TW201043571A

TW201043571A - Argon purification method, argon purification apparatus, target gas purification method and target gas purification apparatus

Info

Publication number: TW201043571A
Application number: TW099118867A
Authority: TW
Inventors: Kazuo Haruna; Masanori Miyake; Junichi Sakamoto; Mitsutoshi Nakatani
Original assignee: Sumitomo Seika Chemicals
Priority date: 2009-06-12
Filing date: 2010-06-10
Publication date: 2010-12-16
Also published as: CN101962179B; JP5134588B2; KR20100133894A; CN101962179A; JP2010285317A; KR101699524B1; TWI468337B

Abstract

The invention provides an argon purification method and apparatus, suitable for obtaining high purity argon at a high yield rate by utilizing TSA (thermal swing adsorption) manner and suitable for seeking to reduce the operation time of TSA. In the argon purification method, the argon-containing mixed gas is stored in a storage tank 10, and gas then is supplied toward a TSA adsorption tower 51A, 51B containing an adsorption pipe which has been filled with an adsorption agent, from the storage tank 10. Afterwards, the cycle containing adsorption, heating desorption and cooling steps is repeated in each TSA adsorption tower. In the adsorption step, under a condition that the adsorption agent in the adsorption pipe is at low temperature, i.e. the adsorption temperature, the gas is introduced into the adsorption pipe to allow the adsorption agent to adsorb impurities within the gas, and the purified gas which has been enriched with argon is introduced out from the adsorption pipe. In the heating desorption step, a liquid form heating medium is utilized to raise temperature of the adsorption agent in the adsorption pipe, and simultaneously the impurities are desorbed from the adsorption agent, and furthermore the purified gas is introduced into the adsorption pipe, and off gas is introduced out from the adsorption pipe at the same time so as to introduce the off gas into the storage tank 10. In the cooling step, a liquid form cooling medium is utilized to reduce the temperature of the adsorption agent within the adsorption pipe.

Description

201043571 51A〜吸附塔； 52A〜熱交換器； 52D〜冷媒幫浦； 52卜熱媒槽； 5 8'線； E2〜精製氣體導出端； Gfl〜原料氣體；〜準精製氣體； G/ ’ ~氣體；201043571 51A ~ adsorption tower; 52A ~ heat exchanger; 52D ~ refrigerant pump; 52 heat medium tank; 5 8 ' line; E2 ~ refined gas outlet end; Gfl ~ raw material gas; ~ quasi-refined gas; G / ' ~ gas;

Ge〜氣體；〜氣體； 51B〜吸附塔； 520冷媒槽； 52E〜鹽水冷卻器； 5 2 G〜熱媒幫浦； E1〜原料氣體導入端； E3〜精製氣體導出端； Gi〜氣體；〇3’〜氣體；Ge ~ gas; ~ gas; 51B ~ adsorption tower; 520 refrigerant tank; 52E ~ brine cooler; 5 2 G ~ heat medium pump; E1 ~ raw material gas introduction end; E3 ~ refined gas outlet end; Gi ~ gas; 3'~ gas;

Gs〜氣體； G〜精製氣體； γ〜氬氣精製裝置。五、本案若有化學式時，請揭示最能顯示發明特徵的化學式：無。 Q 六、發明說明：【發明所屬之技術領域】本發明是關於利用溫度變動吸附法來精製氬的方法及裝置，還有可利用上述方法及裝置的方法及裝置。【先前技術】爐、陶瓷燒結爐、製鋼熔解爐等之中的爐内氣，會因為不純物的混入鼠經常被用來作為單晶矽拉晶用真工脫氣爐、太陽電池用矽電漿氛被用來作為爐内氣氛氣體的氩 201043571 而降低純度。關於被用來作為爐内氣氛氣體的氬，為了再利用，會有將其回收而以溫度變動吸附法（TSA法：Thermai Swing Adsorption)來精製的情況。關於使用TSA法的氬精製技術，揭露於例如以下的專利文獻1〜2。【專利文獻1】特開平7-1 38007號公報【專利文獻2】特開2006-1 1 1506號公報從單晶矽拉晶爐、陶瓷燒結爐、製鋼用真空脫氣爐、太陽電池用矽電漿熔解爐等所排出之以氬氣為主成分的已使用的氣氛氣體，其氩濃度是相對較高（氬濃度例如為 95vol%以上）。在習知技術中，針對這樣高濃度的氬氣，是難以使用TSA法來作進一步的高濃度化並達成高回收率。另外，從單晶石夕拉晶爐、陶瓷燒結爐、製鋼用真空脫氣爐、太陽電池用矽電漿熔解爐等所排出之以氬氣為主成分的已使用的氣氛氣體中，多含有成為不純物的氮。為了充分地將氬尚純度化，有必要除去上述氮。在使用TSA法的氬精製技術中，是使用已充填在低溫區的氮的吸附性高的既定吸附劑的吸附管，但是在使用TSA法的習知的氬精製技術中，是在吸附管重複如下所述的吸附步驟及脫附步驟，以媒求氣的去除。在吸附步驟中’是在將精製對象的粗氬氣冷卻至既定溫度之後，將其導入吸附管。粗氬氣是在吸附管内流通而被導出於吸附管外，而在吸附管内流通的過程中與吸附劑接觸而冷卻吸附劑。藉由與粗氬氣的接觸，吸附劑是徐徐地降溫’而此吸附劑的氮吸附能力則徐徐地提高（也就是粗 201043571 鼠氣疋精势制_ φ &友诚、艾象的氣體’還擔當用以冷卻吸附劑的媒介的在吸附步驟中，氮是被這樣的吸附劑所吸附。 Ο #在脫附步驟中，是將已精製的氬氣以外的其他的加熱用=體加熱至既定溫度之後，將其導人吸附管。加熱用氣苄二、吸附S内流通而被導出於吸附管外，而在吸附管内 ^ γ k旌中與吸附劑接觸而加熱吸附劑。藉由與加熱用 ' 、接觸，吸附劑是徐徐地升溫，而此吸附劑的氮吸附 :力則保你地變低。在吸附步驟中，是從這樣的吸附劑將氮脫附’而與加熱用氣體—起排出至吸附管外。 ^然而，在藉由從吸附劑到粗氬氣的熱傳而使吸附劑降溫L及附㈣中’多有需要較長時間來使吸附劑到達充分的低溫的情況。另外，在吸附劑到達充分的低溫之前，並未充分地從在吸附管内流通的粗氬氣除氣，使吸附劑到達充分的低溫所需要的時間愈長，則未充分除氮的氬氣之從吸附管的導出量就會增加(此情況從氬氣的高純度化的觀點來看為不理想)。除此之外’在藉由從已精製的氬氣以、 …用轧體到及附劑的熱傳而使吸附劑升溫的上述脫附步驟中，多右堂夕有南要較長日可間來使吸附劑到達充分的南溫的情況。【發明内容】有鑑於此’本發明的目的是接徂 π疋徒供一種氬精製方法及裝置，其適用於利用TSA法而以高產率1古〇厓手取侍尚純度氬，且適用於謀求TSA作業時間的縮短，亚鈐供一種目的氣體精製 201043571 方法及裝詈，、* m ^, 、用於利用上述氬精製方法及裝置。本根據本發明的第一特徵，是提供一種氬精製方法。在方法中，疋將含氬的混合氣體收進貯留槽丨另外，從貯留槽向著含已充填吸附劑的吸附管之TSA吸附塔供應混合氣體。然後，在TSA吸附塔中重複進行含吸附（adsQm ι〇η) 步驟、加熱脫附（desorpti〇n)步驟' 及冷卻步驟的循環。 ^吸附步驟中’在吸附管内的吸附劑為相對低溫的吸附用又的狀L下，將混合氣體導入此吸附管，使吸附劑吸附匕此CT氣體中的不純物’且將氬富化後的精製氣體從此吸附管導出。在加熱脫附步驟中，是使吸附管内的吸附劑升溫至相對高溫的溫度並同時使不純物從此吸附劑脫附。另外’在加熱脫附步驟巾，是使用液狀熱媒加熱吸附管内的吸熱劑，且將精製氣體導入吸附管並同時從此吸附管導出廢氣，而將此廢氣導入貯留槽。在冷卻步驟中，是使吸附官内的吸附劑降溫。另外，在冷卻步驟中，是使用液狀冷媒來冷卻吸附管内的吸附劑。在本方法中，是在TSA吸附塔中實行包含上述的吸附步驟、加熱脫附步驟、及冷卻步驟的溫度變動吸附法（TSA 法），藉此謀求混合氣體中的氬的富化乃至高純度化，同時關於高純度氬，容易達成高產率。這是因為在本方法中，在加熱脫附步驟中從TSA吸附塔持續導出的廢氣是回到貯留槽’將此廢氣供作使用TSA法的再一次的氬富化。在本方法的加熱脫附步驟中’是從經過吸附步驟而吸附著氮的吸附劑將氮脫附。為了將此脫附的氮適當地排出TSA吸附 201043571 =.狀將精製氣體導入處於加熱脫附步,驟# TSA °及附塔的吸=S。因此，從處於加熱脫附步驟的TSA吸附塔乃至吸附官導出的廢氣的氬漠度較高。在本方法中，並未將這樣的5排出裝置外而使其回到貯留槽，供作使用TSA法的再人的氬虽化。因此，本方法是適用於以高產率取純度氬。另外，若藉由本方法，則容易縮短TSA作業時間。這 ❹是因為在本方法中，是在實行伴隨著吸附劑的溫度變動的、’時使用液狀熱媒及液狀冷媒來實現吸附劑的溫度變動。具體的步驟是如下所述。在本發明的加熱脫附步驟中，是使用液狀熱媒加熱吸附：内的吸附劑。藉由使液狀熱媒接觸充填著吸附劑的吸附官，而將熱從此液狀熱媒供應至吸附管内的吸附劑，而可以加熱吸附劑。由於游^ 由於液狀熱媒的比熱是有相當程度地大於氣體的比熱，比起使用氣體 u肢忭马用於TSA法中加熱吸附 ◎劑的媒介之情況，如本方法使用液狀熱媒來加熱吸附劑的情況可以較快使吸附劑升溫至所欲的溫度。心設定0 55%乙醇水溶液來作為本方法中的液狀熱媒的情況（第-情況），並設枝用氬氣來作為加熱用的媒介將吸附劑升溫的情況（第二情況），由於⑽乙醇水溶液的比執為 0. 839kcal/kg · t：(在 _2〇 & 户 0. 125kcal/kg· °c (^-23〇C ) 虱氣的比熱為在23C)，關於每單位時間對吸附劑的熱供應里’在第—情況是可以實現第二情況的7倍左右。因此’第—情況(相關於本發明的情況），是可以在以第二 201043571 情況的七分之一的程度的短時間之下使加熱脫附步驟釺束。加熱脫附步驟時間的縮短，是有助於TSA作業時間的縮短。另一方面，本方法的冷卻步驟中，是使用液狀冷媒來冷卻吸附管内的吸附劑。藉由使液狀冷媒接觸充填著吸附劑的吸附管，而藉由此液狀冷媒從吸附管内的吸附劑奪取熱忐，而藉此可以冷卻吸附劑。由於液狀冷媒的比熱是有相當程度地大於氣體的比熱，比起使用氣體作為用於法中冷部吸附劑的媒介之情況，如本方法使用液狀冷媒來冷部吸附劑的情況可以較快使吸附劑降溫至所欲的溫度。假如定使用55%乙醇水溶液來作為本方法中的液狀冷媒的情況（第三情況），並設定使用氬氣來作為冷卻用的媒介將吸附劑降溫的情況（第四情況），由於55%乙醇水溶液及氬氣的比熱是如上所述，關於每單位時間從吸附劑的熱接收量，在第三情況是可以實現第四情況的7倍左右。因此，第三情況(相關於本發明的情況），是可以在以第四情況的七分之一的程度的短時間之下使冷卻步驟結束。冷卻步驟時間的縮短，是有助於TSA作業時間的縮短。如上所述，本發明的第一特徵之氣精製方法，是適用於利用TSA法而以高產率取得高純度氩，且適用於謀求— 作業時間的縮短。〃除此之外，本方法是容易因應氣的精製時之作為原料 =的混合氣體的流量變動、組成變動等。一般而言，從早晶石夕拉晶爐、m結爐、製鋼用真空脫氣爐、太陽電 201043571 Ο 氛氣^電聚溶解爐等所排出之以氯為主成分的已使用的氣二：多有伴隨著排出流量、不純物組成等的變動，亦體作、車5動的清況°因此’ $ 了將從爐中排出的此排放氣的:ά旦:、性地精製處理’有必要構築可以因應此排放氣體作變動、組成變動等的處理系統。在本方法中，關於 =料：體的遇合氣體一旦收進貯留槽之後，就從此㈣日向耆用以實行TSA法的TSA吸附塔作供應。即使是貯留槽之作為原料氣體的混合氣體二變動的情況，，由一旦將此混合氣體收進貯留槽並受 1貝丁 =及藏合’流量變動、組成變動等會在從此貯留槽導、^ 口氣體中文到緩和或抑制（從這樣的流量變動、组成變動等緩和或抑制的觀點，貯留槽之用於收容氣體的容積 i為可變）。因此若藉由本方法，容易因應原料氣體的流量變動 '組成變動等。根據本發明的第二特徵，是提供—種氩精製方法。在〇方法中，是將含氬的混合氣體收進貯留槽；另外，從貯留槽向著從複數個TSA吸附塔選出的TSA吸附塔供應混合氣體，上述TSA吸附塔包含已充填吸附劑的吸附管。然後，在上述複數個TSA吸附塔中，各自重複進行含吸附步驟、加熱脫附步驟、及冷卻步驟的循環。在吸附步驟中，是在吸附官内的吸附劑為相對低溫的吸附用溫度的狀態下，將此合氣體導入此^吸附f，而使„及附劑吸附此混合氣體中的不純物，且將氬富化後的精製氣體從此吸附管導出。在加熱脫附步驟中，是使吸附管内的吸附劑升溫至相對高溫的 201043571 溫度並同時使不純物從此吸附劑脫附。另外，在加熱脫附步驟中’是使用液狀熱媒來加熱吸附管内的吸附劑，且將精製氣體導入吸附管並同時從此吸附管導出廢氣，而將此廢氣導入貯留槽。導入處於加熱脫附步驟的TSA吸附塔的吸附管之精製氣體，是從處於吸附步驟的TSA吸附塔的吸附管導出的精製氣體。在冷卻步驟中，是使吸附管内的吸附劑降溫；另夕卜，在冷卻步驟中’是使用液狀冷媒來冷卻吸附管内的吸附劑。Gs ~ gas; G ~ refined gas; γ ~ argon refining device. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None. Q. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method and apparatus for purifying argon by a temperature fluctuation adsorption method, and a method and apparatus using the above method and apparatus. [Prior Art] Furnace gas in furnaces, ceramic sintering furnaces, steel melting furnaces, etc., is often used as a single crystal crucible for degassing furnaces, and for solar cells. The atmosphere was used as argon 201043571 as the atmosphere gas in the furnace to reduce the purity. The argon used as the atmosphere gas in the furnace may be recovered and recovered by a temperature fluctuation adsorption method (TSA method: Thermai Swing Adsorption) for recycling. The argon-precision technique using the TSA method is disclosed, for example, in the following Patent Documents 1 to 2. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2006-1 1 1506. From a single crystal crucible crystal pulling furnace, a ceramic sintering furnace, a vacuum degassing furnace for steelmaking, and a solar cell. The used atmospheric gas containing argon as a main component discharged from a plasma melting furnace or the like has a relatively high argon concentration (for example, an argon concentration of 95 vol% or more). In the prior art, for such a high concentration of argon gas, it is difficult to further increase the concentration by using the TSA method and achieve high recovery. In addition, the used atmosphere gas containing argon as a main component discharged from a single crystal stone crystal pulling furnace, a ceramic sintering furnace, a vacuum degassing furnace for steelmaking, a tantalum plasma melting furnace for solar cells, etc. Become a nitrogen of impurities. In order to sufficiently purify argon, it is necessary to remove the above nitrogen. In the argon refining technique using the TSA method, a sorbent tube having a predetermined adsorbent having high nitrogen adsorption property in a low temperature region is used, but in the conventional argon refining technique using the TSA method, the sorbent tube is repeated. The adsorption step and the desorption step as described below are used to remove the gas. In the adsorption step, after the crude argon gas to be purified is cooled to a predetermined temperature, it is introduced into the adsorption tube. The crude argon gas is circulated in the adsorption tube and is led out of the adsorption tube, and is in contact with the adsorbent during the flow in the adsorption tube to cool the adsorbent. By contact with crude argon, the adsorbent is slowly cooled, and the nitrogen adsorption capacity of the adsorbent is slowly increased (that is, the crude gas of the 201043571 rat 疋 amp &;; 'In the adsorption step, the nitrogen is adsorbed by such an adsorbent. Ο # In the desorption step, other heating bodies other than the purified argon are heated. After the temperature is reached, the adsorption tube is guided to the adsorption tube. The heating is carried out by the gas and the adsorption S, and is led out of the adsorption tube, and the adsorbent is heated in contact with the adsorbent in the adsorption tube, γ k旌. In contact with heating, the adsorbent is slowly warmed up, and the nitrogen adsorption of the adsorbent: the force is kept low. In the adsorption step, nitrogen is desorbed from such adsorbent, and heating is used. The gas is discharged to the outside of the adsorption tube. However, in order to cool the adsorbent by heat transfer from the adsorbent to the crude argon, and in the case of (4), it takes a long time for the adsorbent to reach a sufficient low temperature. In addition, the sorbent reaches sufficient Before the temperature, the gas is not sufficiently degassed from the crude argon gas flowing in the adsorption tube, and the longer the time required for the adsorbent to reach a sufficient low temperature, the amount of argon gas that is not sufficiently denitrified from the adsorption tube will be Increase (this is not desirable from the viewpoint of high purity of argon gas). In addition, 'adsorption is carried out by heat transfer from the purified argon gas, from the rolled body to the attached agent. In the above desorption step in which the temperature of the agent is raised, there may be a case where the adsorbent reaches a sufficient south temperature for a long period of time. [Invention] In view of the above, the object of the present invention is to connect 徂π疋An argon refining method and apparatus are applied to the use of the TSA method to obtain the purity argon in a high yield of 1 〇〇 ,, and is suitable for shortening the working time of the TSA, and the arsenic is supplied with a target gas refining method 201043571詈,, * m ^, for utilizing the above-described argon refining method and apparatus. According to a first feature of the present invention, there is provided an argon refining method in which cerium is charged into a storage tank by a mixed gas containing argon. In addition, from the storage tank The TSA adsorption column of the adsorbent tube to which the adsorbent has been charged supplies the mixed gas, and then the cycle of the adsorption (adsQm 〇 )) step, the heating desorption (desorpti〇n) step, and the cooling step is repeated in the TSA adsorption column. In the adsorption step, the adsorbent in the adsorption tube is in the form of a relatively low-temperature adsorption, and the mixed gas is introduced into the adsorption tube to adsorb the adsorbent in the CT gas and the argon is enriched. The refined gas is led out from the adsorption tube. In the heating and desorption step, the adsorbent in the adsorption tube is heated to a relatively high temperature and at the same time the impurities are desorbed from the adsorbent. In addition, in the heating desorption step, the liquid is used. The heat medium heats the heat absorbing agent in the adsorption tube, and introduces the purified gas into the adsorption tube and simultaneously discharges the exhaust gas from the adsorption tube, and introduces the exhaust gas into the storage tank. In the cooling step, the adsorbent in the adsorbent is cooled. Further, in the cooling step, the liquid refrigerant is used to cool the adsorbent in the adsorption tube. In the method, a temperature fluctuation adsorption method (TSA method) including the adsorption step, the heating and desorption step, and the cooling step described above is carried out in the TSA adsorption column, thereby achieving argon enrichment or high purity in the mixed gas. At the same time, high purity argon is easy to achieve high yield. This is because in the present process, the exhaust gas continuously derived from the TSA adsorption tower in the heating desorption step is returned to the storage tank. This exhaust gas is supplied as another argon enrichment using the TSA method. In the heating and desorption step of the method, 'the nitrogen is desorbed from the adsorbent which adsorbs nitrogen through the adsorption step. In order to properly discharge the desorbed nitrogen from the TSA adsorption 201043571 =., the refined gas is introduced into the heating desorption step, the step # TSA ° and the absorption of the attached column = S. Therefore, the argon gradient from the TSA adsorption tower in the heating desorption step to the exhaust gas derived from the adsorber is high. In the present method, such a 5 discharge device is not returned to the storage tank, and the argon is replaced by a further person using the TSA method. Therefore, the method is suitable for taking argon in a high yield. Further, with this method, it is easy to shorten the TSA operation time. In this method, the temperature fluctuation of the adsorbent is achieved by using a liquid heat medium and a liquid refrigerant when the temperature fluctuation of the adsorbent is carried out. The specific steps are as follows. In the heating and desorption step of the present invention, the adsorbent in the inside is adsorbed by using a liquid heat medium. The adsorbent can be heated by supplying the liquid heat medium to the adsorbent filled with the adsorbent to supply heat from the liquid heat medium to the adsorbent in the adsorption tube. Since the specific heat of the liquid heat medium is considerably larger than the specific heat of the gas, the liquid heat medium is used as the method for heating the adsorption medium in the TSA method. In order to heat the adsorbent, the adsorbent can be warmed up to a desired temperature. In the case where a 505% aqueous solution of ethanol is set as the liquid heat medium in the present method (the first case), and the argon gas is used as a medium for heating to raise the temperature of the adsorbent (second case), (10) The ratio of ethanol aqueous solution is 0. 839kcal/kg · t: (in _2〇 & household 0. 125kcal/kg· °c (^-23〇C) The specific heat of helium is at 23C), about each unit The time in the heat supply to the adsorbent is 'in the first case, about 7 times that of the second case. Therefore, the 'first case (in the case of the present invention) is that the heating desorption step can be terminated in a short time to the extent of one-seventh of the second 201043571 case. The shortening of the heating desorption step time is helpful for shortening the TSA working time. On the other hand, in the cooling step of the method, the liquid refrigerant is used to cool the adsorbent in the adsorption tube. By bringing the liquid refrigerant into contact with the adsorbing tube filled with the adsorbent, the liquid refrigerant can take heat from the adsorbent in the adsorbing tube, whereby the adsorbent can be cooled. Since the specific heat of the liquid refrigerant is considerably greater than the specific heat of the gas, compared with the case where the gas is used as the medium for the cold-phase adsorbent in the process, the liquid refrigerant can be used as the cold adsorbent in the present method. Allow the adsorbent to cool down to the desired temperature. If a 55% aqueous solution of ethanol is used as the liquid refrigerant in the present method (third case), and argon gas is used as a medium for cooling to cool the adsorbent (fourth case), since 55% The specific heat of the aqueous ethanol solution and the argon gas is as described above, and the amount of heat received from the adsorbent per unit time is about 7 times that of the fourth case in the third case. Therefore, in the third case (in the case of the present invention), it is possible to end the cooling step in a short time to the extent of one-seventh of the fourth case. The cooling step is shortened to help shorten the TSA operation time. As described above, the gas purifying method according to the first aspect of the present invention is suitable for obtaining high-purity argon in a high yield by the TSA method, and is suitable for the purpose of shortening the working time. In addition to this, the method is a flow rate variation, a composition change, and the like of a mixed gas which is easily used as a raw material when the gas is purified. In general, the used gas is mainly composed of chlorine, which is discharged from the early crystal crystallization furnace, the m-ring furnace, the vacuum degassing furnace for steelmaking, the solar power 201043571 Ο atmosphere, the electropolymerization melting furnace, and the like. : There are many changes accompanying the discharge flow rate, the composition of impurities, etc., and the condition of the vehicle and the movement of the vehicle is 5°. Therefore, the exhaust gas discharged from the furnace is: ά:: sexually refined treatment It is necessary to construct a treatment system that can respond to fluctuations in the exhaust gas, composition changes, and the like. In the method, once the gas of the material is absorbed into the storage tank, it is supplied from the (T) day to the TSA adsorption tower for carrying out the TSA method. In the case where the mixed gas as the source gas of the storage tank is changed, the mixed gas is taken into the storage tank and subjected to the fluctuation of the flow rate of the 1st and the storage, the composition change, etc., and the storage tank is guided from the storage tank. ^ The mouth gas is moderately suppressed or suppressed (the volume i for storing the gas in the storage tank is variable from the viewpoint of such fluctuation or suppression of flow rate fluctuation, composition fluctuation, etc.). Therefore, according to this method, it is easy to respond to changes in the flow rate of the material gas, such as composition fluctuations. According to a second feature of the present invention, there is provided an argon refining method. In the crucible method, the mixed gas containing argon is collected into the storage tank; and the mixed gas is supplied from the storage tank to the TSA adsorption tower selected from the plurality of TSA adsorption towers, and the TSA adsorption tower includes the adsorption tube filled with the adsorbent. . Then, in the plurality of TSA adsorption columns, the cycles including the adsorption step, the heating and desorption step, and the cooling step are repeated. In the adsorption step, when the adsorbent in the adsorption unit is at a relatively low temperature for adsorption, the combined gas is introduced into the adsorption f, so that the adsorbent adsorbs the impurities in the mixed gas, and The argon-rich purified gas is led out from the adsorption tube. In the heating and desorption step, the adsorbent in the adsorption tube is heated to a relatively high temperature of 201043571 and at the same time the impurities are desorbed from the adsorbent. In addition, in the heating desorption step The middle is to use a liquid heat medium to heat the adsorbent in the adsorption tube, and introduce the refined gas into the adsorption tube and simultaneously extract the exhaust gas from the adsorption tube, and introduce the exhaust gas into the storage tank. Introduce the TSA adsorption tower in the heating desorption step. The purified gas in the adsorption tube is a purified gas derived from the adsorption tube of the TSA adsorption column in the adsorption step. In the cooling step, the adsorbent in the adsorption tube is cooled; in addition, in the cooling step, 'the liquid is used. The refrigerant cools the adsorbent in the adsorption tube.

