this gasification is obtained is back to part 1 condenser 5, implements partial condensation operation (the 3rd partial condensation operation) again at part 1 condenser 5.Thus, can access the ammonia liquor that the content of the high impurity of volatility is further reduced.The vapour that Fig. 5 obtains gasification from the 1st withdrawing can 6 for expression imports the figure of the position of part 1 condenser 5.The vapour that gasification is obtained from the 1st withdrawing can 6 imports the position of part 1 condenser 5 and can suitably set according to the purity as the ammonia liquor of target.Wherein, in part 1 condenser 5, implement the formation that partial condensation is operated again about the ammonia liquor that will store in the 1st withdrawing can 6, in a plurality of partial condensation 5a of portion, 5b, 5c shown in Figure 4 are connected in series the part 1 condenser 5 that forms, also can be suitable for.
In addition, preferably between part 1 condenser 5 and the 1st withdrawing can 6, equaler 6a is set as shown in Figure 6.Fig. 6 is the figure of the syndeton between expression the 1st withdrawing can 6 and the part 1 condenser 5.Equaler 6a is adjusted into all pressures with the pressure of part 1 condenser 5 and the pressure of the 1st withdrawing can 6.So, by between part 1 condenser 5 and the 1st withdrawing can 6, equaler 6a being set, can part 1 condenser 5 be controlled and be imported to the vapour that gasification obtains from the 1st withdrawing can 6.In addition, about the pressure of the ammonia liquor under the low temperature, only significantly change under the situation of difference degree in temperature.Therefore, by between part 1 condenser 5 and the 1st withdrawing can 6, equaler 6a being set, even the pressure in the 1st withdrawing can 6 is lower than under the situation of the pressure in the fractional distillating tube body 51 of part 1 condenser 5, can prevent that also gas phase composition (concentrating has the high impurity of volatility) from flowing into the 1st withdrawing can 6 from part 1 condenser 5.
Above following such part 2 condenser 3 is operated with the continuous partial condensation in the part 1 condenser 5 and be illustrated: will be supplied to part 1 condenser 5 by the gas phase composition that the partial condensation of part 2 condenser 3 is separated, and in part 1 condenser 5, further implement partial condensation.But the ammonia refining system 100 of present embodiment is not limited to so continuous partial condensation operation, also the partial condensation operation of part 2 condenser 3 and part 1 condenser 5 can be implemented in the gradation mode.The gradation mode refers to constitute in the following manner: will temporarily store returnable by the gas phase composition that the partial condensation of part 2 condenser 3 is separated, and then gas phase composition will be supplied to part 1 condenser 5 from this returnable.
In addition, above following formation is illustrated: part 2 condenser 3 and part 1 condenser 5 are connected in series successively, separate as liquid composition by the partial condensation of part 2 condenser 3 impurity that volatility is low and to remove, separate as gas phase composition by the partial condensation of part 1 condenser 5 impurity that volatility is high then and remove.But, the ammonia refining system 100 of present embodiment also can be following formation: part 1 condenser 5 and part 2 condenser 3 are connected in series successively, separate as gas phase composition by the partial condensation of part 1 condenser 5 impurity that volatility is high and to remove, separate as liquid composition by the partial condensation of part 2 condenser 3 impurity that volatility is low then and remove.Wherein, the formation that part 2 condenser 3 and part 1 condenser 5 are set to be connected in series successively is because gas phase is few with the phase change of liquid phase, so more preferably this mode of connection.
The ammonia liquor that stores in the 1st withdrawing can 6 is exported to the 2nd vaporizer 7.The 7th pipe arrangement 17 is connected between the 1st withdrawing can 6 and the 2nd vaporizer 7, the ammonia liquor that derives from the 1st withdrawing can 6 from the 7th pipe arrangement 17 by being supplied to the 2nd vaporizer 7.
The 7th pipe arrangement 17 is provided with the 7th valve 17a for the stream of the 7th pipe arrangement 17 is open or sealing.In the time will being supplied to the 2nd vaporizer 7 from the ammonia liquor that the 1st withdrawing can 6 is derived, the 7th valve 17a is open, and ammonia liquor flows through in the 7th pipe arrangement 17 from the 1st withdrawing can 6 towards the 2nd vaporizer 7.
The ammonia liquor that is supplied to the 2nd vaporizer 7 from the 1st withdrawing can 6 is vaporized the 2nd vaporizer 7.The gas shape ammonia that gasification obtains in the 2nd vaporizer 7 is supplied to the 1st adsorption tower 8.The 8th pipe arrangement 18 is connected between the 2nd vaporizer 7 and the 1st adsorption tower 8, the gas shape ammonia of deriving from the 2nd vaporizer 7 from the 8th pipe arrangement 18 by being supplied to the 1st adsorption tower 8.
The 8th pipe arrangement 18 is provided with the 8th valve 18a for the stream of the 8th pipe arrangement 18 is open or sealing.In the time will being supplied to the 1st adsorption tower 8 from the gas shape ammonia that the 2nd vaporizer 7 is derived, the 8th valve 18a is open, and gas shape ammonia flows through in the 8th pipe arrangement 18 from the 2nd vaporizer 7 towards the 1st adsorption tower 8.That is, part 2 condenser 3 and part 1 condenser 5 and the 1st adsorption tower 8 Jie are connected in series by the 2nd vaporizer 7.
The water adsorption of the denier that the 1st adsorption tower 8 utilizes sorbent material to gasify in the 2nd vaporizer 7 to contain in the gas shape ammonia that obtains is removed.As the sorbent material that is filled to the 1st adsorption tower 8, can list silica gel, aluminum oxide, zeolite 3A, zeolite 4A, zeolite 5A and zeolite 13X etc.In addition, in the 1st adsorption tower 8, the carbonic acid gas absorption of the denier that contains in the gas shape ammonia can also be removed.
The gas shape ammonia that absorption has been removed behind moisture and the carbonic acid gas in the 1st adsorption tower 8 is exported the 2nd adsorption tower 9.The 9th pipe arrangement 19 is connected between the 1st adsorption tower 8 and the 2nd adsorption tower 9, the gas shape ammonia of deriving from the 1st adsorption tower 8 from the 9th pipe arrangement 19 by being supplied to the 2nd adsorption tower 9.
The 9th pipe arrangement 19 is provided with the 9th valve 19a for the stream of the 9th pipe arrangement 19 is open or sealing.In the time will being supplied to the 2nd adsorption tower 9 from the gas shape ammonia that the 1st adsorption tower 8 is derived, the 9th valve 19a is open, and gas shape ammonia flows through in the 9th pipe arrangement 19 from the 1st adsorption tower 8 towards the 2nd adsorption tower 9.
The 2nd adsorption tower 9 utilizes the hydrocarbon absorption of the denier that sorbent material will contain from the gas shape ammonia that the 1st adsorption tower 8 is derived to remove.As the sorbent material that is filled to the 2nd adsorption tower 9, can list gac etc.
The major part of the impurity that contains in the ammonia can be separated with the partial condensation of part 1 condenser 5 by part 2 condenser 3 and removed, be made as the formation that possesses the 1st adsorption tower 8 and the 2nd adsorption tower 9 by the formation with ammonia refining system 100, can access more highly purified ammonia.Wherein, the sorbent material after the use can re-use by heat treated in the 1st adsorption tower 8 and the 2nd adsorption tower 9.
Above following formation is illustrated: part 2 condenser 3, part 1 condenser 5, the 1st adsorption tower 8, the 2nd adsorption tower 9 are connected in series successively, by the partial condensation of part 2 condenser 3 and part 1 condenser 5 impurity is separated and to remove, in the 1st adsorption tower 8 and the 2nd adsorption tower 9, impurity absorption is removed then.But, the ammonia refining system 100 of present embodiment also can be following formation: the 1st adsorption tower 8, the 2nd adsorption tower 9, part 2 condenser 3, part 1 condenser 5 are connected in series successively, in the 1st adsorption tower 8 and the 2nd adsorption tower 9, impurity absorption is removed, by the partial condensation of part 2 condenser 3 and part 1 condenser 5 impurity is separated then and remove.
Absorption has been removed the gas shape ammonia behind the hydrocarbon and has been exported complete condenser 10 in the 2nd adsorption tower 9.The 10th pipe arrangement 20 is connected between the 2nd adsorption tower 9 and the complete condenser 10, the gas shape ammonia of deriving from the 2nd adsorption tower 9 from the 10th pipe arrangement 20 by being supplied to complete condenser 10.
The 10th pipe arrangement 20 is provided with the 10th valve 20a for the stream of the 10th pipe arrangement 20 is open or sealing.In the time will being supplied to complete condenser 10 from the gas shape ammonia that the 2nd adsorption tower 9 is derived, the 10th valve 20a is open, and gas shape ammonia flows through in the 10th pipe arrangement 20 from the 2nd adsorption tower 9 towards complete condenser 10.
Complete condenser 10 will be from the gas shape ammoniacal liquorization of the 2nd adsorption tower 9 derivation.Ammonia by complete condenser 10 liquefaction is exported goods jar 30.The 11st pipe arrangement 21 is connected between complete condenser 10 and the goods jar 30, the liquid ammonia of deriving from complete condenser 10 from the 11st pipe arrangement 21 by being supplied to goods jar 30.
The 11st pipe arrangement 21 is provided with the 11st valve 21a for the stream of the 11st pipe arrangement 21 is open or sealing.In the time will being supplied to goods jar 30 from the liquid ammonia that complete condenser 10 is derived, the 11st valve 21a is open, and the ammonia through liquefying flows through in the 11st pipe arrangement 21 from complete condenser 10 towards goods jar 30.So, the ammonia after goods jar 30 is made with extra care with storing high purity.
Fig. 7 is the figure of the formation of the ammonia refining system 200 of expression the 2nd embodiment of the present invention.The ammonia refining system 200 of present embodiment is similar with ammonia refining system 100 mentioned above, about corresponding part mark identical label symbol and omission explanation.
Ammonia refining system 200 constitutes in the following manner: part 2 condenser 3, part 1 condenser 5, the 1st adsorption tower 8, the 2nd adsorption tower 9 and be connected in series successively as the 3rd fractional distillating tube 201 of the 3rd partial condensation portion.
In the ammonia refining system 200, open by the 12nd valve 202a, the ammonia of having been removed impurity by part 2 condenser 3, part 1 condenser 5, the 1st adsorption tower 8 and the 2nd adsorption tower 9 by the 2nd adsorption tower 9 from the 12nd pipe arrangement 202 by being supplied to the 3rd fractional distillating tube 201.
The 3rd fractional distillating tube 201 is separated into gas phase composition and liquid composition by the gas shape ammonia of deriving from the 2nd adsorption tower 9 is carried out partial condensation, thereby the impurity that the volatility of the denier that contains in the ammonia is high (low-boiling point gas and carbonatoms are 1～8 hydrocarbon) separates as gas phase composition and removes.The gas phase composition that separates by the 3rd fractional distillating tube 201, namely concentrate the high impurity of volatility is arranged gas phase composition from the 13rd pipe arrangement 203 that is provided with the 13rd valve 203a that is connected with the 3rd fractional distillating tube 201 by being discharged into the system outside.