本發明的第二特徵相關之氬精製方法，是包含本發明的第—特徵相關之氬精製方法的構成。因此，若藉由第二特徵相關之氬精製方法，關於第一特徵相關之氬精製方法，可以取得與上述同樣的技術效果。具體而言，第二特徵之氩精製方法，是適用於利用TSA法而以高產率取得高純度氬，且適用於謀求TSA作業時間的縮短。除此之外〇第二特徵之氬精製方法，是容易因應作為原料氣體的混合氣體的流量變動、組成變動等。The argon purification method according to the second feature of the present invention is a configuration including the argon purification method according to the first aspect of the present invention. Therefore, the same technical effect as described above can be obtained with respect to the argon purification method relating to the first feature by the argon purification method according to the second feature. Specifically, the second characteristic argon purifying method is suitable for obtaining high-purity argon in a high yield by the TSA method, and is suitable for shortening the TSA working time. In addition, the argon purification method of the second feature is a flow rate variation, a composition change, and the like of the mixed gas which is easily used as the material gas.

根據本發明的第三特徵，是提供一種氬精製裝置。 =是包含一 TSA吸附塔’其具有一第一氣體通過口 :第二氣體通過口 ’並具有一吸附管，上述吸附管與此 -及第二氣體通過口連通且充填有吸附劑；一貯留槽，以在將含氬的混合氣體供應至TSA吸附塔之前，聍=上 ’昆合虱體；一冷媒貯槽’以冷卻吸附管内的吸附劑為目自用以存玫供應至TSA吸附塔的液狀冷媒；一熱媒貯槽，加熱吸附管内的吸附劑為目％，用以存放供應至二 10 201043571 塔的液狀熱媒；一第一氣體線，連結貯留槽及TSA吸附塔之間，而得以將混合氣體從貯留槽供應至TSA吸附塔的第一氣體通過口側；一第二氣體線，其連接TSA吸附塔及貯留槽之間’而得以將從TSA吸附塔的第一氣體通過口側導出的氣體供應至貯留槽；一第一冷媒線，用以將冷媒從冷媒貯槽供應至TSA吸附塔；一第二冷媒線，用以將冷媒從 TSA吸附塔回送至冷媒貯槽；一第一熱媒線，用以將熱媒從熱媒貯槽供應至TSA吸附塔；以及一第二熱媒線，用以將熱媒從TSA吸附塔回送至熱媒貯槽。若藉由具備這樣的結構的本裝置，可以適當地實行本發明的第一特徵相關之上述的氬精製方法。根據本發明的第四特徵，是提供一種氬精製裝置。本裝置是包含：複數個TSA吸附塔，其具有一第一氣體通過口與一第二氣體通過口，並具有一吸附管，上述吸附管與According to a third feature of the present invention, an argon refining device is provided. = comprising a TSA adsorption tower 'having a first gas passage port: a second gas passage port' and having a adsorption tube, the adsorption tube being in communication with the second gas passage port and filled with an adsorbent; a tank, before the supply of the argon-containing mixed gas to the TSA adsorption tower, the 聍=upper 昆昆 ;; a refrigerant sump' is used to cool the sorbent in the sorbent tube for the purpose of supplying the scent to the TSA adsorption tower a refrigerant medium; a heat medium storage tank, which heats the adsorbent in the adsorption tube to store the liquid heat medium supplied to the tower of 201010571; a first gas line connects the storage tank and the TSA adsorption tower, and The mixed gas can be supplied from the storage tank to the first gas passage port side of the TSA adsorption tower; a second gas line connecting the TSA adsorption tower and the storage tank can be used to pass the first gas passage port from the TSA adsorption tower The side-derived gas is supplied to the storage tank; a first refrigerant line is used to supply the refrigerant from the refrigerant storage tank to the TSA adsorption tower; and a second refrigerant line is used to return the refrigerant from the TSA adsorption tower to the refrigerant storage tank; Hot media line The heat medium to the heat medium supplied from the sump to the TSA adsorption column; and a second heat medium lines to the TSA adsorption tower from the heat medium to the heat medium return sump. According to the present apparatus having such a configuration, the above-described argon purification method according to the first feature of the present invention can be suitably carried out. According to a fourth feature of the present invention, an argon refining device is provided. The apparatus comprises: a plurality of TSA adsorption towers having a first gas passage opening and a second gas passage opening, and having a adsorption tube, the adsorption tube and