In addition, the liquid composition that separates by the 3rd fractional distillating tube 201, be that the condensation ammonia (ammonia liquor) that the content of the high impurity of volatility has reduced passes through from the 14th pipe arrangement 204 that is provided with the 14th valve 204a that is connected with the 3rd fractional distillating tube 201, store in goods jar 30.
So remove owing to the impurity of not removing fully in part 2 condenser 3, part 1 condenser 5, the 1st adsorption tower 8 and the 2nd adsorption tower 9 being separated as gas phase composition in the ammonia refining system 200 that constitutes, therefore can access more highly purified ammonia.
Fig. 8 is the figure of the formation of the ammonia refining system 300 of expression the 3rd embodiment of the present invention.The ammonia refining system 300 of present embodiment is similar with ammonia refining system 100 mentioned above, for the part mark of correspondence identical label symbol and omission explanation.
Ammonia refining system 300 constitutes in the following manner: part 2 condenser 3, the 1st adsorption tower 8, the 2nd adsorption tower 9 and part 1 condenser 5 are connected in series successively.In the ammonia refining system 300, the gas shape ammonia of having removed impurity by part 2 condenser 3 is open by the 15th valve 301a, from the 15th pipe arrangement 301 by being supplied to the 1st adsorption tower 8, then from the 9th pipe arrangement 19 by being supplied to the 2nd adsorption tower 9, utilize sorbent material that impurity absorption is removed.So, open by the 16th valve 302a, the gas shape ammonia of deriving from the 2nd adsorption tower 9 from the 16th pipe arrangement 302 by being supplied to part 1 condenser 5.
Part 1 condenser 5 is separated into gas phase composition and liquid composition by the gas shape ammonia of deriving from the 2nd adsorption tower 9 is carried out partial condensation, thereby the impurity that the volatility of the denier that contains in the ammonia is high (low-boiling point gas and carbonatoms are 1～8 hydrocarbon) separates as gas phase composition and removes.The gas phase composition that separates by part 1 condenser 5, be the gas phase composition that concentrated of the high impurity of volatility from the 18th pipe arrangement 304 that is provided with the 18th valve 304a that is connected with part 1 condenser 5 by being discharged into the system outside.
In addition, the liquid composition that separates by part 1 condenser 5, be that the condensation ammonia (ammonia liquor) that the content of the high impurity of volatility has reduced passes through from the 17th pipe arrangement 303 that is provided with the 17th valve 303a that is connected with part 1 condenser 5, store in goods jar 30.Wherein, open by the 17th valve 303a, the ammonia liquor of separating by part 1 condenser 5 flows through in the 17th pipe arrangement 303 from part 1 condenser 5 towards goods jar 30.
Fig. 9 is the figure of the formation of the ammonia refining system 400 of expression the 4th embodiment of the present invention.The ammonia refining system 400 of present embodiment is similar with ammonia refining system 100 mentioned above, for the part mark of correspondence identical label symbol and omission explanation.
Ammonia refining system 400 constitutes in the following manner: the 1st adsorption tower 8, the 2nd adsorption tower 9 and part 1 condenser 5 are connected in series successively.Ammonia refining system 400 is constituted as and makes it possible to store jar 1 from raw material thick ammonia extracted out with gas and this two states of liquid.
The 19th pipe arrangement 401 that is provided with the 19th valve 401a and the 20th valve 401b is connected raw material and stores between jar the 1 and the 1st adsorption tower 8, under the 19th valve 401a and the 20th valve 401b opened state, from raw material store jar 1 thick ammonia of gas shape of deriving from the 19th pipe arrangement 401 by being supplied to the 1st adsorption tower 8.
In addition, the 1st pipe arrangement 11 that is provided with the 1st valve 11a is connected raw material and stores between jar the 1 and the 1st vaporizer 2, under the 1st valve 11a opened state, from raw material store jar 1 liquid thick ammonia of deriving from the 1st pipe arrangement 11 by being supplied to the 1st vaporizer 2.The liquid thick ammonia that is supplied to the 1st vaporizer 2 gasifies in the 1st vaporizer 2.Being connected with on the 1st vaporizer 2 becomes the stream that gasification obtains in the 1st vaporizer 2 the thick ammonia of gas shape flows towards the 19th pipe arrangement 401 and the 20th pipe arrangement 402 that is provided with the 21st valve 402a.The 20th pipe arrangement 402 is connected between the 19th valve 401a and the 20th valve 401b on the 19th pipe arrangement 401.Under the 19th valve 401a sealing, the 20th valve 401b and the 21st valve 402a opened state, the thick ammonia of gas shape of deriving from the 1st vaporizer 2 from the 20th pipe arrangement 402 and the 19th pipe arrangement 401 by being supplied to the 1st adsorption tower 8.
In the ammonia refining system 400, the gas shape ammonia that is supplied to the 1st adsorption tower 8 after from the 9th pipe arrangement 19 by being supplied to the 2nd adsorption tower 9, in the 1st adsorption tower 8 and the 2nd adsorption tower 9, utilize sorbent material that impurity absorption is removed.So, open by the 22nd valve 403a, the gas shape ammonia of deriving from the 2nd adsorption tower 9 from the 21st pipe arrangement 403 by being supplied to part 1 condenser 5.