此第一及第二氣體通過口連通且充填有吸附劑；一貯留槽，用以在將含氬的混合氣體供應至TSA吸附塔之前，貯留上述混合氣體；—冷媒貯槽，以冷卻吸附管内的吸附劑為目的，用以存放供應至TSA吸附塔的液狀冷媒；一熱媒貯槽’以加熱吸附管内的吸附劑為㈣用以存放供應至 TSA吸附塔的液狀熱媒；一第—氣體線，連結貯留槽及各 A吸附塔之間’而得以將混合氣體從貯留槽供應至各 —第二氣體線，具有一主幹吸附塔的第一氣體通過口側路及複數個分支路，上述分支路是設置於每一 #tsa吸附塔並連接此TSA吸附塔的吸附管的第二氣體通過口側；一 201043571 第二氣體線》具有—主另王幹路及複數個分支路，上述主幹路是連接於貯留槽，上述分支路县< 文峪疋6又置於母—個TSA吸附塔並連接此TSA吸附塔的¢5(5(4答。幻及附官的弟一氣體通過口側；一第冷媒線’用以將冷媒從；人據目^ω e T妹徒々媒I了槽供應至吸附劑冷卻對象的TSA吸附塔；一第-)入Mm 弟一〜媒線，用以將冷媒從TSA吸附塔回送至冷媒貯槽；一第一埶據娃弟’、、、媒線’用以將熱媒從熱媒貯槽供應至吸附劑加熱對象的TSA吸附塔；以及一第二熱媒線1以將熱媒從TSA吸附塔回送至熱媒貯槽。若藉由具備這樣的結構的本裝置，可以適當地實行本發明的第一特徵相關之上述的氬精製方法、第二特徵相關之上述的氬精製方法。根據本發明的第五特徵，是提供—種目的氣體精製方法:在本方法中，是㈣TSA吸附塔供應含目的氣體的混口乳體’上述TSA吸附塔包含已充填吸附劑的吸附管。然後’在TSA吸附塔中重複進行含吸附步驟、加熱脫附步驟、及冷卻步驟的循環。在吸附步驟中，是在吸附管内的吸附劑為相對低溫的吸附用溫度的狀態下，將混合氣體導入此吸附管，而使此吸附劑吸附此混合氣體中的純物，且將目的氣體富化後的精製氣體從此吸附管導出。在加熱脫附步驟中’使吸时㈣吸㈣升溫至相對高溫的溫度並同時使不純物從此吸附劑脫附。另夕卜，在加熱脫附步驟中，是使^液狀熱媒來加熱吸附管内的吸附劑。在冷卻步驟中，是使吸附管内的吸附劑降溫。另外，在冷卻步驟中，疋使用液狀冷媒來冷卻吸附管内的吸附劑。作為使用本方 201043571 ‘*之精製對象的目的氣體者，除了氬之外，可列舉出的有氦、氖、氪、及氙等的稀有氣體等。 ★具備這樣構成的本方法，可以適當地應用於本發明的第特徵相關之上述的氬精製方法、第二特徵相關之上述的氬精製方法等之中。另外，若藉由本方法，與關於第一㈣相關之上述的氬精製方法之上述内容同樣，在精製既疋的目的氣體之時，容易縮短TSA的作業時間。這是因為在本方法中，在貫行伴隨著吸附劑的溫度變動之TSA法之時’使用液狀熱媒及液狀冷媒來實現吸附劑的溫度變動。、、根據本發明的第六特徵，是提供一種目的氣體精製方法在本方法中，是向著從複數個TSA吸附塔選出的TSA 吸附塔供應含目的氣體的混合氣體，上述m吸附塔包含已充填吸附劑的吸附管。然後，在複數個m吸附塔中，各自重複進行含吸附步驟、加熱脫附步驟、及冷卻步驟的循環。在吸附步驟中，是在吸附管内的吸附劑為相對低溫〇的吸附用溫度的狀態下，將混合氣體導入此吸附管，而使吸附劑吸附此混合氣體中的不純物，且將目的氣體富化後的精製氣體從此吸附管導出。在加熱脫附步驟中，是使吸附官内的吸附劑升溫至相對高溫的溫度並同時使不純物從此吸附劑脫附。另外，在加熱脫附步驟中，是使用液狀熱媒來加熱吸附管内的吸附劑。在冷卻步驟中，是使吸附管内的吸附劑降溫。另外，在冷卻步驟中，是使用液狀冷媒來冷卻吸附管内的吸附劑。作為使用本方法之精製對象的目的氣體者，除了氬之外，可列舉出的有氦、氖、氪、及 13 201043571 iSL等的稀有氣體等。根據本發明的第七，置。在本裝置中，… 疋如供-種目的氣體精製裝洛駚、s $ ώ 疋ι 3 . — TSA吸附塔，其具有一第一耽體通過口與—第二氣體通過口，吸附管與此第一及第二氣 :、 …上u -冷媒貯槽，以冷卻具’及關’ 内的吸附劑為目的，用以存放供應至TSA吸附塔的液狀入 μ 7媒，一熱媒貯槽，以加熱吸附官内的吸附劑為㈣’用以存放供應至⑽吸附塔的液狀The first and second gas passages are connected and filled with an adsorbent; a storage tank for storing the mixed gas before supplying the mixed gas containing argon to the TSA adsorption tower; and a refrigerant storage tank for cooling the inside of the adsorption tube The adsorbent is for the purpose of storing the liquid refrigerant supplied to the TSA adsorption tower; the heat medium storage tank is for heating the adsorbent in the adsorption tube to (4) for storing the liquid heat medium supplied to the TSA adsorption tower; a line connecting the storage tank and each of the adsorption towers to supply mixed gas from the storage tank to each of the second gas lines, having a first gas passage side passage and a plurality of branch passages of a main adsorption tower, The branch road is disposed on each #tsa adsorption tower and connected to the second gas passage side of the adsorption tube of the TSA adsorption tower; a 201043571 second gas line has a main king road and a plurality of branch roads, the above trunk The road is connected to the storage tank, and the above-mentioned branch road county < Wenyu 6 is placed in the mother-side TSA adsorption tower and connected to the TSA adsorption tower ¢5 (5 (4 answer. Oral side; one cold The line 'is used to supply the refrigerant from the tank to the TSA adsorption tower of the sorbent cooling object; a -) into the Mm brother-media line to remove the refrigerant from the source The TSA adsorption tower is sent back to the refrigerant storage tank; a first TSA adsorption tower for supplying the heat medium from the heat medium storage tank to the adsorbent heating object according to the ',, and the medium line'; and a second heat medium line 1 The heat medium is returned from the TSA adsorption tower to the heat medium storage tank. By the present apparatus having such a configuration, the above-described argon purification method according to the first feature of the present invention and the second feature described above can be appropriately performed. Argon refining method According to a fifth feature of the present invention, there is provided a gas purifying method of the present invention: in the method, (4) a TSA adsorption tower supplies a mixed emulsion containing a target gas, wherein the TSA adsorption tower comprises a packed adsorbent. The adsorption tube is then repeatedly subjected to a cycle including an adsorption step, a heating desorption step, and a cooling step in the TSA adsorption column. In the adsorption step, the adsorbent in the adsorption tube is in a relatively low temperature adsorption temperature state. Will mix The gas is introduced into the adsorption tube, and the adsorbent adsorbs the pure substance in the mixed gas, and the purified gas obtained by enriching the target gas is led out from the adsorption tube. In the heating and desorption step, the suction time (four) is sucked (four) and the temperature is raised to Relatively high temperature and at the same time, the impurities are desorbed from the adsorbent. In addition, in the heating and desorption step, the liquid heat medium is used to heat the adsorbent in the adsorption tube. In the cooling step, the inside of the adsorption tube is made. In the cooling step, the liquid refrigerant is used to cool the adsorbent in the adsorption tube. The target gas used in the purification of the product of 201043571 '*, in addition to argon, is exemplified. a rare gas such as 氖, 氪, 氙, or the like. The present method having such a configuration can be suitably applied to the argon purification method according to the first aspect of the present invention, the argon purification method according to the second feature, or the like. Among them. Further, according to the above-described content of the above-described argon purification method relating to the first (fourth), it is easy to shorten the working time of the TSA when purifying the target gas. This is because in the present method, the temperature fluctuation of the adsorbent is achieved by using a liquid heat medium and a liquid refrigerant at the time of the TSA method accompanying the temperature fluctuation of the adsorbent. According to a sixth feature of the present invention, there is provided a method for purifying a target gas. In the method, a mixed gas containing a target gas is supplied to a TSA adsorption column selected from a plurality of TSA adsorption columns, wherein the m adsorption column comprises a filled gas. Adsorbent tube for adsorbent. Then, in a plurality of m adsorption columns, a cycle including an adsorption step, a heating desorption step, and a cooling step is repeated. In the adsorption step, when the adsorbent in the adsorption tube is at a temperature lower than the adsorption temperature of the low temperature, the mixed gas is introduced into the adsorption tube, so that the adsorbent adsorbs the impurities in the mixed gas, and the target gas is enriched. The subsequent refined gas is led out from this adsorption tube. In the heating and desorption step, the adsorbent in the adsorbing member is heated to a relatively high temperature and at the same time the impurities are desorbed from the adsorbent. Further, in the heating and desorption step, a liquid heat medium is used to heat the adsorbent in the adsorption tube. In the cooling step, the adsorbent in the adsorption tube is cooled. Further, in the cooling step, the liquid refrigerant is used to cool the adsorbent in the adsorption tube. Examples of the target gas to be purified by the method include rare gases such as ruthenium, osmium, iridium, and 13 201043571 iSL. According to the seventh aspect of the present invention. In the present device, for example, for the purpose of purifying a gas, a s $ ώ 疋 3 3 - a TSA adsorption tower having a first gas passage opening and a second gas passage opening, the adsorption tube and The first and second gas:, ... the u-refrigerant storage tank, for the purpose of storing the adsorbent in the 'and off' of the cooling device, for storing the liquid into the TSA adsorption tower, a heat medium storage tank To heat the adsorbent in the adsorbent to (4) 'to store the liquid supplied to the (10) adsorption tower

·、'、媒 ^ —媒線’用以將冷媒從冷媒貯槽供應至TSA 吸附塔第二冷媒線，用以將冷媒從说吸附塔回送至冷媒貯槽，帛-熱媒線，用以將熱媒從該熱媒貯槽供應至TSA吸附塔；以及一箪_舳丄甘成 " 及第一熱媒線，用以將熱媒從該TSA 吸附塔回送至熱媒貯槽。若藉由具備這樣的結構的本裝置’可以適當地實行本發明的第五特徵相關之上述的目的氣體精製方法。根據本發明的第八特徵，是提供一種目的氣體精製裝置。在本裝置中，是包含：複數個丁SA吸附塔，其具有一第一氣體通過口與一第二氣體通過口，並具有一吸附管，上述吸附管與此第一及第二氣體通過口連通且充填有吸附劑，一冷媒貯槽，以冷卻吸附管内的吸附劑為目的，用以存放供應至TSA吸附塔的液狀冷媒；一熱媒貯槽，以加熱吸附管内的吸附劑為目的，用以存放供應至TSA吸附塔的液狀熱媒；一氣體線’具有一主幹路及複數個分支路，上述分支路是設置於每一個TSA吸附塔並連接此TSA吸附塔 14 201043571 • 的第二氣體通過口側；一笙— '人丄甘& « 1Λ 第冷媒線，用以將冷媒從冷媒貯槽供應至吸附劑冷卻對象的TSA吸附塔；一第二冷媒線’用謂冷媒從tsAd及附塔回送至冷媒貯槽；一^執媒線，用以將熱媒從熱媒貯槽供應至吸附劑加熱對象的吸附塔；以及-第二熱媒線，用以將熱媒從m吸附塔回送至熱媒貯槽。 Ο 【實施方式】【用以實施發明的最佳形態】第1圖是顯示本發明相關的氬精製裝置γ的全體概略結構。氬氣精製裝置Y是具有貯留系統卜前處理系統2、 PSA(Pressure Swing Ads〇rpti〇n)系统 3、回1線 4、鱼 mmermalSwingAdsorpti()n)_54^M_ 收3氬的原料氣體G。並同時連續式地精製氬。原料氣體G。是被用於單晶石夕拉晶爐、陶究燒結爐、製鋼用真空脫氣爐、太陽電池时電_解料中的爐内氣氛氣體而混入不純物的氬，而從至少一個既定的爐且(省：其圖示则性或斷續性地排出。此排放氣體(原料氣體㈠的排出流量、壓力、組成等，常會隨著在爐中的實施中的步驟、爐子的操作條件等而變動，也會有急遽變動的情況。原料氣體h是含有氬氣作為主成分，且 Μ 虱、一氧化碳、虱、及二氧化碳。主要的不純物例如為氮。成為氬氣精製裝置Υ的一部分之貯留系統ι，是如Ρ 所不’具有緩衝槽(buffer tank)1。、除塵器u、升魔 15 201043571 吹風器(bl〇wer)12、濃度分析計13、流量控制部η、及具有原料氣體導入端的綾^ 37深15。除塵器11'緩衝槽1〇、升 Μ吹風器12、及流量控制部u, 一 4疋在線I 5内成直列配置。緩衝槽1 0是用以暫時貯叙a _ 曰 > 、丁留3風的5氣體（包含原料氣體G。）的貯留槽。另外，扃 Γ在本貫施形態中，是將緩衝槽 10構成為用於收容氣體的容 J 谷積可變動的緩衝槽10，例如是藉由内部空間間可擴大、縮小的袋狀物體來形成貯留空間。除塵器11是將來自爐具的的排放軋體之原料氣體G。中所含的夕量的粉塵、金屬粉等 ./取乃攸原枓軋體Gfl除去。這樣的除塵器1〗，是配 a— 在緩衝槽丨〇的上流側，而有例如既疋的除塵過濾器而成。升壓σ人風益12是配置在緩衝择仗後衡糟1 〇的下流側，了將原料氣體G。收進緩衝槽1〇而疋為 19 6Α a 動。藉由升壓吹風器 12的作動，負壓作用於緩衝槽i 〇原料氣體〇。適當地流入緩衝槽10。内另I氣體貯留空間，使 12的作動，將氣體^從緩衝槽^出卜，藉由升壓吹風器統2送出此氣體G” U ’而㈣前處理系派度分析計1 3是測定經過緩衝 - M r ^ ^ , 衝槽丨〇及升壓吹風器12 的虱體G!所含的各不純物的濃度。 1 q - ί,ι ^ r 具體而言，濃度分析計 13疋測疋軋體Gl所含的氮、— 乳π妷、氣、氫、及二 ❹I自It b ^ 乳化流量控制部14是控制供庫$舒+ 4 r ^ θ 别處理系統2等的後段的軋體G)的〜置。這樣的流量控 J P 14是例如可控制開合 201043571 度的閥所構成。 Ο Ο 一成為氬精製裝置Υ的一部分的前處理系統2，是從氣除去以後段的PSA系統3中所實行的壓力變動吸附法 (PSA法）、後段的TSA系統5中所實行的溫度變動吸附法 (TSA法）等所難以除去的不純物。作為精製氬之時藉由法、TSA法等難以除去的不純物者，可列舉出的有氧及氫。另卜因為氧$對將精製後的氬氣作為爐内氣氛氣體而再 :用之％有害’有很尚的除去必要性。前處理系統2是如第1圖所π ’具有刖處理槽2〇Α、2〇β、、預熱器2卜 ’、P器22A 22B、22C、氧供應量控制部23Α、23β、2儿、氫供應量控制部24、溫度計25A、25B、25c、氮濃度分析計26、及線27。前處理槽m、2〇β、抓，是在線π内配置成直列的狀態。線27目,丨七人&。深 ^ 貝]包含線 27A、27B、27C、27D。月ίΐ處理槽2 0 A是轉化及；^ μ " 疋轉化夂應槽，其用於將氣體匕中的一氧化石厌變成二氧化碳而管皙μ队丄，厌而貫貝上除去（一氧化碳會有對於充填於後段的前處理槽2〇R、9nr 20C的觸媒而言為觸媒毒的情況）。在前處理槽20A中，早*话# _ 甲疋充填著促進下列的反應式（1) 所表示的轉化反應的觸媒。、可用來作為此觸媒者，例如在白系觸媒、鈀系觸媒等的貴金屬觸媒。【化1】 CO+(l/2)〇2->C〇2 · .⑴ 刖處理槽20B是轉化斤虛祕 W化反應槽，其用於將經過前處理槽 20A中的處理而由前處理械9ηΛ 月J爽理槽20A導出的氣體Gl中的氫及氧變成水而將其低遭度化或實暂, 、貝上除去。在前處理槽2〇β 201043571 示的轉化反應的觸媒' 鈀系觸媒等的中’是充填著促進下列的反應式（2)所表媒。可用來作為此觸媒者，例如銘系觸貴金屬觸媒。【化2】·, ', medium ^ - media line' is used to supply the refrigerant from the refrigerant storage tank to the second refrigerant line of the TSA adsorption tower for returning the refrigerant from the adsorption tower to the refrigerant storage tank, and the heat medium line for heat The medium is supplied from the heat medium storage tank to the TSA adsorption tower; and a first heat medium line is used to return the heat medium from the TSA adsorption tower to the heat medium storage tank. The above-described target gas purification method according to the fifth feature of the present invention can be suitably carried out by the present device having such a configuration. According to an eighth feature of the present invention, a target gas refining device is provided. In the device, the method comprises: a plurality of D-SA adsorption towers having a first gas passage port and a second gas passage port, and having a adsorption tube, the adsorption tube and the first and second gas passage ports Connected and filled with an adsorbent, a refrigerant storage tank for cooling the adsorbent in the adsorption tube for storing the liquid refrigerant supplied to the TSA adsorption tower; a heat medium storage tank for heating the adsorbent in the adsorption tube for the purpose To store the liquid heat medium supplied to the TSA adsorption tower; a gas line 'haves a trunk road and a plurality of branch roads, and the branch roads are disposed in each of the TSA adsorption towers and connected to the TSA adsorption tower 14 201043571. The gas passes through the mouth side; one 笙 - '人丄甘& « 1Λ The second refrigerant line is used to supply the refrigerant from the refrigerant storage tank to the TSA adsorption tower of the adsorbent cooling target; a second refrigerant line 'uses the refrigerant from tsAd and The attached tower is sent back to the refrigerant storage tank; a control medium for supplying the heat medium from the heat medium storage tank to the adsorption tower of the adsorbent heating object; and a second heat medium line for returning the heat medium from the m adsorption tower To the heat medium Storage tank. [Embodiment] [Best Mode for Carrying Out the Invention] Fig. 1 is a view showing the overall configuration of an argon refining device γ according to the present invention. The argon gas refining device Y is a material gas G having a storage system pretreatment system 2, a PSA (Pressure Swing Ads 〇〇 ti ti) system 3, a 1 line 4, a fish mmermal Swing Adsorpti () n) _54 ^ M_ 3 argon. At the same time, argon is continuously purified. Raw material gas G. It is used in a single crystal stone crystallization furnace, a ceramics sintering furnace, a vacuum degassing furnace for steelmaking, and an argon in which the atmosphere in the furnace is mixed with impurities in the solar cell, and at least one predetermined furnace is used. And (province: the illustration is discharged intermittently or intermittently. The discharge gas (the discharge flow rate, pressure, composition, etc. of the raw material gas (1)) often follows the steps in the implementation of the furnace, the operating conditions of the furnace, and the like. In the case of a change, there is a case where there is a sudden change. The raw material gas h contains argon as a main component, and ruthenium, carbon monoxide, ruthenium, and carbon dioxide. The main impurity is, for example, nitrogen. The storage system that is part of the argon refining unit Υ ι, Ρ Ρ 具有具有具有具有具有具有具有具有具有具有具有具有具有具有具有具有具有具有具有具有具有具有 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 The end of the 绫 ^ 37 depth 15. The dust collector 11 'buffer tank 1 〇, the rising hair dryer 12, and the flow control unit u, a 4 疋 line I 5 in-line configuration. The buffer tank 10 is used for temporary storage a _ 曰>, Dingliu 3 wind 5 gas (package In the present embodiment, the buffer tank 10 is configured to accommodate a variable buffer tank 10 for accommodating gas, for example, by internal space. The bag-like object can be expanded and contracted to form a storage space. The dust remover 11 is a dust, metal powder, etc. contained in the raw material gas G of the discharge rolled body from the stove. The rolling body Gfl is removed. Such a precipitator 1 is equipped with a- on the upstream side of the buffer tank, and has a dust filter such as a sputum. The boost σ 人风益12 is arranged in the buffer. On the downstream side of the balance 11, the raw material gas G is taken into the buffer tank 1〇 and 疋 is 19 Α a. By the action of the booster blower 12, the negative pressure acts on the buffer tank i 〇 the raw material gas 〇 Appropriately flow into the buffer tank 10. The other I gas storage space allows the operation of 12 to discharge the gas from the buffer tank, and the booster blower unit 2 sends the gas G" U ' and (4) the pretreatment system The dispatch analyzer 1 3 is measured by buffer - M r ^ ^, punching and boosting blower The concentration of each impurity contained in the carcass G! of 12: 1 q - ί,ι ^ r Specifically, the concentration analyzer 13 measures the nitrogen contained in the rolling body G1, - π 妷, gas, hydrogen, And the second ❹I from It b ^ emulsified flow rate control unit 14 is a set of the rolling body G) for controlling the rear stage of the storage system $4 + 4 r ^ θ. The flow control JP 14 is, for example, controllable. It is composed of a valve of 201043571. Ο Ο A pretreatment system 2 that is part of the argon refining unit 是 is a pressure fluctuation adsorption method (PSA method) and a TSA in the latter stage of the PSA system 3 that removes gas from the later stage. The impurities which are difficult to remove, such as the temperature fluctuation adsorption method (TSA method) carried out in the system 5. Examples of the impurities which are difficult to remove by a method such as a method or a TSA method when argon is purified include aerobic and hydrogen. In addition, because oxygen is used to treat the argon gas after purification as the atmosphere gas in the furnace, it is harmful to use. There is a great need for removal. The pretreatment system 2 is π' having a treatment tank 2〇Α, 2〇β, a preheater 2', a P device 22A 22B, 22C, an oxygen supply amount control unit 23Α, 23β, 2 as shown in Fig. 1 The hydrogen supply amount control unit 24, the thermometers 25A, 25B, and 25c, the nitrogen concentration analyzer 26, and the line 27. The pre-processing tanks m, 2 〇 β, and grab are arranged in an in-line state in the line π. Line 27, 丨 seven people & Deep ^ Bay] contains lines 27A, 27B, 27C, 27D. The month ΐ treatment tank 2 0 A is a conversion and; ^ μ " 疋 conversion 夂槽 tank, which is used to turn the oxidized stone in the gas enthalpy into carbon dioxide and the tube 皙丄 , , , , , , , , , , , , , , , , , , , , , , , , , , There may be a case where the catalyst of the pretreatment tank 2〇R, 9nr 20C filled in the subsequent stage is catalytically poisonous). In the pretreatment tank 20A, the catalyst is promoted by a catalyst which promotes the conversion reaction represented by the following reaction formula (1). It can be used as a catalyst for the catalyst, for example, a noble metal catalyst such as a white catalyst or a palladium catalyst. [Chemical Formula 1] CO+(l/2)〇2->C〇2 · (1) The treatment tank 20B is a conversion tank, which is used to pass the treatment in the pretreatment tank 20A. The hydrogen and oxygen in the gas G1 derived from the processing device 9A 爽爽理 20 20A are turned into water, and are temporarily reduced or temporarily removed. In the catalyst 'palladium catalyst or the like of the conversion reaction shown in the pretreatment tank 2 〇β 201043571, the medium of the reaction formula (2) which promotes the following is filled. Can be used as a catalyst for this, such as the touch of precious metal catalyst. [Chemical 2]

11 2U 月ϋ處理槽2 Π Γ θ + 2〇β t ® 疋％槽，其用於將經過前處理槽 20B中的處理而由前處理槽僧變成水而將其低濃度化或實的虱及氣中，是充填著促進上列的反所月^理槽2〇〔媒，來作為此觸媒者反應的觸貴金屬觸媒。麵系觸媒、把系觸媒等的預熱器21是A τ * μ & , 為了在到達前處理槽0 # 如由電熱器所構成。氧供庫量彳4體Gl，例留部連結，且與線27A連結。：樣° 3A是與圖外的氧貯是為了控制因應需求而從氧貯留:广供應量控制部23A 量，例如由可控制開合度：；：至線2^的氧的流溫度物是測定導入前處理槽冷卻器22A是為了冷卻 ^乳體^的溫度。由前處理槽20A的出口端2〇別处理槽2〇A中的處理而 ⑽。這樣的冷卻器2^^導出的氣體G”而設置於線熱交換器所構成。氧供應量為冷卻媒介的部連結，且與線27β連結 / β疋與圖外的氧貯留為了控制因應需求而從氧貯留部的/供應量控制部挪是量，例如由可控制開合度；供應至線27β的氧的流打開狀態時間等的閥所構成。 201043571 * 溫度計2 5 B是测定導人ι占冷卻器⑽是為Λ=Λ0β之前的氣體G】的溫度。由前處理槽20B導出的广處理槽2〇B中的處理而 J礼體G]，而設置於峻27f 冷卻器22Β是例如為於踝延樣的構成。氧供應量控:部為冷卻媒介的熱交換器所與線27C連結。這产^ π與圖外的氧貯留部連結，且。水、氧供應量控制部Me是為了扣在丨應需求而從氧貯留卹也處 ^扎疋馬了控制因人, 應至線27C的氧的流量，例如由可控制開合度' 打開妝能n±⑽ n观田可心夺間等的閥所構〇部24是與圖外的氫飞供應量控制 l 丁 W 口 (5連結，且盘 _ 氫供應量控制部24 a盔π 一，、’ C連、·Ό。廷樣的廡$结97厂了控制因應需求而從氫貯留部供應至線27C的虱的流量例如由可控制〜時間等的閥所構成。又打開狀悲11 2U ϋ ϋ 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 In the gas, it is filled with the anti-small metal tank that promotes the above-mentioned reaction. The preheater 21 of the surface catalyst, the catalyst, etc. is A τ * μ & , in order to form the pre-treatment tank 0 # as constituted by an electric heater. The oxygen supply amount is 4, G1, and the remaining portion is connected, and is connected to the line 27A. : Sample ° 3A is the oxygen storage outside the figure to control the demand from the oxygen storage: the wide supply control unit 23A amount, for example, the controllable opening degree:;: to the line 2 ^ oxygen flow temperature is measured The pre-treatment tank cooler 22A is introduced to cool the temperature of the emulsion. The processing in the processing tank 2A is discriminated by the outlet end 2 of the pretreatment tank 20A (10). The gas G" derived from the cooler 2^^ is provided in the line heat exchanger. The oxygen supply amount is the connection of the cooling medium, and is connected to the line 27β/β疋 and the oxygen storage outside the figure in order to control the demand. In addition, the amount of the oxygen storage unit/supply amount control unit is increased by, for example, a valve that can control the degree of opening and closing, the flow of the oxygen supplied to the line 27β, and the like. 201043571 * The thermometer 2 5 B is the measurement guide ι The chiller (10) is the temperature of the gas G before Λ = Λ 0β. The processing in the wide processing tank 2 〇 B derived from the pretreatment tank 20B is the J ritual G], and the cooler 27 设置 is provided, for example. The composition of the oxygen supply is controlled by the heat exchanger of the cooling medium, and is connected to the line 27C. This product is connected to the oxygen storage unit outside the figure, and the water and oxygen supply control unit Me In order to buckle in the demand for sputum, the oxygen storage shirt is also in control of the person, the flow of oxygen to the line 27C, for example, by the controllable opening degree 'open makeup ability n ± (10) n Guan Tian can heart The damming portion 24 of the valve is the hydrogen supply supply control outside the figure. 5 is connected, and the disk_hydrogen supply amount control unit 24a is a helmet π1, 'C 连, Ό Ό. The 样结结 97 97 factory controls the flow rate of 虱 supplied from the hydrogen storage unit to the line 27C according to the demand. For example, it consists of a valve that can be controlled ~ time, etc.

計26是在流動於線饥的亂體Gi添加虱、氧箄夕今 ^ J 虱等之别，測定氣體Gl的氫 25C是測定導入前處理槽又，皿度计、 ZUL之則的氣體Gi的溫度。冷卻器22C是為了冷卻姐义 7 P、，工過則處理槽20C中的處理而由前處理槽20C導出的氣體G，慝而〇體Gl而設置於線27D。這樣的冷卻器22C是例如為以冷卻 k像的作為冷㈣介的熱交換器所構成。本實施形態中的前處理系統2，θ 疋具有如上所述的三段的轉化反應槽。然而，因應將氣 — L篮（η供應至後段（pSA系統3、TSA系統5)之前從此氣體G ” 所欲除去的不純物的種類及量，亦可以將前處理系統2構成為具備一段的轉化反應槽、或二段的轉化反應槽、或四又的轉化反應槽。或者是，將氣體供應至後段（PSA系統 iSA系統5)之前並 19 201043571 無從此氣體G,所欲除去的氮以外的不純物的情況，則亦可不設置前處理系統2。成為氬氣精製裝置Y的一部分的PSA系統3，是如第i 圖及第2圖所示’具有PSA裝置30。PSA裝置3〇是具有吸附塔31A ' 31B、31C、升壓機32、冷卻器33、線34〜37，其構成是可利用來自前處理系統2的氣體Gi的壓力變動吸附法（PSA法）’而濃縮分離氬。吸附塔31A、31B、31C各自在兩端具有氣體通過口 31a、31b，並在氣體通過口 31a、31b之間，充填有用以選擇性吸附氣體G,所含的不純物的吸附劑。例如，可使用式沸石（zeol ite)來作為用以吸附作為不純物的氮、一氧化碳、二氧化碳等的吸附劑。例如，可使用碳分子篩（carb〇n molecular sieves; CMS)來作為用以吸附作為不純物的二氧化碳的吸附劑。例如，可使用氧化鋁來作為用以吸附作為不純物的水分的吸附劑。可以在吸附塔31a、3ib、3ic 充填一種的吸附劑，亦可以在吸附塔31Α、31β、3ic層積、充填複數種的吸附劑。關於充填於吸附$ 3 i A、3 i B、3丄c 内的吸附劑的種類、數量等，是因應欲在吸附塔31A、31B、 31C除去的不純物的種類及量來決定。升壓機32疋具有氣體吸入口 32a及氣體送出口 32b。氣體吸入口 32a是與前處理系統2中的線27D連結。這樣的升壓機32的目的是將從氣體吸入口 32a吸引的氣體G) 從氣體送出口 32b向著吸附塔3U、31B、31C供應及送出，例如為壓縮機。 201043571 冷卻器33是在將氣體L供應至吸附塔31A、31B、31C 之前’將此氣體G!冷卻。線34是具有主幹路34，及分支路34Α、34β、34C，主幹路34’是連接升壓機32的氣體送出口 32b，分支路34a、 34B、34C疋各自連接吸附塔31A' 31B、31C的各氣體通過口 31a側。在分支路34A、34B、34C，是附設有可以在開狀態與閉狀態之間切換的自動M 34a、34b、34c。另外， 0在線34的主幹路34’，是配置著上述的冷卻器33。線35是具有主幹路35,及分支路35A、35B、35(：，分支路35A、3 5B、35C是各自連接吸附塔31A、31B、31(：的各氣體通過口 31b側。在分支路35A、35B、35C，是附設有可以在開狀態與閉狀態之間切換的自動閥35a、35b、35c。線36是具有主幹路36,及分支路36A、36B、36C，分支路36A、36B、36C是各自連接吸附塔31A、31B、31(：的各氣體通過口 31b側。在分支路36A、36B、36c，是附設 Ο 有可以在開狀態與閉狀態之間切換的自動閥36a、36b、36c。線37是具有主幹路37’及分支路37A、37B、37C，主幹路37是具有氣體排出端E2，分支路37A、37B、37C是各自連接吸附塔31A、31B、31C的各氣體通過口 31a側。在分支路37A、37B、37C，是附設有可以在開狀態與閉狀心之間切換的自動閥3 7a、37b、37c ;在主幹路37，，是附 °又有可以在開狀態與閉狀態之間切換的自動閥3 7 d。本實施形態中的PSA系統3或PSA裝置30是具有如上所述的吸附塔31A、31B、31C。然而，亦可以將PSA系統3 21 201043571 t成為具備—個吸附塔、亦可以構成為具備二個吸附塔、 :、：以構成為具備四個以上的吸附塔者。或者是，將氣體〜至後奴的TSA系統5之前並無從此氣體所欲除去的氮以外的不純物的情況，則亦可不設置m系統3。成為氬氣精製裝置Y的一部分的回收線4,是如第i 圖所示，連結PSA系統3或PSA裝置3〇中的上述線3?、與貯m 1中的上述緩衝槽1G。在回收線4，是附設有可以在開狀態與閉狀態之間切換的自動閥4a。這樣的回收線4’是使從PSA裝置中的吸附塔31A、31B、川的各氣體通過口 31a側排出的既定氣體回到緩衝槽ι〇。成為氬精製裝置Y的一部分的TSA系統5,是如第i 圖及第3圖所示，具有TSA裝置5〇。TSA裝置5〇是具有吸附塔51A、51B、熱交換器52A、冷卻器52β、冷媒槽52〇、冷媒幫浦52D、鹽水冷卻器（brine c〇〇ler)52E、熱媒槽 52F '熱媒幫浦52G、成為氣體流路的線53〜58、與冷媒熱媒線，其中上述冷媒熱媒線是包含與冷媒流動及熱媒流動相關的線59a〜59f，且在既定部位附有自動閥。TSA裝置 5 0疋構成為利用溫度變動吸附法（TSA法），而可以從來自 PSA系統3的準精製氣體G2進一步地濃縮分離氬。吸附塔51Α、51β是分別具有氣體通過口 51a、51b、至少一根吸附管51c、二片分隔板51d、與空間部51e、51f。吸附塔51A、51B是被縱向放置。在吸附管51c中，是充填有用以選擇性吸附作為氣體所含的不純物之默的吸附劑。可使用例如，可使用CaX式沸石、Ca絲光沸石 22 201043571 (mordenite)式沸石、及LiX式沸石來作為此類的吸附劑。可以在吸附管51c内充填一種的吸附劑，亦可以在吸附塔 51A、51B内層積、充填複數種的吸附劑。這樣的吸附管 51c，是在塔内受到分隔板51d的支撐，而連通吸附管5ic 内部與空間部51e乃至氣體通過口 51a、51b。另外，空間部51 e是氣體流路的一部分；而空間部5丨f是接受容納冷媒、熱媒等的部位；而上述空間部51e、51f是藉由分隔板 51d而分隔出來。 0 熱交換器52A是冷卻從PSA裝置3〇導出的準精製氣體 G2 ’冷卻器52B是冷卻已經過熱交換器52A的準精製氣體 G2 ’冷媒槽52C是存放液狀的冷媒M1。作為冷媒叽者可使用例如乙醇水溶液、甲醇水溶液、氣化鈣水溶液、氯化甲、元或乙一醇。冷媒幫浦52D是將冷媒槽52C内的冷媒 Ml运至鹽水冷卻器52E側而至吸附塔5lA、5ib側。鹽水冷部益52E是附有冷;東機的冷媒冷卻器，其是為了在冷媒〇 M1到達吸附塔51A、51B之前，將此液狀冷媒冷卻至既定狐度為止。熱媒槽52f是存放液狀的熱媒m2並加熱熱媒 M2而在熱媒槽52F是設置有既定的加熱工具（省略其圖不）。作為熱媒M2者，可使用例如乙醇水溶液、甲醇水溶液氣化鈣水溶液、氣化甲烷、或乙二醇。在本實施形態中々媒Ml及熱媒M2是同一種類的液體。熱媒幫浦52G 是將熱媒槽52F内的熱媒M2送至吸附塔5U、51β側。線53是具有主幹路53,及分支路53a、53B，分支路 53Α 53β疋各自連接吸附塔51Α、51β的各氣體通過口 51a 23 201043571 側。在分支路53A、53B ’是附設有可以在開狀態與閉狀離 ^間切換的自動閥53a、53b。上述的熱交換器52A及冷卻器52B’是設置於線53的主幹路53’。線54是具有主幹路54’及分支路54Α、54β，分支路 B疋各自連接吸附塔51A、51B的各氣體通過口 51b 側。在分支路54A、54B ’是附設有可以在開狀態與閉狀態之間切換的自動閥54a、54b。線54的主幹路54，，是連接於上述的熱交換器52A。線55是具有精製氣體導出端E3，並經由熱交換器與線5 4連通。線％是具有主幹路56,及分支路56a、56B，分支路 56A、56B是各自連接吸附塔51八、516的各氣體通過口 5比側。在分支路56A ' 56B ’是附設有可以在開狀態與閉狀態之間切換的自動閥56a、56卜另外，線56的主幹路56,，是與上述的線55連結，而在主幹路56，，是附設有可以在開狀態與閉狀態之間切換的自動閥56c。線57是具有主幹路57，及分支路57Α、57β，分支路 57八、578是各自連接吸附塔51八、518的各氣體通過口511) 側。在分支路57A、57B，是附設有可以在開狀態與閉狀態之間切換的自動閥57a、57b。另外，線57的主幹路57,，是連結於線54的主幹路54’。線58是具有主幹路58’及分支路58A、58B，分支路 58A、58B疋各自連接吸附塔51A、51B的各氣體通過口 51a 側。在分支路58A、58B，是附設有可以在開狀態與閉狀態 201043571 之間切換的自動間。s al ,, 阀wa 58b另外，線58的主幹路58，，是連結於上述的貯留系統1的緩衝槽丨〇。已3於~媒熱媒線的線59a，是供應到吸附塔51A、51 β 的冷媒供應用線，其直列地連結冷媒槽孤、冷媒幫浦 ⑽、鹽水冷卻器52E，且其設置是可以與吸附塔5ια、5ΐβ 的各自的空間部51 f的下端側連通。The meter 26 is a gas that flows in the line of hunger, Gi, 箄, 箄, 今, J, J, 虱, etc., and the hydrogen 25C of the gas G1 is measured before the introduction of the treatment tank, and the gas of the meter, ZUL, Gi temperature. The cooler 22C is a gas G which is led out from the pretreatment tank 20C in order to cool the spurs 7 P, and is processed in the treatment tank 20C, and is disposed on the line 27D. Such a cooler 22C is constituted, for example, as a heat exchanger that cools the k-image as a cold junction. In the pretreatment system 2 of the present embodiment, θ 疋 has the three-stage conversion reaction tank as described above. However, the pretreatment system 2 may be configured to have a transition in response to the type and amount of impurities to be removed from the gas-G basket (n is supplied to the gas (G) before the supply of the gas to the rear stage (pSA system 3, TSA system 5). a reaction tank, or a two-stage conversion reaction tank, or a four-stage conversion reaction tank. Alternatively, the gas is supplied to the rear stage (PSA system iSA system 5) and 19 201043571 is free from the gas G, except for the nitrogen to be removed. In the case of an impurity, the pretreatment system 2 may not be provided. The PSA system 3 which is a part of the argon refining device Y has the PSA device 30 as shown in Fig. 1 and Fig. 2. The PSA device 3 has adsorption. The towers 31A' 31B, 31C, the booster 32, the cooler 33, and the lines 34 to 37 are configured to concentrate and separate argon by a pressure fluctuation adsorption method (PSA method) of the gas Gi from the pretreatment system 2. The towers 31A, 31B, and 31C each have gas passage openings 31a and 31b at both ends, and between the gas passage ports 31a and 31b, are filled with an adsorbent for selectively adsorbing the impurities contained in the gas G. For example, it can be used. Zeolite Ie) is used as an adsorbent for adsorbing nitrogen, carbon monoxide, carbon dioxide, or the like as an impurity. For example, carbon molecular sieves (CMS) can be used as an adsorbent for adsorbing carbon dioxide as an impurity. For example, Alumina may be used as an adsorbent for adsorbing moisture as an impurity. One type of adsorbent may be charged in the adsorption towers 31a, 3ib, and 3ic, or a plurality of types of adsorption may be stacked in the adsorption towers 31, 31, and 3ic. The type and amount of the adsorbent charged in the adsorbed $3 i A, 3 i B, and 3丄c are determined in accordance with the type and amount of the impurities to be removed in the adsorption towers 31A, 31B, and 31C. The press 32A has a gas suction port 32a and a gas delivery port 32b. The gas suction port 32a is connected to the wire 27D in the pretreatment system 2. The purpose of such a booster 32 is to attract the gas G from the gas suction port 32a. It is supplied and sent from the gas delivery port 32b to the adsorption towers 3U, 31B, 31C, for example, a compressor. 201043571 The cooler 33 is before supplying the gas L to the adsorption towers 31A, 31B, 31C. The gas G is cooled. The line 34 has a main road 34, and branch circuits 34A, 34β, 34C. The main road 34' is a gas delivery port 32b connected to the booster 32, and the branch paths 34a, 34B, 34C are connected to each other. Each of the gas passages 31a and 31C of the towers 31A' 31B and 31C is provided with automatic M 34a, 34b, and 34c that can be switched between an open state and a closed state. Further, the trunk line 34' of the 0 line 34 is the cooler 33 described above. The line 35 has the trunk line 35 and the branch paths 35A, 35B, and 35 (: the branch paths 35A, 35B, and 35C are connected to the respective gas passage ports 31b of the adsorption towers 31A, 31B, and 31. 35A, 35B, 35C are provided with automatic valves 35a, 35b, 35c that can be switched between an open state and a closed state. Line 36 has a main road 36, and branch paths 36A, 36B, 36C, branch paths 36A, 36B 36C is a side of each of the gas passage openings 31b to which the adsorption towers 31A, 31B, and 31 are connected. The branch passages 36A, 36B, and 36c are provided with an automatic valve 36a that can be switched between an open state and a closed state. 36b, 36c. The line 37 has a trunk road 37' and branch paths 37A, 37B, 37C, the trunk road 37 has a gas discharge end E2, and the branch paths 37A, 37B, 37C are each connected to the adsorption towers 31A, 31B, 31C. The gas passage port 31a side. The branch passages 37A, 37B, and 37C are provided with automatic valves 37a, 37b, and 37c that are switchable between an open state and a closed center; in the main road 37, An automatic valve 3 7 d that can be switched between an open state and a closed state. The PSA system 3 or the PSA device in this embodiment 30 is the adsorption towers 31A, 31B, and 31C as described above. However, the PSA system 3 21 201043571 t may be provided with one adsorption tower, or may be configured to include two adsorption towers: For example, if there is no impurity other than nitrogen to be removed from the gas before the TSA system 5 of the gas to the slave, the m system 3 may not be provided. The recovery line 4 of a part of Y is connected to the above-mentioned line 3? in the PSA system 3 or the PSA unit 3, and the above-mentioned buffer tank 1G in the storage m1 as shown in Fig. i. There is an automatic valve 4a that can be switched between an open state and a closed state. Such a recovery line 4' is such that a predetermined gas discharged from the adsorption towers 31A, 31B in the PSA apparatus and the respective gas passage openings 31a of the river is returned to the buffer. The TSA system 5 which is a part of the argon refining device Y has a TSA device 5 as shown in Fig. 1 and Fig. 3. The TSA device 5 has an adsorption tower 51A, 51B and a heat exchanger 52A. , cooler 52β, refrigerant tank 52〇, refrigerant pump 52D, brine cold (bine c〇〇ler) 52E, heat medium tank 52F 'heat medium pump 52G, lines 53 to 58 which become gas flow paths, and refrigerant heat medium line, wherein the refrigerant heat medium line contains and flows with refrigerant and heat The medium flow-related lines 59a to 59f are provided with an automatic valve at a predetermined portion. The TSA device 500 is configured to be further concentrated from the quasi-refined gas G2 from the PSA system 3 by a temperature fluctuation adsorption method (TSA method). Argon was separated. The adsorption towers 51A and 51β respectively have gas passage ports 51a and 51b, at least one adsorption tube 51c, two partition plates 51d, and space portions 51e and 51f. The adsorption towers 51A, 51B are placed longitudinally. The adsorption tube 51c is filled with an adsorbent for selectively adsorbing impurities which are impurities contained in the gas. For example, CaX type zeolite, Ca mordenite 22 201043571 (mordenite) type zeolite, and LiX type zeolite can be used as such an adsorbent. One type of adsorbent may be filled in the adsorption tube 51c, or a plurality of adsorbents may be stacked and filled in the adsorption towers 51A and 51B. The adsorption tube 51c is supported by the partition plate 51d in the tower, and communicates with the inside of the adsorption tube 5ic and the space portion 51e or the gas passage ports 51a and 51b. Further, the space portion 51 e is a part of the gas flow path; the space portion 5 丨 f is a portion for receiving the refrigerant, the heat medium, and the like; and the space portions 51e and 51f are partitioned by the partition plate 51d. The heat exchanger 52A cools the quasi-purified gas G2 derived from the PSA unit 3'. The cooler 52B cools the quasi-purified gas G2 that has passed through the heat exchanger 52A. The refrigerant tank 52C is a liquid refrigerant M1. As the refrigerant, for example, an aqueous ethanol solution, an aqueous methanol solution, an aqueous calcium carbonate solution, a methyl chloride, a methyl group or an ethyl alcohol can be used. The refrigerant pump 52D transports the refrigerant M1 in the refrigerant tank 52C to the brine cooler 52E side to the adsorption towers 51A and 5ib. The brine cold section benefit 52E is a refrigerant cooler attached to the east machine to cool the liquid refrigerant to a predetermined degree before the refrigerant 〇 M1 reaches the adsorption towers 51A and 51B. The heat medium tank 52f stores the liquid heat medium m2 and heats the heat medium M2, and the heat medium tank 52F is provided with a predetermined heating tool (not shown). As the heat medium M2, for example, an aqueous solution of ethanol, a solution of calcium carbonate in an aqueous solution of methanol, vaporized methane, or ethylene glycol can be used. In the present embodiment, the medium M1 and the heat medium M2 are the same type of liquid. The heat medium pump 52G sends the heat medium M2 in the heat medium tank 52F to the adsorption tower 5U, 51β side. The line 53 has a trunk line 53, and branch paths 53a and 53B, and the branch passages 53A, 53β are connected to the respective gas passage ports 51a 23 201043571 side of the adsorption towers 51A and 51β. The branch passages 53A, 53B' are provided with automatic valves 53a, 53b that are switchable between an open state and a closed state. The heat exchanger 52A and the cooler 52B' described above are the main roads 53' provided on the line 53. The line 54 has a trunk passage 54' and branch passages 54A and 54β, and the branch passages B疋 are connected to the respective gas passage ports 51b side of the adsorption towers 51A and 51B. The branch passages 54A, 54B' are provided with automatic valves 54a, 54b that are switchable between an open state and a closed state. The main road 54 of the line 54 is connected to the heat exchanger 52A described above. Line 55 has a refined gas outlet end E3 and is in communication with line 504 via a heat exchanger. The line % has a main road 56 and branch paths 56a and 56B, and the branch paths 56A and 56B are connected to the respective gas passage ports 5 of the adsorption towers 51 and 516, respectively. The branch path 56A '56B' is provided with automatic valves 56a, 56 that can be switched between the open state and the closed state. In addition, the main road 56 of the line 56 is connected to the line 55 described above, and is connected to the main line 56. , is an automatic valve 56c that can be switched between an open state and a closed state. The line 57 has a main path 57, and branch paths 57A and 57β, and the branch paths 578 and 578 are side of the respective gas passage ports 511) to which the adsorption towers 51 and 518 are connected. The branch paths 57A and 57B are provided with automatic valves 57a and 57b which are switchable between an open state and a closed state. Further, the trunk road 57 of the line 57 is a trunk road 54' connected to the line 54. The line 58 has a trunk line 58' and branch paths 58A, 58B, and the branch passages 58A, 58B are connected to the respective gas passage ports 51a side of the adsorption towers 51A, 51B. The branch circuits 58A and 58B are provided with an automatic room that can be switched between an open state and a closed state 201043571. s al , valve wa 58b In addition, the trunk road 58 of the line 58 is a buffer tank connected to the above-described storage system 1. The line 59a of the medium-to-medium heat medium line is a refrigerant supply line supplied to the adsorption towers 51A and 51β, and is connected in series to the refrigerant tank orphan, the refrigerant pump (10), and the brine cooler 52E, and the setting thereof is The lower end sides of the respective space portions 51 f of the adsorption towers 5 ια and 5 ΐ β communicate with each other.