Part 1 condenser 5 is separated into gas phase composition and liquid composition by the gas shape ammonia of deriving from the 2nd adsorption tower 9 is carried out partial condensation, thereby the impurity that the volatility of the denier that contains in the ammonia is high (low-boiling point gas and carbonatoms are 1～8 hydrocarbon) separates as gas phase composition and removes.The gas phase composition that separates by part 1 condenser 5, be the gas phase composition that concentrated of the high impurity of volatility from the 6th pipe arrangement 16 that is provided with the 6th valve 16a that is connected with part 1 condenser 5 by being discharged to the system outside.
In addition, the liquid composition that separates by part 1 condenser 5, be that the condensation ammonia (ammonia liquor) that the content of the high impurity of volatility has reduced passes through from the 22nd pipe arrangement 404 that is provided with the 23rd valve 404a that is connected with part 1 condenser 5, store in goods jar 30.Wherein, open by the 23rd valve 404a, the ammonia liquor of separating by part 1 condenser 5 flows through in the 22nd pipe arrangement 404 from part 1 condenser 5 towards goods jar 30.So, the ammonia after making with extra care in the goods jar 30 with storing high purity.
Figure 10 is the figure of the formation of the ammonia refining system 500 of expression the 5th embodiment of the present invention.The ammonia refining system 500 of present embodiment is similar with ammonia refining system 100 mentioned above, for the part mark of correspondence identical label symbol and omission explanation.
In the ammonia refining system 500, the 1st adsorption tower 8, the 2nd adsorption tower 9, part 2 condenser 3 and part 1 condenser 5 are connected in series successively.
In the ammonia refining system 500, under the 1st valve 11a opened state, from raw material store jar 1 liquid thick ammonia of deriving from the 1st pipe arrangement 11 by being supplied to the 1st vaporizer 2.The liquid thick ammonia that is supplied to the 1st vaporizer 2 gasifies in the 1st vaporizer 2.Being connected with on the 1st vaporizer 2 becomes the stream that gasification obtains in the 1st vaporizer 2 the thick ammonia of gas shape flows towards the 1st adsorption tower 8 and the 23rd pipe arrangement 501 that is provided with the 24th valve 501a.Under the 24th valve 501a opened state, the thick ammonia of gas shape of deriving from the 1st vaporizer 2 from the 23rd pipe arrangement 501 by being supplied to the 1st adsorption tower 8.
In the ammonia refining system 500, the gas shape ammonia that is supplied to the 1st adsorption tower 8 after from the 9th pipe arrangement 19 by being supplied to the 2nd adsorption tower 9, in the 1st adsorption tower 8 and the 2nd adsorption tower 9, utilize sorbent material that impurity absorption is removed.So, open by the 25th valve 502a, the gas shape ammonia of deriving from the 2nd adsorption tower 9 from the 24th pipe arrangement 502 by being supplied to part 2 condenser 3.
Part 2 condenser 3 carries out partial condensation by the gas shape ammonia that impurity has been removed in absorption in the 1st adsorption tower 8 and the 2nd adsorption tower 9 and is separated into gas phase composition and liquid composition, thereby the impurity that the volatility that contains in the ammonia is low (moisture and carbonatoms are the hydrocarbon more than 9) separates as liquid composition and removes.The liquid composition that separates by part 2 condenser 3, be that the liquid composition that the low impurity of volatility has concentrated passes through from the 4th pipe arrangement 14 that is provided with the 4th valve 14a that is connected with part 2 condenser 3, store in the 2nd withdrawing can 4.The liquid composition that stores in the 2nd withdrawing can 4 can also return raw material and store jar 1 and again as the raw material ammonia utilization.
In addition, under the 3rd valve 13a opened state, the gas phase composition that separates by part 2 condenser 3, be the gas shape ammonia that reduced of the content of the low impurity of volatility from the 3rd pipe arrangement 13 by being supplied to part 1 condenser 5.
Part 1 condenser 5 is by carrying out partial condensation and be separated into gas phase composition and liquid composition separate the gas shape ammonia removed the low impurity of volatility in part 2 condenser 3, thereby the impurity that the volatility of the denier that contains in the ammonia is high (low-boiling point gas and carbonatoms are 1～8 hydrocarbon) separates as gas phase composition and removes.The gas phase composition that separates by part 1 condenser 5, be the gas phase composition that concentrated of the high impurity of volatility from the 6th pipe arrangement 16 that is provided with the 6th valve 16a that is connected with part 1 condenser 5 by being discharged into the system outside.
In addition, the liquid composition that separates by part 1 condenser 5, be that the condensation ammonia (ammonia liquor) that the content of the high impurity of volatility has reduced passes through from the 25th pipe arrangement 503 that is provided with the 26th valve 503a that is connected with part 1 condenser 5, store in goods jar 30.Wherein, open by the 26th valve 503a, the ammonia liquor of separating by part 1 condenser 5 flows through in the 25th pipe arrangement 503 from part 1 condenser 5 towards goods jar 30.So, the ammonia after making with extra care in the goods jar 30 with storing high purity.
Figure 11 is the figure of the formation of the ammonia refining system 600 of expression the 6th embodiment of the present invention.The ammonia refining system 600 of present embodiment is similar with ammonia refining system 100 mentioned above, for the part mark of correspondence identical label symbol and omission explanation.
Ammonia refining system 600 is connected in series to constitute with part 1 condenser 5 and the 1st adsorption tower 8 successively.In addition, ammonia refining system 600 is constituted as and makes it possible to store jar 1 from raw material thick ammonia extracted out with gas and this two states of liquid.