Ο 線59b是從吸附塔51A、51B回收冷媒的冷媒回收用線，其設置是可以與吸附塔51Α、5ΐβ的各自的空間部5“ 的上端側連通、且可以與空間部51f的下端側連通。另外，線59b是連接於冷媒槽52C。線59c是均麼用 '線，其設置是可以與吸附塔5ΐΑ、51β 的各自的空間部⑴的上端側連通、且連接於冷媒槽Me。線59d是供應到吸附塔51a、5_熱媒供應用線，其直列地連結熱媒槽52F及熱媒^⑽，且其設置是可以與吸附塔51A、51B的各自的空間部51f的下端側連通。線59e是從吸附塔51A、51B回收熱媒的熱媒回收用線，其設置是可以與吸附塔51Α、51β的各自的空間部… 的上端側連通、且可以與空間部51f的下端側連通。另外，線59e是連接於熱媒槽52f。線59f是均壓用、線，其設置是可以與吸附塔…、的各自的空間部⑴的上端側連通、且連接於熱媒請。使用具有如以上構造的氬精製裝置γ，則可以以如已下的要領來實行本發明相關的氬精製方法。在貯留系統i中’使升壓吹風器12作動，而從㈣ 25 201043571 的原料氣體導入端El收到原料氣體G。。收到的原料氣體 G〇因通過除塵器11而除去既定的固形成分之後，被收進緩衝槽10。在緩衝槽10中，亦從pSA系統3收進經過回收線4而來自PSA系統3的排放氣體，另外，亦從線58收進來自TSA系統5的排放氣體。然後，將氣體&從緩衝槽1〇導出。關於氣體Gi ’是藉由流量控制部丨4來調節流量。在流量控制部14受到流量控制的氣體g!，是被供應至前處理系統2。在前處理系統2中，是依序對氣體G進行在前處理槽20A的一氧化碳的除去（第一處理）、在前處理槽20B的氳濃度的降低或氫的除去（第二處理）、在前處理槽20C的第二處理後殘存的氫的除去（第三處理具體而言，在前處理槽20A中，如上所述，是藉由反應式（1)所表的轉化反應而將氣體G!中的一氧化碳變成二氧化碳來將其實質上除去。在W處理槽2 0B中’如上所述，是藉由反應式（2)所表的轉化反應而將氣體G] _的氫及氧變成水來將其低濃度化或實質上除去。在前處理槽2〇c中，如上所述，是藉由反應式（2)所表的轉化反應而將氣體&中的氫及氧變成水來將其實質上除去。在將氣體G!導入前處理槽20A之前，調節氣體Gi的溫度。具體而言，氣體G,的由溫度計25A所測定的溫度，是在線27A中通過預熱益21之時而升溫至例如【go〜150 °C。藉此，使前處理槽的反應溫度為例如2 5 〇 t以下。對於促進上述反應式（1)所表的轉化反應而言，前處理槽2〇A中的反應溫度較好為130C以上。對於在前處理槽2〇a中充分 26 201043571 抑制產生甲烷的反應而言，前處理槽2〇A中的反應溫度較好為250°C以下。在將氣體Gi導入則處理槽2〇A之前，在氣體Gi，藉由氧供應量控制部23A的作動而添加視需求之既定量的氧。氧的添加量，是根據以上述的濃度分析計13所測定的一氧化碳濃度及氧濃度所決定。為了促進上述反應式（1)所表的轉化反應而在前處理槽20A充分地除去一氧化碳，導入前處理槽的氣MG!所含的^ ’較好為導入前處理槽2〇A的氣體G,所含的一氧化碳的104.5倍當量。在前處理槽2〇八中，如上所述，發生上述反應式（1)所表的轉化反應，而將氣體Gi中的一氧化碳變成二氧化碳而將其實質上地除去。在前處理槽20A之後、將氣體Gi導入前處理槽2〇B之前’藉由通過冷卻器22A來調節氣體匕的的溫度。將氣體導入前處理槽20B之前調節氣體匕的的溫度，而使以溫度計25B所測定的溫度為例如5〇〜6(rc。藉此，使前處理〇槽2〇B中的反應溫度為例如100〜36(TC。對於促進上述反應式（2)所表的轉化反應而言，前處理槽2〇β中的反應溫度較好為ioo~36〇r。另外，假設前段的前處理槽2〇A中發生因氫與氧的反應而產生作為副產物的水的情況，由於水分會成為前處理槽20B内的觸媒的活性阻害要因，導入至前處理槽20B的氣體G!的溫度，較好為凝結溫度（例如5〇 °C )以上。在將氣體G!導入前處理槽2〇B之前，在氣體匕，藉由氧供應量控制部23B的作動而添加視需求之既定量的氧。 27 201043571 氧的添加量，是根據以上述的濃度分析計13所測定的一氧化碳濃度及氧濃度、還有在前處理槽20A之前添加的氧量所決定。上述反應式⑵所表的轉化反應為發熱反靡，導入前處理槽20B的氣體匕所含的氧，較好為使前處理槽2〇β 中的反應溫度不超過36(rc的量。在前處理槽2〇β中，如上所述’發生上述反應式（2)所表的轉化反應，而將氣體中的氫及氧變成水而將其實質上地除去或低漠度化。义在前處理槽20B之後、將氣體匕導入前處理槽2〇c之月’J ’藉由通過冷卻器2 2 R炎哨# # raA /> 1裔孓3周即氣體的的溫度。將氣體The enthalpy line 59b is a refrigerant recovery line for recovering the refrigerant from the adsorption towers 51A and 51B, and is provided so as to be able to communicate with the upper end side of each of the space portions 5' of the adsorption towers 51A and 5?, and to communicate with the lower end side of the space portion 51f. Further, the line 59b is connected to the refrigerant tank 52C. The line 59c is a 'wire' which is provided so as to be connectable to the upper end side of each of the space portions (1) of the adsorption towers 5A, 51β, and is connected to the refrigerant tank Me. 59d is supplied to the adsorption towers 51a and 5_the heat medium supply line, and the heat medium tank 52F and the heat medium (10) are connected in series, and are provided at the lower end side of the respective space portions 51f of the adsorption towers 51A and 51B. The line 59e is a heat medium recovery line for recovering the heat medium from the adsorption towers 51A and 51B, and is provided so as to be connectable to the upper end side of each of the space portions of the adsorption towers 51A and 51β, and to the lower end of the space portion 51f. The line 59e is connected to the heat medium tank 52f. The line 59f is a pressure equalizing line and is provided so as to be connected to the upper end side of each space portion (1) of the adsorption tower, and is connected to the heat medium. Using an argon refining device having the above configuration By setting γ, the argon refining method according to the present invention can be carried out in the following manner. In the reserving system i, the boosting blower 12 is operated, and the raw material gas is received from the raw material gas introduction end E of (4) 25 201043571. G. The received raw material gas G〇 is removed into the buffer tank 10 after passing through the precipitator 11 to remove a predetermined solid component. In the buffer tank 10, it is also taken from the pSA system 3 through the recovery line 4 from the PSA. The exhaust gas of system 3, in addition, also receives the exhaust gas from TSA system 5 from line 58. Then, the gas & is derived from buffer tank 1 。. With respect to gas Gi', flow is regulated by flow control unit 丨4 The gas g! that is subjected to the flow rate control in the flow rate control unit 14 is supplied to the pretreatment system 2. In the pretreatment system 2, the gas G is sequentially removed from the pretreatment tank 20A (first treatment) The reduction of the ruthenium concentration in the pretreatment tank 20B or the removal of hydrogen (second treatment) and the removal of hydrogen remaining after the second treatment of the pretreatment tank 20C (third treatment, specifically, in the pretreatment tank 20A) In, as mentioned above, yes The carbon monoxide in the gas G! is substantially converted into carbon dioxide by the conversion reaction represented by the reaction formula (1). In the W treatment tank 20B, as described above, it is represented by the reaction formula (2). The conversion reaction converts hydrogen and oxygen of the gas G]_ into water to reduce or substantially remove it. In the pretreatment tank 2〇c, as described above, it is represented by the reaction formula (2). In the conversion reaction, hydrogen and oxygen in the gas &ample are turned into water to be substantially removed. Before the gas G! is introduced into the pretreatment tank 20A, the temperature of the gas Gi is adjusted. Specifically, the gas G, by the thermometer 25A The measured temperature is raised to, for example, [go to 150 °C] by the time of preheating 21 in line 27A. Thereby, the reaction temperature of the pretreatment tank is made, for example, 2 5 〇 t or less. In order to promote the conversion reaction shown in the above reaction formula (1), the reaction temperature in the pretreatment tank 2A is preferably 130 C or more. For the reaction for suppressing the generation of methane in the pretreatment tank 2〇a, the reaction temperature in the pretreatment tank 2A is preferably 250 °C or less. Before the gas Gi is introduced into the treatment tank 2A, a predetermined amount of oxygen is added to the gas Gi by the operation of the oxygen supply amount control unit 23A. The amount of oxygen added is determined based on the concentration of carbon monoxide and the concentration of oxygen measured by the concentration analyzer 13 described above. In order to promote the conversion reaction shown in the above reaction formula (1), carbon monoxide is sufficiently removed in the pretreatment tank 20A, and the gas G introduced into the pretreatment tank is preferably a gas G introduced into the pretreatment tank 2A. It contains 104.5 equivalents of carbon monoxide. In the pretreatment tank 2, as described above, the conversion reaction shown in the above reaction formula (1) occurs, and carbon monoxide in the gas Gi is turned into carbon dioxide to be substantially removed. After the pretreatment tank 20A, before the gas Gi is introduced into the pretreatment tank 2B, the temperature of the gas crucible is adjusted by passing through the cooler 22A. The temperature of the gas crucible is adjusted before introducing the gas into the pretreatment tank 20B, and the temperature measured by the thermometer 25B is, for example, 5 〇 to 6 (rc). Thereby, the reaction temperature in the pretreatment tank 2 〇 B is, for example, 100 to 36 (TC. For promoting the conversion reaction shown in the above reaction formula (2), the reaction temperature in the pretreatment tank 2 〇β is preferably ioo~36〇r. In addition, the pretreatment tank 2 in the preceding stage is assumed. In the case where 水A generates water as a by-product due to the reaction between hydrogen and oxygen, the moisture causes the activity of the catalyst in the pretreatment tank 20B, and the temperature of the gas G! introduced into the pretreatment tank 20B. Preferably, the condensation temperature (for example, 5 〇 ° C ) or more is added. Before the gas G! is introduced into the pretreatment tank 2 〇 B, the gas enthalpy is added to the gas enthalpy by the operation of the oxygen supply amount control unit 23B. 27 201043571 The amount of oxygen added is determined based on the carbon monoxide concentration and oxygen concentration measured by the concentration analyzer 13 described above, and the amount of oxygen added before the pretreatment tank 20A. The conversion shown in the above reaction formula (2) The reaction is fever ruminant, pre-introduction The oxygen contained in the gas enthalpy of 20B is preferably such that the reaction temperature in the pretreatment tank 2 〇β does not exceed 36 (rc). In the pretreatment tank 2 〇β, as described above, the above reaction formula occurs (2 The conversion reaction shown in the table, and the hydrogen and oxygen in the gas are turned into water to be substantially removed or inferior. The meaning of the gas enthalpy is introduced into the pretreatment tank 2〇c after the pretreatment tank 20B. 'J' by passing the cooler 2 2 R Yan whistle # # raA /> 1 孓孓 3 weeks is the temperature of the gas.