The 26th pipe arrangement 601 that is provided with the 27th valve 601a and the 28th valve 601b is connected raw material and stores between jar 1 and the part 1 condenser 5, under the 27th valve 601a and the 28th valve 601b opened state, from raw material store jar 1 thick ammonia of gas shape of deriving from the 26th pipe arrangement 601 by being supplied to part 1 condenser 5.
In addition, the 1st pipe arrangement 11 that is provided with the 1st valve 11a is connected raw material and stores between jar the 1 and the 1st vaporizer 2, under the 1st valve 11a opened state, from raw material store jar 1 liquid thick ammonia of deriving from the 1st pipe arrangement 11 by being supplied to the 1st vaporizer 2.The liquid thick ammonia that is supplied to the 1st vaporizer 2 gasifies in the 1st vaporizer 2.Being connected with on the 1st vaporizer 2 becomes the stream that gasification obtains in the 1st vaporizer 2 the thick ammonia of gas shape flows towards the 26th pipe arrangement 601 and the 27th pipe arrangement 602 that is provided with the 29th valve 602a.The 27th pipe arrangement 602 is connected between the 27th valve 601a and the 28th valve 601b on the 26th pipe arrangement 601.Under the 27th valve 601a sealing, the 28th valve 601b and the 29th valve 602a opened state, the thick ammonia of gas shape of deriving from the 1st vaporizer 2 from the 27th pipe arrangement 602 and the 26th pipe arrangement 601 by being supplied to part 1 condenser 5.
Part 1 condenser 5 is separated into gas phase composition and liquid composition by the thick ammonia of gas supplied shape is carried out partial condensation, thereby the impurity that the volatility that contains in the thick ammonia is high (low-boiling point gas and carbonatoms are 1～8 hydrocarbon) separates as gas phase composition and removes.Utilize gas phase composition that part 1 condenser 5 separates, be the gas phase composition that concentrated of the high impurity of volatility from being connected with part 1 condenser 5 and being provided with the 6th pipe arrangement 16 of the 6th valve 16a by being discharged into the system outside.
In addition, utilize liquid composition that part 1 condenser 5 separates, to be the condensation ammonia (ammonia liquor) that reduced of the content of the high impurity of volatility pass through from being connected with part 1 condenser 5 and being provided with the 5th pipe arrangement 15 of the 5th valve 15a, store in the 1st withdrawing can 6.Wherein, open by the 5th valve 15a, the ammonia liquor of utilizing part 1 condenser 5 to separate flows through in the 5th pipe arrangement 15 from part 1 condenser 5 towards the 1st withdrawing can 6.
Under the 7th valve 17a opened state, store ammonia liquor at the 1st withdrawing can 6 from the 7th pipe arrangement 17 by being supplied to the 2nd vaporizer 7.The ammonia liquor that is supplied to the 2nd vaporizer 7 from the 1st withdrawing can 6 gasifies the 2nd vaporizer 7.Under the 8th valve 18a opened state, in the 2nd vaporizer 7 the gas shape ammonia that obtains of gasification from the 8th pipe arrangement 18 by being supplied to the 1st adsorption tower 8.
The impurity that the 1st adsorption tower 8 utilizes sorbent material to gasify in the 2nd vaporizer 7 to contain in the gas shape ammonia that obtains, namely in part 1 condenser 5, separate the impurity absorption of removing fully and remove.Be filled with stacked state in the 1st adsorption tower 8 moisture is had the sorbent material (for example silica gel, aluminum oxide, zeolite 3A, zeolite 4A, zeolite 5A and zeolite 13X etc.) of high adsorptive power and the sorbent material (for example gac etc.) that hydrocarbon is had high adsorptive power.
The gas shape ammonia behind the impurity has been removed in absorption in the 1st adsorption tower 8 exported to complete condenser 10.The 28th pipe arrangement 603 that is provided with the 30th valve 603a is connected between the 1st adsorption tower 8 and the complete condenser 10, the gas shape ammonia of deriving from the 1st adsorption tower 8 from the 28th pipe arrangement 603 by being supplied to complete condenser 10.
Complete condenser 10 will be from the gas shape ammoniacal liquorization of the 1st adsorption tower 8 derivation.Utilize the ammonia of complete condenser 10 liquefaction to be exported to goods jar 30.The 11st pipe arrangement 21 that is provided with the 11st valve 21a is connected between complete condenser 10 and the goods jar 30, the liquid ammonia of deriving from complete condenser 10 from the 11st pipe arrangement 21 by being supplied to goods jar 30.So, the ammonia after making with extra care in the goods jar 30 with storing high purity.
About above-mentioned ammonia refining system 100,200,300,400,500, be illustrated to possess for dewatered the 1st adsorption tower 8 of absorption with for the example that constitutes of absorption except the 2nd adsorption tower 9 of dealkylation.
Moisture for except denier residual in the deammoniation in most cases needs to be provided for adsorbing dewatered the 1st adsorption tower 8, but does not in most cases need to be provided for adsorbing the 2nd adsorption tower 9 except dealkylation.For example, the situation that the starting point concentration of the hydrocarbon that contains in thick ammonia is low is inferior, separates with the partial condensation of part 1 condenser 5 by part 2 condenser 3 and removes, and hydrocarbon fully can be removed, and in this case, does not need to arrange the 2nd adsorption tower 9.In addition, as indicated above, even under the high situation of the hydrocarbon concentration in the thick ammonia of raw material, also can the hydrocarbon concentration in the ammonia be reduced by repeatedly carrying out partial condensation, therefore do not need to arrange the 2nd adsorption tower 9 in this case yet.But, the partial condensation operation is being carried out 1 time, still under the residual situation about having as the hydrocarbon of impurity, remove by the hydrocarbon absorption of in the 2nd adsorption tower 9, carrying out in the ammonia liquor that obtains after the partial condensation, can under the situation of the rate of recovery that does not reduce ammonia, obtain highly purified ammonia.