Gl導入前處理槽-之前，調節氣體Μ溫度將，而Μ 溫度計況所測定的溫度為例如^_。藉此，使前處理槽20C中的反應溫度為例如1〇〇〜36〇。〇。對於促進上述 =應式⑵所表的轉化反應而言，前處理槽中的反應溫、，由於氣體G!中的水分可能會成為月ίι處理槽2 0 C内的觸據沾、、羊ω 扪觸媒的活性阻害要因，導入至前處理槽20C的氣體G】的溫度，較好以上。車乂好為凝結溫度(例如5。。〇在將氣體G!導入前處理槽2〇上_ —,斤曲 oc 谓之刖，在以氫濃度分析叶26測定氣體Gl的氫濃 * 又後’错由氧供應量控制部23C 的作動而添加視需求之既定吾 ^ 无疋里的虱，又藉由氫供應量控制邛24的作動而添加視需 ^ &乏既疋置的氫。氧的添加量，是根據以上述的濃度分析、*电 3所測定的一氧化碳濃度及氧展度、在前處理槽20A之前六士 &二 .^ . 添加的氧量、在前處理槽20Β 之W添加的氧量、還有由詩、.曲飞/辰度为析計26所測定的氫濃度 201043571 所決定。為了藉由上述反應式（2)所表的轉化反應而在前處理槽20C除去氫，導入至前處理#20以氣體^所含的氧，較好為導入至前處理槽20C的氣體G,所含的氫的1/2當量。在前處理槽20C中，如上所述，發生上述反應式（2) 所表的轉化反應，而將氣體Gl中的氫及氧變成水而將其實質上地除去。在從以氬精製裝置Y所精製的氬除去氫及氧的情況中，在前處理槽20B可以充分除去氫及氧的情況中’則不一定要設置前處理槽2〇c等。〇在經過前處理槽20C之後，藉由通過冷卻器22C來調節氣體G,的溫度。通過冷卻器22C之後的氣體匕的溫度例如為20〜40。(：。在别處理系統2中已受到既定的前處理的氣體G i，是將其供應至PSA系統3。供應至PSA系統3的氣體Gi，是藉由升壓機32而被壓縮成例如〇·8〜iMpaG(G是代表表壓 (gage pressure)，以下皆同）之後，藉由通過冷卻器μ而〇被冷郃至既定溫度。在PSA系統3及回收線4中，在pSA 裝置30的驅動之時，以第4圖至第6圖所示的樣態來切換自動閥 34a〜34c、35a〜35c、36a〜36c、37a〜37d、4a，藉此貫見裝置内的所欲的氣體的流動狀態，而可以重複以下的步驟1〜15所構成的循環（在第4圖至第6圖中，以〇來表不各自動閥的開狀態、且以X來表示閉狀態）。在本方法的 1個楯環中，是在吸附塔31A、31B、31C各自進行吸附步驟、第一減壓步驟、第二減壓步驟、第一脫附步驟、第二脫附步驟、第一清潔步驟、第二清潔步驟、第一升壓步驟、 29 201043571 及第二升壓步驟。第7圖是顯下步驟1〜5中的在PSA裝置 3 0的氣體的流動狀態。第8圖是_千牛Before Gl is introduced into the pretreatment tank - the gas enthalpy temperature is adjusted, and the temperature measured by the 温度计 thermometer condition is, for example, ^_. Thereby, the reaction temperature in the pretreatment tank 20C is, for example, 1 〇〇 to 36 Torr. Hey. In order to promote the above-mentioned conversion reaction according to the formula (2), the reaction temperature in the pretreatment tank may be due to the moisture in the gas G!, which may become a touch in the month of the treatment tank, and the sheep ω The temperature of the gas G] introduced into the pretreatment tank 20C is preferably more than the temperature of the catalyst. The rutting speed is preferably the condensing temperature (for example, 5. 〇 in the gas G! is introduced into the pretreatment tank 2 _ _, 斤曲谓刖在在刖刖刖刖刖测定测定测定测定测定测定测定测定测定测定测定测定测定测定测定测定测定测定测定测定The error is caused by the operation of the oxygen supply amount control unit 23C, and the hydrogen in the required state is added by the operation of the hydrogen supply amount control unit 24, and the hydrogen which is required to be disposed is added. The amount of oxygen added is based on the concentration analysis described above, the concentration of carbon monoxide measured by *Electrical 3, and the oxygen spread, the amount of oxygen added before the pretreatment tank 20A, and the amount of oxygen added in the pretreatment tank 20Β. The amount of oxygen added by W is also determined by the hydrogen concentration 201043571 measured by Shishi, Qu Fei/Chang degree 26, in the pretreatment tank 20C by the conversion reaction shown by the above reaction formula (2). The hydrogen is removed, and the oxygen contained in the gas is introduced into the pretreatment #20, preferably 1/2 equivalent of hydrogen contained in the gas G introduced into the pretreatment tank 20C. In the pretreatment tank 20C, as described above The conversion reaction shown in the above reaction formula (2) occurs, and hydrogen and oxygen in the gas G1 are turned into water to substantially In the case where hydrogen and oxygen are removed from the argon purified by the argon refining device Y, in the case where the pretreatment tank 20B can sufficiently remove hydrogen and oxygen, it is not necessary to provide the pretreatment tank 2〇c or the like. After passing through the pretreatment tank 20C, the temperature of the gas G is adjusted by passing through the cooler 22C. The temperature of the gas crucible after passing through the cooler 22C is, for example, 20 to 40. (:. Has been subjected to the treatment system 2 The predetermined pre-treated gas G i is supplied to the PSA system 3. The gas Gi supplied to the PSA system 3 is compressed by the booster 32 to, for example, 〇·8~iMpaG (G is representative of gauge pressure) (gage pressure), after the same, is cooled to a predetermined temperature by passing through the cooler μ. In the PSA system 3 and the recovery line 4, at the time of driving the pSA device 30, as shown in Fig. 4 In the state shown in Fig. 6, the automatic valves 34a to 34c, 35a to 35c, 36a to 36c, 37a to 37d, and 4a are switched, whereby the flow state of the desired gas in the apparatus is observed, and the following steps can be repeated. The cycle consisting of 1 to 15 (in the 4th to 6th drawings, the automatic valves are indicated by 〇 In the open state, the closed state is represented by X. In one of the loops of the method, each of the adsorption towers 31A, 31B, and 31C performs an adsorption step, a first pressure reduction step, a second pressure reduction step, and a first a desorption step, a second desorption step, a first cleaning step, a second cleaning step, a first step of boosting, 29 201043571 and a second step of boosting. Figure 7 is a diagram showing the PSA device in steps 1 to 5 The flow state of the gas of 30. Figure 8 is _ kN

疋顯不步驟6〜1〇中的在PSA 裝置30的氣體的流動狀態。第9圖熹翱圃疋顯不步驟11〜15中的在PSA裝置30的氣體的流動狀態。在步驟1中，如第4圖所示遝摆欠ώ + Τ不選擇各自動閥的開閉狀態、且错由升壓機32的作動，而達成如第又即乐^圖（8)所不的氣體流動狀態，而在吸附塔31A進行吸附步驟、在吸附塔3ΐβ 進行第一清潔步驟、在吸附塔31C進行第—減壓步驟。The flow state of the gas in the PSA unit 30 in steps 6 to 1 is not shown. Fig. 9 is a view showing the flow state of the gas in the PSA unit 30 in steps 11 to 15. In step 1, as shown in Fig. 4, the 开 ώ ώ + Τ does not select the opening and closing state of each automatic valve, and the operation of the booster 32 is wrong, and the result is as follows: In the gas flow state, the adsorption step is performed in the adsorption column 31A, the first cleaning step is performed in the adsorption column 3?β, and the first depressurization step is performed in the adsorption column 31C.

一併參照第3圖及第7圖（a)而可以更容易理解，在步驟1中，將氣體G!導入處於既定的高壓狀態的吸附塔3) A 的氣體通過口 31a側’使吸附塔31 a内的吸附劑吸附此氣體G,中的不純物（二氧化碳、水、氮等），將氩氣富化後的準精製氣體G2從吸附塔31A的氣體通過口 31b側導出。準精製氣體G2是經由線35而向著TSA系統5而被送出。在此同時，在步驟1中，將已經經過後文所述的步驟丨丨~丨5 (吸附步驟）的吸附塔31C的内部降壓，而從吸附塔31 c的氣體通過口 31b側導出氣體G3。此氣體G3是經由線36而被導引至吸附塔31B。在此同時，在步驟1中，將來自吸附塔 31C的氣體G3作為清潔氣體而導入至經過後文所述的步驟 15(第二脫附步驟）的吸附塔31B的氣體通過口 31b側，同時並從吸附塔31B的氣體通過口 31 a側導出氣體g3’（沖洗用氣體）。此氣體Gs’是經由線37而從氣體排出端E2被排出到裝置外。在步驟2中，如第4圖所示選擇各自動閥的開閉狀態、 30 201043571 且藉由升壓機32的作動，而達成如第7圖所示的氣體流動狀態，而在吸附塔31A進行吸附步驟、在吸附塔3ΐβ 進行第二清潔步驟、在吸附塔31C進行第一減壓步驟。一併參照第3圖及第7圖❶）而可以更容易理解，在步驟2中’在吸附塔31A接續步驟i而進行吸附步驟，而導出準精製氣體G2。在此同時，在步驟2 接續步⑽而進行第-減壓步驟。在此同時，在步驟2中，Referring to Fig. 3 and Fig. 7(a) together, it can be more easily understood that in step 1, the gas G! is introduced into the adsorption tower 3) of the adsorption tower 3) A in a predetermined high pressure state. The adsorbent in 31 a adsorbs impurities (carbon dioxide, water, nitrogen, and the like) in the gas G, and the quasi-purified gas G2 rich in argon gas is led out from the gas passage port 31b side of the adsorption tower 31A. The quasi-refined gas G2 is sent to the TSA system 5 via the line 35. At the same time, in step 1, the inside of the adsorption tower 31C which has undergone the steps 丨丨~丨5 (adsorption step) described later is stepped down, and the gas is led out from the gas passage opening 31b side of the adsorption tower 31c. G3. This gas G3 is guided to the adsorption tower 31B via the line 36. At the same time, in step 1, the gas G3 from the adsorption tower 31C is introduced as a cleaning gas to the side of the gas passage port 31b of the adsorption tower 31B which has passed through the step 15 (second desorption step) described later, while The gas g3' (flushing gas) is led out from the gas passage opening 31a side of the adsorption tower 31B. This gas Gs' is discharged from the gas discharge end E2 to the outside of the apparatus via the line 37. In step 2, as shown in Fig. 4, the opening and closing state of each automatic valve is selected, 30 201043571, and the operation of the booster 32 is performed to achieve the gas flow state as shown in Fig. 7, and is performed in the adsorption tower 31A. In the adsorption step, the second cleaning step is performed in the adsorption column 3ΐβ, and the first depressurization step is performed in the adsorption column 31C. Referring to Fig. 3 and Fig. 7 together, it can be more easily understood that in step 2, the adsorption step is carried out in the adsorption column 31A, and the adsorption step is carried out to introduce the quasi-refined gas G2. At the same time, the step-decompression step is carried out in step 2 following step (10). At the same time, in step 2,

接續步驟1將來自吸附塔31C的氣體G3作為清潔氣體而導入至吸㈣31B的氣體通過口 311)側’並從吸附塔3ΐβ的氣體通過口 31a侧導出氣體G3,，（沖洗用氣體此氣體G3，，是經由線37及回收線4而導入至緩衝槽ι〇，而被貯留於緩衝槽1 0。在步驟3中，如第4圖所示選擇各自動閥的開且藉由升壓機32的作動’而達成如第7圖(〇所示的氣體流動狀態，而在吸附塔31A進行吸附步驟、在吸附塔川進行第-升壓步驟、在吸附塔31C進行第二減壓步驟。一併參照第3圖及第7圖(〇而可以更容易理解，在步驟3中，在吸附塔31八接續步驟2而進行吸附步驟，而導出準精製氣體G”在此同時，在步驟3中，在吸附塔31C 接續步驟2而將吸附塔31c的内部降壓，從吸附塔的氣體通過口 31 b側導出氣體。被導引至吸附塔31B。在此同時附^ 31C的氣體G4作為升壓氣體體通過口 31b側，將吸附塔31B的内部升壓此氣體G4是經由線36而 ’在步驟3中，將來自吸而導入至吸附塔31B的氣 31 201043571 在步驟4中’如第4圖所示選握夂占车選擇各自動閥的開閉狀態、且精由升壓機32的作動，而達，如笛，士成如第7圖（d)所示的氣體 >狀動狀態’而在吸附塔31A進杆In the subsequent step 1, the gas G3 from the adsorption tower 31C is introduced as a cleaning gas to the gas passage port 311) side of the suction (4) 31B, and the gas G3 is led out from the gas passage port 31a side of the adsorption tower 3ΐβ, (the flushing gas is this gas G3) , is introduced into the buffer tank 10 via the line 37 and the recovery line 4, and is stored in the buffer tank 10. In step 3, as shown in Fig. 4, each of the automatic valves is opened and the booster is used. In the operation of 32, the gas flow state shown in Fig. 7 (〇 is performed, the adsorption step is performed in the adsorption column 31A, the first pressure increase step is performed in the adsorption tower, and the second pressure reduction step is performed in the adsorption column 31C. Referring to FIG. 3 and FIG. 7 together, it can be more easily understood that in step 3, the adsorption step is performed in the adsorption tower 31 and the subsequent adsorption step, and the quasi-refined gas G is extracted, at the same time, in step 3 In the adsorption tower 31C, the inside of the adsorption tower 31c is stepped down in step 2, and the gas is led out from the gas passage opening 31b side of the adsorption tower. The gas is led to the adsorption tower 31B. At the same time, the gas G4 of the 31C is used as The pressurized gas body passes through the port 31b side, and the inside of the adsorption tower 31B is The part pressurizes this gas G4 via the line 36 and 'in step 3, the gas 31 introduced from the suction to the adsorption tower 31B 201043571 is selected in step 4 as shown in Fig. 4 The opening and closing state is finely controlled by the booster 32, and the gas is moved into the adsorption tower 31A as shown in Fig. 7(d).

^ 丁及附步驟、在吸附塔31B 進行第二升壓步驟、在吸附塔3 1L進仃第一脫附步驟。一併參照第3圖及第7圖I、圃以）而可以更容易理解，在步驟4中，在吸附塔3U接續步驟3 少鄉3而進行吸附步驟，而導出準精製氣體G2。準精製氣體G2的一 J °丨分則被導引至吸附塔31B。在此同時’在步驟4中，目丨、 γ 則將來自吸附塔31A的〇準精製氣體G2作為升壓氣體而道入Ε Ώ 虱筱而導入至吸附塔31Β的氣體通過口 31b側’而將吸附塔31Β的内邱 ^ + «J ΙΛ1沖升壓。在此同時，在步驟4中，將吸附塔31C的内部卩备厭二_ 争壓’而將不純物從吸附塔31C内的吸附劑脫附，而從吸附塔3κ的氣體通過口… 側導出氣體G5(廢氣）。此氣體G5是經由線％及回收線* 而導入至緩衝槽10，而被貯留於緩衝槽1〇。在步驟5中，如第4圖所示遁捏女a 乂圃町不選擇各自動閥的開閉狀態、且藉由升壓機32的作動，而達成如笛/ 、 ❹ 逆战如弟7圖（e)所示的氣體流動狀態，而在吸附塔31A進行吸附步驟、在吸附塔3ΐβ 進行第二升壓步驟、在吸附塔加進行第二脫附步驟。 -併參照第3圖及第7圖(e)而可以更容易理解，在步驟5中’在吸附塔31A接續步驟4而進行吸附步驟，而導出準精製氣體G” |精製氣體G2的一部分則被導引至吸附塔31B。在此同時’在步驟5中，在吸附塔3ΐβ接續步驟4 而將内部升璧。在此同時’在步驟5中，接續步驟4將吸附塔31C内部降壓，而將不純物從吸附塔ye内的吸附劑 32 201043571 進一步脫附，而從吸附塔31C的氣體通墀口 31&側導出氣體Ge(廢氣）。此氣體G6是經由線37而從氣體排出端E2被排出到裝置外。在步驟1〜5中，處於吸附步驟的吸附塔31人的内部的最高壓力’例如是700〜800kPaG。步驟1的第一清潔步驟的終了時間點的吸附塔31C的内部的壓力是例如 500〜600kPaG。橫跨步驟1〜2的第一減壓步驟的終了時間點中的吸附塔31C的内部的壓力（第一中間壓力）是例如〇 30 0〜4 0 0kPaG。步驟3的第二減壓步驟的終了時間點的吸附塔 31C 的内部的壓力（第二中間壓力）是例如 150〜20OkPaG。步驟4的第一脫附步驟的終了時間點的吸附塔31C的内部的壓力是例如1 〇〇kpaG。步驟5的第二脫附步驟的終了時間點的吸附塔31C的内部的壓力是例如〇〜30kPaG 。在步驟6〜10中，與在步驟1〜5在吸附塔31A所進4亍者 Q 相同，在吸附塔31B中進行如第8圖所示的吸附步驟。在此同時，在步驟6〜1〇中，與在步驟卜5在吸附塔31B所進行者相同’在吸附塔31C進行如第8圖所示的第一清潔步驟（步驟6 )、第二清潔步驟（步驟7 )、第一升壓步驟（步驟 8)、及第二升壓步驟（步驟9、1〇)。在此同時，在步驟6〜10 中，與在步驟卜5在吸附塔31(：所進行者相同，在吸附塔 31A中進行第8圖所示的第—減壓步驟（步驟6、7)、第二減壓步驟（步驟8)、第一脫附步驟（少驟9)、及第二脫附步驟（步驟1〇)。 33 201043571 在步驟11〜15中，與在步驟1〜5在吸附塔31A所進行者相同，在吸附塔31C中進行如第9圖所示的吸附步驟。在此同時，在步驟11〜15中，與在步驟1〜5在吸附塔所進行者相同，在吸附塔31A進行如第9圖所示的第—清潔步驟（步驟11)、第二清潔步驟（步驟12)、第一升壓步驟 (步驟13)、及第二升壓步驟（步驟14、15)。在此同時，在步驟11〜15中，與在步驟1~5在吸附塔31C所進行者相同，在吸附塔31B中進行第9圖所示的第一減壓步驟（步驟u、 12)、苐一減壓步驟（步驟13)、第一脫附步驟（步驟η)、及第二脫附步驟（步驟1 5)。如上，從PSA系統3或PSA裝置30 ’持續取出氬氣富化後的準精製氣體G2。 r·* 1 10圖及第11圖所示的樣態來切換自動閥53a' 53b、5“ ⑽、56a、56b、56c、57a、仍、服、训，藉此實現」置内的所欲的氣體的流動狀態，@可以重複以下的步; 1 1 0所構成的循環（在第i 〇圖及第i】圖中，以〇來表。各自動間的開狀態、且來表不閉狀態）。在本方法的個循衣中，是在吸附塔r 1 ώ^ Ding and the additional step, the second step of stepping up in the adsorption column 31B, and the first desorption step in the adsorption column 31L. Referring to Fig. 3 and Fig. 7 and Fig. 1 and Fig. 7 together, it can be more easily understood that in step 4, the adsorption column 3U is followed by the step 3 to carry out the adsorption step, and the quasi-refined gas G2 is introduced. A J ° minute of the quasi-refined gas G2 is led to the adsorption tower 31B. At the same time, in the step 4, the target γ and the γ are introduced into the 通过 Ώ 作为 as the step-up gas from the adsorption tower 31A, and are introduced into the gas passage port 31b side of the adsorption tower 31A. The inner Qiu ^ + «J ΙΛ 1 of the adsorption tower 31Β is boosted. At the same time, in the step 4, the internal portion of the adsorption tower 31C is deviated from the adsorbent in the adsorption tower 31C, and the gas is discharged from the gas passage port of the adsorption tower 3K. G5 (exhaust gas). This gas G5 is introduced into the buffer tank 10 via the line % and the recovery line*, and is stored in the buffer tank 1〇. In step 5, as shown in Fig. 4, the kneading female a 乂圃不 does not select the opening and closing state of each automatic valve, and the action of the booster 32 is achieved, such as the flute/, ❹, the war, the brother 7 In the gas flow state shown in (e), the adsorption step is performed in the adsorption column 31A, the second pressure increasing step is performed in the adsorption column 3?β, and the second desorption step is performed in the adsorption column. - Referring to Fig. 3 and Fig. 7(e), it can be more easily understood that in step 5, 'the adsorption step is carried out in the adsorption column 31A following the step 4, and the quasi-refined gas G is extracted"; a part of the refined gas G2 is It is guided to the adsorption tower 31B. At the same time, 'in step 5, the internal adsorption is carried out in the adsorption tower 3ΐβ following the step 4. At the same time, in the step 5, the subsequent step 4 steps down the interior of the adsorption tower 31C. The impurity is further desorbed from the adsorbent 32 201043571 in the adsorption tower ye, and the gas Ge (exhaust gas) is derived from the gas passage port 31 & side of the adsorption tower 31C. This gas G6 is from the gas discharge end E2 via the line 37. It is discharged to the outside of the apparatus. In steps 1 to 5, the highest pressure inside the person of the adsorption tower 31 in the adsorption step is, for example, 700 to 800 kPa G. The inside of the adsorption tower 31C at the end of the first cleaning step of the step 1 The pressure is, for example, 500 to 600 kPa G. The pressure (first intermediate pressure) inside the adsorption tower 31C in the end time of the first decompression step of steps 1 to 2 is, for example, 〇30 0 to 400 kPa. The end of the second decompression step of 3 The pressure inside the adsorption tower 31C (second intermediate pressure) at the intermediate point is, for example, 150 to 20 OkPa G. The pressure inside the adsorption tower 31C at the end of the first desorption step of the step 4 is, for example, 1 〇〇 kpaG. The pressure inside the adsorption tower 31C at the end of the second desorption step of 5 is, for example, 〇30 kPaG. In steps 6 to 10, it is the same as the Q in the adsorption tower 31A in steps 1 to 5, The adsorption step shown in Fig. 8 is carried out in the adsorption column 31B. At the same time, in the step 6 to 1, the same as the one performed in the adsorption column 31B in the step 5, the eighth step is performed in the adsorption column 31C. The first cleaning step (step 6), the second cleaning step (step 7), the first step of boosting (step 8), and the second step of boosting (steps 9, 1) shown in the figure. At the same time, In steps 6 to 10, the first-decompression step (steps 6, 7) and the second subtraction shown in Fig. 8 are performed in the adsorption tower 31A in the same manner as in the adsorption tower 31 (in the case of the adsorption tower 31). a pressing step (step 8), a first desorption step (small step 9), and a second desorption step (step 1). 33 201043571 In steps 11 to 15, the adsorption step as shown in Fig. 9 is performed in the adsorption column 31C in the same manner as in the adsorption steps 31A in steps 1 to 5. At the same time, in steps 11 to 15, In steps 1 to 5, the same is performed in the adsorption tower, and the first cleaning step (step 11), the second cleaning step (step 12), and the first step (step) are performed in the adsorption tower 31A as shown in Fig. 9. 13) and the second step of boosting (steps 14, 15). At the same time, in steps 11 to 15, the same as in the steps 1 to 5 in the adsorption tower 31C, the ninth in the adsorption tower 31B. The first depressurization step (steps u, 12), the decompression step (step 13), the first desorption step (step n), and the second desorption step (step 15) are shown. As above, the argon-enriched quasi-refined gas G2 is continuously taken out from the PSA system 3 or the PSA unit 30'. r·* 1 10 and the pattern shown in Fig. 11 to switch the automatic valves 53a' 53b, 5 "(10), 56a, 56b, 56c, 57a, still, service, training, thereby achieving the desired The flow state of the gas, @ can repeat the following steps; 1 10 0 of the cycle (in the i-th diagram and the i-th), the table is represented by 〇. The open state of each automatic, and the table is not closed status). In the process of the method, it is in the adsorption tower r 1 ώ

° A、51Β各自進行吸附步驟、冷:J 抽出步驟、加熱脫附步驟、埶 …、跺柚出步驟、冷部步驟、』田£步驟。第12〜21圖疋‘4不步驟卜10中的在TSA裝」 50的乳體、冷媒Mi及熱媒M2的流動狀態。各自動/1巾h第Μ所示適#地選擇冷媒熱媒線^ 各自動閱的開閉狀態、且選擇氣體線的各自動間的開閉d 34 201043571 態’而達成如第1 2圖所示的冷媒流動狀態及氣體流動狀態，而在吸附塔51A進行吸附步驟、在吸附塔5丨B進行冷媒抽出步驟。具體的步驟是如下所述。在步驟1中’是從冷媒槽52C經由線59a而將冷媒Ml 供應至吸附塔51A的空間部51f的下端側。此冷媒M1，是藉由冷媒幫浦52D將其從冷媒槽52c抽出，而通過鹽水冷部器52E而受到冷卻。藉由鹽水冷卻器52E而達成的冷媒 ❽ M1的冷卻溫度為-50 — 4(TC。在此同時，從吸附塔5U的空間部51f的上端側經由線59b而將冷媒骱回收至冷媒槽 52C °此冷媒Ml是在被回收至冷媒槽52c之前通過冷卻器 52B’而被用來冷卻準精製氣體⑺。由於冷媒们與準精製氣體Gs之間的比熱之差大，在冷卻器52B可以有效率地冷卻準精製氣體G2。冷媒Ml是在吸附塔51A的空間部51f與鹽水冷卻器52E之間巡迴，藉此吸附塔5ia的吸附管51c 内的吸附劑持續受到冷卻而維持在低溫的吸附用溫度。吸〇附用溫度最低為—501、較好為-4(TC以上。在本實施形態中，吸附用溫度是例如為—35〇c。在此同時，經由線53將準精製氣體G2導入吸附塔5丨a的氣體通過口 5丨a侧，使吸附塔51A的吸附管51C内的吸附劑吸附此氣體G2中的不純物氧’且將完成氬富化的精製氣體⑺從吸附塔51a的氣體通過口 51b側導出。精製氣體&是經由線54、55而從精製氣體導出端E3被排出到裝置外。此精製氣體g?是在被拆出到裝置外之前通過熱交換器52A，而被用來冷卻準精製氣體Gw在此同時，從已經經過後文所述的步驟6〜1〇(吸 35 201043571 附步驟）的吸附塔51B的空間部51f的下端側經由線挪，而將冷媒回收至冷媒槽52C(此時，使線59c的自動間為開狀態，將冷媒槽52C與吸附塔5ΐβ的空間部均壓）。處於吸附步驟的吸附塔51A的吸附管5ic的内部壓力為〇_ 01〜IMPaG的範圍。在步驟2中，如第10圖所示適當地選擇冷媒熱媒線各自動閥的開閉狀態、、且選擇氣體線的各自動閥的開閉狀態，而達成如f 13圖所示的冷媒流動狀態、熱媒流動狀態、及氣體流動狀態，而在吸附塔5U進行吸附步驟、在吸附塔51B進行加熱脫附步驟。具體的步驟是如下所述。在步驟2中，是在吸附塔51A中接續步驟i而進行吸附步驟，導出精製氣體Gt。在此同時，藉由熱媒幫浦似將熱媒M2抽出，從熱媒槽52F經由線59d而將熱媒们供應至吸附塔51B的空間部51f的下端側。在熱媒槽52ρ内，疋將熱媒M2加熱至例如45〜501：。在此同時，從吸附塔51B 的空間部51f的上端侧經由線59e而將熱媒M2回收至熱媒槽52F。熱媒M2是在吸附塔51B的空間部51f與熱媒槽52F 之間巡迴，藉此吸附塔51 β的吸附管51 c内的吸附劑持續受到加熱而被升溫至到達例如4(rc為止。在加熱脫附步驟中的吸附劑的最高到達溫度會高達5(rc。在此同時，經由線56而將從吸附塔51Α導出的精製氣體G?的一部分，導入吸附塔51B的氣體通過口 5lb側，同時將完氣體I，從吸附塔51B的氣體通過口 5丨a側導出。此氣體是經由線 5 8 (回收線）而被導入至緩衝槽丨〇，而被貯留於緩衝槽1 〇。 201043571 另外，處於加熱脫附步驟的吸附塔51B的吸附管51 c的内部壓力是在限定於低於吸附步驟中的吸附管51 c的内部壓力的情況中，是大氣壓至〇. 〇5MPaG之間。° A, 51 Β each of the adsorption step, cold: J extraction step, heating desorption step, 埶 ..., 跺 pomelo step, cold step, 』 step. In the 12th to 21st drawings, the flow state of the milk, the refrigerant Mi, and the heat medium M2 in the "4" is not in the TSA. Each of the automatic / 1 towel h is the same as the selection of the refrigerant heat medium wire ^ each open and closed state of the automatic reading, and the selection of the automatic opening and closing of the gas line d 34 201043571 state" and as shown in Figure 1 In the refrigerant flow state and the gas flow state, the adsorption step is performed in the adsorption tower 51A, and the refrigerant extraction step is performed in the adsorption tower 5B. The specific steps are as follows. In the step "1", the refrigerant M1 is supplied from the refrigerant tank 52C to the lower end side of the space portion 51f of the adsorption tower 51A via the line 59a. This refrigerant M1 is taken out from the refrigerant tank 52c by the refrigerant pump 52D, and is cooled by the brine cooler 52E. The cooling temperature of the refrigerant ❽ M1 by the brine chiller 52E is -50 - 4 (TC. At the same time, the refrigerant enthalpy is recovered from the upper end side of the space portion 51f of the adsorption tower 5U via the line 59b to the refrigerant tank 52C. The refrigerant M1 is used to cool the quasi-refined gas (7) through the cooler 52B' before being recovered to the refrigerant tank 52c. Since the difference in specific heat between the refrigerant and the quasi-refined gas Gs is large, the cooler 52B may have The quasi-purified gas G2 is efficiently cooled. The refrigerant M1 is circulated between the space portion 51f of the adsorption tower 51A and the brine cooler 52E, whereby the adsorbent in the adsorption tube 51c of the adsorption tower 5ia is continuously cooled and maintained at a low temperature. The temperature at which the suction is applied is at most -501, preferably -4 (TC or more. In the present embodiment, the adsorption temperature is, for example, -35 〇c. At the same time, the quasi-refined gas is passed through the line 53. G2 is introduced into the adsorption gas column 5丨a through the port 5丨a side, so that the adsorbent in the adsorption tube 51C of the adsorption column 51A adsorbs the impurity oxygen in the gas G2 and the argon-rich purified gas (7) is removed from the adsorption tower. The gas of 51a is led out through the port 51b side The purified gas & is discharged from the purified gas outlet end E3 to the outside of the apparatus via lines 54, 55. This refined gas g? is passed through the heat exchanger 52A before being removed to the outside of the apparatus, and is used to cool the quasi-refining At the same time, the gas Gw is recovered from the lower end side of the space portion 51f of the adsorption tower 51B which has passed through the steps 6 to 1 后 (sucking 35 201043571), which will be described later, to recover the refrigerant to the refrigerant tank 52C ( At this time, the automatic interval between the line 59c is opened, and the space between the refrigerant tank 52C and the adsorption tower 5?β is equalized. The internal pressure of the adsorption tube 5ic of the adsorption tower 51A in the adsorption step is in the range of 〇_01 to IMPaG. In step 2, as shown in Fig. 10, the opening and closing states of the automatic valves of the refrigerant heat medium are appropriately selected, and the opening and closing states of the automatic valves of the gas lines are selected to achieve the refrigerant flow as shown in Fig. The state, the flow state of the heat medium, and the state of the gas flow, the adsorption step is performed in the adsorption column 5U, and the heating and desorption step is performed in the adsorption column 51B. The specific steps are as follows. In the step 2, in the adsorption column 51A. Continue with step i In the same manner, the heat medium M2 is taken out by the heat medium pump, and the heat medium is supplied from the heat medium tank 52F to the lower end side of the space portion 51f of the adsorption tower 51B via the line 59d. In the heat medium tank 52ρ, the heat medium M2 is heated to, for example, 45 to 501: At the same time, the heat medium M2 is recovered from the upper end side of the space portion 51f of the adsorption tower 51B via the line 59e to the heat medium tank 52F. The heat medium M2 is circulated between the space portion 51f of the adsorption tower 51B and the heat medium tank 52F, whereby the adsorbent in the adsorption tube 51c of the adsorption tower 51β is heated and heated to reach, for example, 4 (rc) . The maximum reaching temperature of the adsorbent in the heating and desorption step may be as high as 5 (rc. At the same time, a part of the purified gas G? derived from the adsorption tower 51A via the line 56 is introduced into the gas passage port 5b of the adsorption tower 51B. On the side, the gas I is simultaneously discharged from the gas passage port 5丨a side of the adsorption tower 51B. This gas is introduced into the buffer tank through the line 58 (recovery line), and is stored in the buffer tank 1 In addition, in the case where the internal pressure of the adsorption tube 51c of the adsorption tower 51B in the heating desorption step is limited to the internal pressure of the adsorption tube 51c which is lower than the adsorption step, it is atmospheric pressure to 〇. 〇5MPaG between.