In addition, in the ammonia refining system 100,200,300,400,500,600 of present embodiment, the order of connection of part 2 condenser 3, part 1 condenser 5, the 1st adsorption tower 8 and the 2nd adsorption tower 9 is unrestricted.
In addition, in the above-mentioned ammonia refining system 100,200,600, behind feasible will the 2nd vaporizer 7, the gasification from the ammonia liquor that the 1st withdrawing can 6 is derived, gas shape ammonia is directed into the 1st adsorption tower 8.But, in the ammonia refining system 100,200,600 of present embodiment, also can not make the ammonia liquor gasification that stores in the 1st withdrawing can 6 and be directed into the 1st adsorption tower 8 with the state of ammonia liquor.
Embodiment
Below the present invention describes in further detail based on embodiment, but the present invention is not limited in these embodiment.
(embodiment 1)
The thick ammonia of＜raw material＞
With respectively with the concentration shown in the table 3 contain hydrogen, nitrogen, oxygen, argon gas, carbon monoxide and carbonic acid gas as low-boiling point gas, as the high hydrocarbon of volatility methane, ethane, propane, normal butane, Skellysolve A, normal hexane, normal heptane, octane, as the ammonia of the n-decane of the low hydrocarbon of volatility and moisture as the thick ammonia of raw material, make with extra care experiment.In addition, normal hexane, normal heptane, octane, n-decane are added in the raw material, carry out concentration adjustment.
＜ammonia refining system＞
Use ammonia refining system 100 shown in Figure 1.Part 2 condenser 3 is the condenser of following shell-and-tube type: the diameter of fractional distillating tube body 31 is that 100mm, length are 500mm, and wherein the diameter that refrigeration agent passed through is 14 of pipeline 32 configurations of 10mm.In addition, the liquid outlet opening portion 35 of part 2 condenser 3 is configured in than gas inlet opening part 33 more by the lower side of vertical direction, and from horizontal direction 5 degree that tilt.Part 1 condenser 5 is the condenser of following shell-and-tube type: the diameter of fractional distillating tube body 51 is that 100mm, length are 500mm, and wherein the diameter that refrigeration agent passed through is 14 of pipeline 52 configurations of 10mm.In addition, the liquid outlet opening portion 55 of part 1 condenser 5 is configured in than gas inlet opening part 53 more by the lower side of vertical direction, and from horizontal direction 5 degree that tilt.
The 1st adsorption tower 8 uses respectively and has filled zeolite 13X(F-9, TOSOH corporate system as 30mm, length as the upstream side of the tower of 1000mm at diameter with identical volume), filled zeolite 3A(A-3, TOSOH corporate system in the downstream side) adsorption tower that forms.The 2nd adsorption tower 9 uses at diameter and has filled the adsorption tower that gac (KURARAY GG, KURARAY CHEMICAL corporate system) forms in as 30mm, the tower of length as 500mm.
Store jar 1 liquid thick ammonia at raw material and import to the 1st vaporizer 2 that is heated to 150 ℃ and make its gasification by storing.The thick ammonia of the gas shape speed with per minute 100mL under standard state that obtains that so gasifies is directed into part 2 condenser 3.Making the absolute pressure in the part 2 condenser 3 is 0.30MPa.In addition ,-15 ℃ water coolant is circulated in pipeline 32.In the part 2 condenser 3 that so constitutes, make 5% condensation of ammonia, the condensation ammonia that condensation obtains is discharged fast from liquid outlet opening portion 35.
Making the absolute pressure in the part 1 condenser 5 is 0.20MPa.In addition ,-30 ℃ water coolant is circulated in pipeline 52.In the part 1 condenser 5 that so constitutes, make 95% condensation of ammonia, the condensation ammonia that condensation obtains is derived fast from liquid outlet opening portion 35.
Be directed into the 2nd vaporizer 7 that is heated to 150 ℃ by the partial condensation that will utilize part 1 condenser 5 as the condensation ammonia that liquid composition obtains and make its gasification.Be to import to the 1st adsorption tower 8 and the 2nd adsorption tower 9 under the 0.6MPa with gas shape ammonia of obtaining of gasification like this in absolute pressure.Ventilation speed is per minute 90mL under the standard state.
＜experimental result＞
After importing from from the thick ammonia of gas shape to part 2 condenser 3 began 2 hours, part 2 condenser 3 and part 1 condenser 5 reached steady state.The thick ammonia of analytical gas shape to the importing of part 2 condenser 3 begin the phlegma (liquid composition) of deriving from part 2 condenser 3 after 5 hours, the uncondensed gas (gas phase composition) that derives from part 2 condenser 3, the impurity concentration (mol-ppm) of the outlet of the outlet of the phlegma (liquid composition) of deriving from part 1 condenser 5, the 1st adsorption tower 8 and the 2nd adsorption tower 9.Analytical results is shown in table 3.Wherein, about analytical equipment, hydro carbons uses GC-FID(GC-2014, Shimadzu Seisakusho Ltd.'s system with analytical equipment), moisture uses optical cavity ring-down spectrum analysis device (HALO, Tiger Optics corporate system) with analytical equipment.
[table 3]
Figure BDA00003361512800341
From the analytical results of table 3 as can be known, compare with the thick ammonia of raw material, the moisture concentration from the uncondensed gas that part 2 condenser 3 is derived reduces.Hence one can see that, by the partial condensation of part 2 condenser 3, can be that hydrocarbon more than 9 separates as liquid composition and removes with moisture and carbonatoms.
In addition, compare with the thick ammonia of raw material, hydrogen, nitrogen, oxygen, argon gas, carbon monoxide, carbonic acid gas and the carbonatoms from the phlegma that part 1 condenser 5 is derived is that the concentration of 1～8 hydrocarbon reduces.Hence one can see that, by the partial condensation of part 1 condenser 5, can be that 1～8 hydrocarbon separates as gas phase composition and removes with low-boiling point gas and carbonatoms.
In addition, the impurity concentration in the 1st adsorption tower 8 and the exit of the 2nd adsorption tower 9 is compared with the thick ammonia of raw material fully and is reduced.Hence one can see that, by being set to possess the formation of the 1st adsorption tower 8 and the 2nd adsorption tower 9, can access more highly purified ammonia.
The present invention can implement by other variety of ways under the situation that does not break away from its spirit or principal character.Therefore, embodiment mentioned above all only is example from which aspect, and scope of the present invention is shown in claims, is not subjected to any restriction of description.In addition, belong to claim distortion or the change also all within the scope of the invention.
Nomenclature
1 raw material stores jar
2 the 1st vaporizers
3 part 2 condensers
4 the 2nd withdrawing cans
5 part 1 condensers
6 the 1st withdrawing cans
7 the 2nd vaporizers
8 the 1st adsorption towers
9 the 2nd adsorption towers
10 complete condensers
30 goods jars
100,200,300,400,500,600 ammonia refining systems
201 the 3rd fractional distillating tubes

Claims (20)

1. the process for purification of an ammonia, it is the method that the thick ammonia that contains impurity is made with extra care, it is characterized in that, comprise the partial condensation operation, in this operation thick ammonia is carried out partial condensation and is separated into gas phase composition and liquid composition, thereby the impurity that contains in the thick ammonia is removed as gas phase composition or liquid composition separation.
2. the process for purification of ammonia according to claim 1, it is characterized in that, described partial condensation operation comprises part 1 condensation operation, in this operation is that 1～8 hydrocarbon separates as gas phase composition and removes with hydrogen, nitrogen, oxygen, argon gas, carbon monoxide, carbonic acid gas and the carbonatoms that contains as impurity in the thick ammonia.
3. the process for purification of ammonia according to claim 2 is characterized in that, described partial condensation operation comprises part 2 condensation operation, in this operation is that hydrocarbon more than 9 separates as liquid composition and removes with the moisture that contains as impurity in the thick ammonia and carbonatoms.
4. the process for purification of ammonia according to claim 3 is characterized in that, in the described partial condensation operation, described part 1 condensation operation is the subsequent handling of described part 2 condensation operation.
5. the process for purification of ammonia according to claim 2, it is characterized in that, described partial condensation operation comprises the 3rd partial condensation operation, will be by in described part 1 condensation operation, thick ammonia being carried out the liquid composition gasification that partial condensation obtains in this operation, the vapour that this gasification is obtained carries out partial condensation and is separated into gas phase composition and liquid composition, the impurity for ammonia that contains in the vapour is separated as gas phase composition remove.
6. the process for purification of ammonia according to claim 2, it is characterized in that, described part 1 condensation operation comprises a plurality ofly carries out partial condensation stage of partial condensation to thick ammonia, along with the partial condensation stage that enters back segment, at low temperatures thick ammonia is carried out partial condensation.
7. the process for purification of ammonia according to claim 2 is characterized in that, in the described part 1 condensation operation, under-77～50 ℃ temperature thick ammonia is carried out partial condensation.
8. the process for purification of ammonia according to claim 2 is characterized in that, in the described part 1 condensation operation, under the absolute pressure of 0.007～2MPa thick ammonia is carried out partial condensation.
9. the process for purification of ammonia according to claim 1 is characterized in that, also comprises the absorption that utilizes sorbent material that the impurity absorption that contains in the thick ammonia is removed and removes operation.
10. the process for purification of ammonia according to claim 9 is characterized in that, described absorption is removed operation and comprised the 1st absorption that utilizes sorbent material that the water adsorption that contains as impurity in the thick ammonia is removed and remove operation.
11. the process for purification of ammonia according to claim 9 is characterized in that, described absorption is removed operation and is comprised the 2nd absorption that utilizes sorbent material that the absorption of the hydrocarbon that contains as impurity in the thick ammonia is removed and remove operation.
12. the process for purification of ammonia according to claim 9 is characterized in that, preceding continuous operation or the subsequent handling that operation is described partial condensation operation removed in described absorption.
13. the process for purification of ammonia according to claim 4, it is characterized in that, comprise the absorption that utilizes sorbent material that the impurity absorption that contains in the thick ammonia is removed and remove operation, it is operation between described part 2 condensation operation and the described part 1 condensation operation that operation is removed in described absorption.
14. an ammonia refining system, it is the ammonia refining system that the thick ammonia that contains impurity is made with extra care, and it is characterized in that possessing:
The part 1 condensation part, it carries out partial condensation and is separated into gas phase composition and liquid composition thick ammonia, thereby is that 1～8 hydrocarbon separates as gas phase composition and removes with hydrogen, nitrogen, oxygen, argon gas, carbon monoxide, carbonic acid gas and the carbonatoms that contains as impurity in the thick ammonia; With
The part 2 condensation part, it carries out partial condensation and is separated into gas phase composition and liquid composition thick ammonia, thereby is that hydrocarbon more than 9 separates as liquid composition and removes with the moisture that contains as impurity in the thick ammonia and carbonatoms.
15. ammonia refining system according to claim 14 is characterized in that, also possesses the absorption that utilizes sorbent material that the impurity absorption that contains in the thick ammonia is removed and removes portion.
16. ammonia refining system according to claim 15 is characterized in that, described part 2 condensation part, described part 1 condensation part and the described absorption portion of removing are connected in series successively,
Described part 1 condensation part to utilize described part 2 condensation portion from gas phase composition carry out partial condensation and be separated into gas phase composition and liquid composition,
The described absorption portion of removing utilize sorbent material will utilize described part 1 condensation portion from liquid composition in the impurity absorption that contains remove.
17. ammonia refining system according to claim 15 is characterized in that, portion is removed in described part 2 condensation part, described absorption and described part 1 condensation part is connected in series successively,
The described absorption portion of removing utilize sorbent material will utilize described part 2 condensation portion from gas phase composition in the impurity absorption that contains remove,
Partial condensation is carried out to the ammonia that utilizes the absorption of the described absorption portion of removing to remove impurity in described part 1 condensation part.
18. ammonia refining system according to claim 16, it is characterized in that, also possess the 3rd partial condensation portion, it carries out partial condensation and is separated into gas phase composition and liquid composition utilizing the absorption of the described absorption portion of removing to remove the ammonia behind the impurity, impurity is separated as gas phase composition remove.
19. ammonia refining system according to claim 15 is characterized in that, portion is removed in described absorption and described part 1 condensation part is connected in series successively,
Partial condensation is carried out to the ammonia that utilizes the absorption of the described absorption portion of removing to remove impurity in described part 1 condensation part.
20. ammonia refining system according to claim 15 is characterized in that, described absorption is removed portion, described part 2 condensation part and described part 1 condensation part and is connected in series successively,
Partial condensation is carried out to the ammonia that utilizes the absorption of the described absorption portion of removing to remove impurity in described part 2 condensation part,
Described part 1 condensation part to utilize described part 2 condensation portion from gas phase composition carry out partial condensation and be separated into gas phase composition and liquid composition.
CN2012800041903A 2011-03-31 2012-02-07 Method for purifying ammonia and ammonia purification system Pending CN103269980A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106132873A (en) * 2014-03-05 2016-11-16 贝克特尔碳氢技术解决方案股份有限公司 System and method for ammonia purification

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5988285B1 (en) * 2015-10-21 2016-09-07 株式会社島川製作所 Apparatus and method for treating exhaust gas containing ammonia
CN111960436A (en) * 2020-09-03 2020-11-20 福建省宜品生物科技有限公司 Ultrapure ammonia production device and production method

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6065306A (en) * 1998-05-19 2000-05-23 The Boc Group, Inc. Method and apparatus for purifying ammonia
CN1623900A (en) * 2003-12-03 2005-06-08 大阳东洋酸素株式会社 Refining method and device for ammonia

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD159259A3 (en) * 1979-10-16 1983-03-02 Wolfgang Renker PROCESS FOR THE PRODUCTION OF HIGH-PURITY AMMONIA
JPH01257453A (en) * 1988-04-08 1989-10-13 Naoaki Ono Method for treating food
DE4239021A1 (en) * 1992-11-19 1994-05-26 Linde Kca Dresden Gmbh Impurity esp. ammonia sepn. from synthesis purge gas contg. hydrogen - by two stage partial condensation with thermodynamic coupling through common heat exchanger to increase efficiency, prod. purity and economy
US5426944A (en) * 1993-08-31 1995-06-27 American Air Liquide, Inc. Chemical purification for semiconductor processing by partial condensation
JPH10120415A (en) * 1996-10-21 1998-05-12 英正 ▲鶴▼田 Recovery of liquid ammonia from aqueous solution
ES2239236T3 (en) * 2001-07-24 2005-09-16 Dsm Ip Assets B.V. METHOD FOR OBTAINING A SOLUTION OF CARBAMATE AMMONIUM FROM A GAS MIXTURE CONTAINING AMMONIA, WATER AND CARBON DIOXIDE.
NL1022526C2 (en) * 2003-01-30 2004-08-04 Dsm Nv Process for separating NH3, and optionally also CO2 and H2O, from a mixture containing NH3, CO2 and H2O.
US7297181B2 (en) * 2004-07-07 2007-11-20 Air Liquide America L.P. Purification and transfilling of ammonia
JP4605705B2 (en) * 2005-01-31 2011-01-05 日本エア・リキード株式会社 Ammonia purification system and purification method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6065306A (en) * 1998-05-19 2000-05-23 The Boc Group, Inc. Method and apparatus for purifying ammonia
CN1623900A (en) * 2003-12-03 2005-06-08 大阳东洋酸素株式会社 Refining method and device for ammonia

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106132873A (en) * 2014-03-05 2016-11-16 贝克特尔碳氢技术解决方案股份有限公司 System and method for ammonia purification
US10266418B2 (en) 2014-03-05 2019-04-23 Bechtel Hydrocarbon Technology Solutions, Inc. Systems and methods for ammonia purification

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