在步驟3中，如第10圖所示適當地選擇冷媒熱媒線的各自動閥的開閉狀態、且選擇氣體線的各自動閥的開閉狀知’而達成如第1 4圖所示的冷媒流動狀態、熱媒流動狀態、及氣體流動狀態’而在吸附塔51A進行吸附步驟、在吸附塔51B進行熱媒抽出步驟。具體的步驟是如下所述。在步驟3中，是在吸附塔51A中接續步驟2而進行吸附步驟，導出精製氣體Gt。在此同時，從吸附塔gig的空間部51 f的下端侧經由線59e，將熱媒M2回收至熱媒槽 52F(此時，使線59f的自動閥為開狀態，將熱媒槽與吸附塔51B的空間部51 f均壓）。在步驟4中，如第10圖所示適當地選擇冷媒熱媒線的各自動閥的開閉狀態、且選擇氣體線的各自動閥的開閉狀 $，而達成如第15圖所示的冷媒流動狀態及氣體流動狀態’而在吸附塔51A進行吸附步驟、在吸附塔51β進行冷卻步驟。具體的步驟是如下所述。？在步驟4中，是在吸附塔51A中接附步驟，導出精製氣體Gt。在此同時，亦從冷媒槽⑽ 由線59a而將冷媒M1供應至吸附塔51β的空間部白知側此/7媒，是藉由冷媒幫浦52D將其從冷媒槽抽出，而通過鹽水冷卻3 52E而受到冷卻。在此同時吸附塔51B的空間部51f的上端侧經由線训而將冷嫖 37 201043571 回收至冷媒槽520 此+媒Μ1是在吸附塔51 bIn step 3, as shown in Fig. 10, the opening and closing states of the automatic valves of the refrigerant heat medium line are appropriately selected, and the opening and closing states of the automatic valves of the gas lines are selected, and the refrigerant shown in Fig. 14 is obtained. In the flow state, the heat medium flow state, and the gas flow state, the adsorption step is performed in the adsorption tower 51A, and the heat medium extraction step is performed in the adsorption tower 51B. The specific steps are as follows. In the step 3, the adsorption step is carried out in the adsorption tower 51A, and the adsorption step is carried out to derive the purified gas Gt. At the same time, the heat medium M2 is recovered from the lower end side of the space portion 51f of the adsorption tower gig via the line 59e to the heat medium tank 52F (at this time, the automatic valve of the line 59f is opened, and the heat medium tank is adsorbed. The space portion 51 f of the tower 51B is equalized). In step 4, as shown in Fig. 10, the opening and closing states of the automatic valves of the refrigerant heat medium line are appropriately selected, and the opening and closing states of the automatic valves of the gas lines are selected to achieve the refrigerant flow as shown in Fig. 15. In the state and gas flow state, the adsorption step is performed in the adsorption tower 51A, and the adsorption step is performed in the adsorption tower 51β. The specific steps are as follows. ? In the step 4, the adsorption step is performed in the adsorption tower 51A to derive the purified gas Gt. At the same time, the refrigerant M1 is supplied from the refrigerant tank (10) to the space portion of the adsorption tower 51β from the line 59a, and is sucked out from the refrigerant tank by the refrigerant pump 52D, and is cooled by the brine. 3 52E is cooled. At the same time, the upper end side of the space portion 51f of the adsorption tower 51B recovers the cold water 37 201043571 to the refrigerant tank 520 via the line training. The + medium 1 is in the adsorption tower 51 b.

的空間部51 f }之間巡迴，藉此吸附塔51B的吸附管51c 1受到冷卻而被降溫至例如-351：(吸附用溫同時，經由線57將從吸附塔51A導出的精平分導入吸附塔51B的氣體通過口 51b側，從吸附塔51B的氣體通過口 51a側導出。被 B的精製氣體G7是對吸附塔51 β的吸附管的冷卻有貢獻。另外，氣體G7，是經由線導入至緩衝槽10，而被貯留於緩衝槽1〇。〇在步驟5中，如第10圖所示適當地選擇冷媒熱媒線的各自動__狀態、且選擇氣體線的各自動_開閉狀態，而達成如第1 6圖所示的冷媒流動狀態及氣體流動狀態，而在吸附塔51A進行吸附步驟、在吸附塔5丨B進行蓄壓步驟。具體的步驟是如下所述。在步驟5中，是在吸附塔51A中接續步驟4而進行吸附步驟，導出精製氣體G7。在此同時，接續步驟4而將冷媒Μ1在吸附塔51B的空間部51 f與鹽水冷卻器5 2 E之間巡迴，而吸附塔51B的吸附管51 c内的吸附劑則受到冷卻。在此同時，經由線57將從吸附塔51A導出的精製氣體G? 的一部分導入吸附塔51B的氣體通過口 51 b側，而將吸附塔51B的吸附管51c内蓄壓。吸附塔51B的吸附管51c内，是被升壓至例如0 · 01〜1 MPaG的範圍的既定壓力為止。在步驟6〜1〇中’與在步驟1〜5在吸附塔51A所進行者相同，在吸附塔51B中進行吸附步驟。在此同時，在步驟 38 201043571 6〜10中，與在步附塔5U進行冷1〜5在吸附塔31B所進行者相同’在吸 Ίλ ^ ^ ± 7媒抽出步驟（步驟6)、加熱脫附步驟（步驟 /、，、、、媒抽出步赖广止驟（步驟1〇)。牛驟8)、冷卻步驟（步驟9)、及蓄壓步態、及氣體流：：1°中的冷媒流動狀態、熱媒流動狀勒狀態’是示於第17〜21圖。如上所述，你$ —# —〜風精製裝置Y或TSA裝置，持續取出已元成氣富化的精製氣體G”The space portion 51 f } is patrolled between the space portions 51 f }, whereby the adsorption tube 51 c 1 of the adsorption tower 51B is cooled and cooled to, for example, -351 : (At the same time as the adsorption temperature, the fine aliquot derived from the adsorption tower 51A is introduced into the adsorption via the line 57 The gas passing through the port 51b side of the column 51B is led out from the gas passage opening 51a side of the adsorption tower 51B. The purified gas G7 of B contributes to the cooling of the adsorption pipe of the adsorption column 51 β. Further, the gas G7 is introduced via the line. The buffer tank 10 is stored in the buffer tank 1A. In step 5, as shown in Fig. 10, the respective automatic__states of the refrigerant heat medium line are appropriately selected, and the automatic_opening and closing states of the gas lines are selected. On the other hand, the refrigerant flow state and the gas flow state shown in Fig. 16 are obtained, and the adsorption step is performed in the adsorption column 51A, and the pressure accumulation step is performed in the adsorption column 5A. The specific steps are as follows. In the adsorption tower 51A, the adsorption step is carried out in the adsorption step 51A to extract the purified gas G7. At the same time, the refrigerant crucible 1 is connected between the space portion 51f of the adsorption tower 51B and the brine cooler 5 2 E in the subsequent step 4 Tour, and adsorption of adsorption tower 51B At the same time, a part of the purified gas G? derived from the adsorption tower 51A is introduced into the gas passage opening 51b side of the adsorption tower 51B via the line 57, and the adsorption tube of the adsorption tower 51B is used. The pressure is accumulated in 51c. The inside of the adsorption tube 51c of the adsorption tower 51B is pressurized to a predetermined pressure in the range of, for example, 0·01 to 1 MPaG. In the step 6 to 1〇, and in the adsorption tower in steps 1 to 5 In the same manner as in the case of 51A, the adsorption step is carried out in the adsorption column 51B. At the same time, in the step 38 201043571 6 to 10, the same as the one performed in the adsorption tower 31B in the step-attachment column 5U is performed. Ίλ ^ ^ ± 7 medium extraction step (step 6), heating desorption step (step /,,,,, medium extraction step (step 1 〇). cattle step 8), cooling step (step 9), And the pressure accumulation gait, and the gas flow: the refrigerant flow state in 1° and the heat medium flow state are shown in Figures 17 to 21. As described above, you $##~~ the air refining device Y or TSA device, continuously extracting the refined gas G which has been enriched by gas

法可5由進行氬精製裝置Y的使用之以上的氬精製方 1取侍成為精製氣體G7之99. 999°/。以上的高純度的氬（精製氣體G7中的_ :隹ώ 、 I ’農度可以減低至0. 1體積ppm以下）。另外’在本方法中，是在TSA裝置50的吸附塔51A、 51B各自實杆句人l 、匕3如上所述的吸附步驟、冷媒抽出步驟、加熱脫附步驟、熱媒抽出步驟、冷卻步驟、及蓄壓步驟，藉此謀求作為準精製氣體⑺中的氛的富化乃至高純度化。若错由本方法，可以容易達成高純度化的氬的高產率。這疋因為在本方法中’在加熱脫附步驟中從吸附塔51Α、5ΐβ 持續導出的廢氣（氣體G?’）是回到緩衝槽丨〇，將此廢氣供作使用PSA法及TSA法的再一次的氬富化。在本方法的加熱脫附步驟中，是從經過吸附步驟而吸附著氮的吸附劑將氮脫附。為了將此脫附的氮適當地排出吸附管5丨c外，將精製氣體G7(高純度氬氣）導入處於加熱脫附步驟的吸附塔 51A、51B的吸附管51 c。因此，從處於加熱脫附步驟的吸附塔51A、51B的吸附管51c導出的廢氣（氣體G/ )的氬濃度較高。在本方法中，並未將這樣的廢氣（氣體G/)排出裝 39 201043571 η卜而使其回到緩衝槽1G，供作使用psA法及m法的再一次的氬富化。因此’本方法是適用於以高產率取得高純度氬。除此之外’若藉由本方法，則容易縮短在TSA裝置5〇的TSA作業時間。這是因為在本方法中，是在實行伴隨著吸附劑的溫度變動的TSA法之時，使用液狀的冷媒们及液片、勺…、媒M2來貝ί見α及附劑的溫度變動。具體的步驟是如所述。在本發明的加熱脫附步驟中，是使用液狀的熱媒加熱吸附管51c内的吸附劑。藉由使液狀的熱媒…接觸充填著吸附劑的吸附管51c ’而將熱從此液狀的熱媒M2供應至寸b 51 c内的吸附劑，而加熱吸附劑。由於液狀的熱媒 M2的比熱是有相當程度地大於氣體的比熱，比起使用氣體作為用於TSA法中加熱吸附劑的媒介之情;兄，如本方法使用液狀的熱媒M2來加熱吸附劑的情況可以較快使吸附劑升溫至所欲的溫度。假如設定使用55%乙醇水溶液來作為本方法中的熱媒M2的情況（第一情況），並設定使用氬氣來作為加熱用的媒介將吸附劑升溫的情況（第二情況），由於 55%乙醇水溶液的比熱為〇. 839kcal/kg · °C (在-20°c )、氬風的比熱為〇. 125kcal/kg · t：(在-23t：),關於每單位時間對吸附劑的熱供應量，在第一情況是可以實現第二情況的7倍左右。因此，第一情況（相關於本發明的情況），是可以在以第二情況的七分之一的程度的短時間之下使加埶脫附步驟結束。加熱脫附步驟時間的縮短，是有助於了以 40 201043571 作業時間的縮短。另一方面’本方法的冷卻步驟中，是使用液狀的冷媒 Ml來冷卻吸附管5丨c内的吸附劑。藉由使液狀的冷媒鼢接觸充填著吸附劑的吸附管51c，而藉由此冷媒M1從吸附官51 c内的吸附劑奪取熱能，而藉此冷卻吸附劑。由於液狀的冷媒Ml的比熱是有相當程度地大於氣體的比熱，比起冷卻吸附劑的媒介之情況，如來冷卻吸附劑的情況可以較快。假如設定使用55%乙醇水溶的情況（第三情況），並設定使將吸附劑降溫的情況（第四情鼠氣的比熱是如上所述，關於收量’在第三情況是可以實現 ’第三情況（相關於本發明的情七分之一的程度的短時間之下時間的縮短，是有助於TSA作 Ο999度。 The argon purification unit 1 of the argon purification unit Y is used as the refined gas G7 99.999 ° /. The above-mentioned high-purity argon (the degree of _: 、, I' in the refined gas G7 can be reduced to 0.1 volume ppm or less). Further, in the present method, the adsorption steps, the refrigerant extraction step, the heat removal step, the heat medium extraction step, and the cooling step of the respective adsorption columns 51A and 51B of the TSA device 50 are as described above. And the pressure accumulation step, thereby achieving enrichment or high purity of the atmosphere in the quasi-purified gas (7). If the method is wrong, a high yield of highly purified argon can be easily achieved. This is because in the present method, the exhaust gas (gas G?') continuously derived from the adsorption towers 51Α, 5ΐβ in the heating desorption step is returned to the buffer tank, and the exhaust gas is supplied as the PSA method and the TSA method. Once again argon enrichment. In the heating and desorption step of the method, nitrogen is desorbed from an adsorbent which adsorbs nitrogen through an adsorption step. In order to appropriately discharge the desorbed nitrogen out of the adsorption tube 5?c, the purified gas G7 (high purity argon gas) is introduced into the adsorption tube 51c of the adsorption columns 51A, 51B in the heating desorption step. Therefore, the argon concentration of the exhaust gas (gas G/) derived from the adsorption tubes 51c of the adsorption towers 51A, 51B in the heating and desorption step is high. In the present method, such exhaust gas (gas G/) is not discharged to the buffer tank 1G for further argon enrichment using the psA method and the m method. Therefore, the method is suitable for obtaining high purity argon in high yield. In addition, by this method, it is easy to shorten the TSA operation time of the TSA device 5〇. This is because, in the present method, when the TSA method accompanying the temperature fluctuation of the adsorbent is performed, the liquid refrigerant, the liquid sheet, the spoon, and the medium M2 are used to see the temperature change of the α and the auxiliary agent. . The specific steps are as described. In the heating and desorption step of the present invention, the adsorbent in the adsorption tube 51c is heated by using a liquid heat medium. The adsorbent is supplied from the liquid heat medium M2 to the adsorbent in the b 51 c by bringing the liquid heat medium into contact with the adsorbent tube 51c' filled with the adsorbent, thereby heating the adsorbent. Since the specific heat of the liquid heat medium M2 is considerably greater than the specific heat of the gas, compared with the use of the gas as a medium for heating the adsorbent in the TSA method; brother, as the method uses the liquid heat medium M2 Heating the adsorbent allows the adsorbent to warm up to the desired temperature relatively quickly. If a 55% aqueous solution of ethanol is used as the heat medium M2 in the present method (first case), and argon gas is used as a medium for heating to raise the temperature of the adsorbent (second case), since 55% The specific heat of the aqueous ethanol solution is 839. 839kcal/kg · °C (at -20 °c), and the specific heat of the argon wind is 125. 125kcal/kg · t: (at -23t:), the heat of the adsorbent per unit time In the first case, the supply is about 7 times that of the second case. Therefore, in the first case (in the case of the present invention), it is possible to end the twisting desorption step at a short time to the extent of one seventh of the second case. The shortening of the heating desorption step time is helpful for shortening the working time of 40 201043571. On the other hand, in the cooling step of the method, the liquid refrigerant M1 is used to cool the adsorbent in the adsorption tube 5丨c. By bringing the liquid refrigerant 接触 into contact with the adsorption tube 51c filled with the adsorbent, the refrigerant M1 takes heat energy from the adsorbent in the adsorption unit 51c, thereby cooling the adsorbent. Since the specific heat of the liquid refrigerant M1 is considerably greater than the specific heat of the gas, the case of cooling the adsorbent can be faster than in the case of the medium for cooling the adsorbent. If it is set to use 55% ethanol to dissolve in water (the third case), and set the temperature to cool the adsorbent (the specific heat of the fourth mouse is as described above, the yield is 'achievable in the third case' The three cases (the shortening of the time under the short time related to the degree of one-seventh of the present invention is helpful to TSA

使用氣體作為用於TSA法中本方法使用液狀的冷媒Μ1 使吸附劑降溫至所欲的溫度液來作為本方法中的冷媒Ml 用氬氣來作為冷卻用的媒介況）’由於55%乙醇水溶液及母單位時間從吸附劑的熱接第四情況的7倍左右。因此況）’是可以在以第四情況的使冷卻步驟結束。冷卻步驟業時間的縮短。方法’是適用於利用適用於謀求TSA作業如上所述，本發明相關之氬精製 TSA法而以高產率取得高純度氬，且時間的縮短。 ^ /…「叼吸附劑的吸ρ 用·酿度’如上所述為—5(rc以上。坆樣的構成，從簡便地1 本方法的觀點來說是較佳的。 f # π ςη。為將冷媒ΜΙ冷卻j 貫見低至-50C的吸附用溫度之程 β a疋可以藉由較容易写 201043571 得的冷卻機等來實現。本方法之在TSA系統5的加熱脫附步驟中受到加熱的吸濕劑的溫度’如上所述’最高為5〇。將熱媒M2加熱至貫現加熱脫附步驟中最咼為50 °C的加熱溫度之程度，是可以藉由較容易取得的電熱器等來實現。本方法之在TSA系統5的處於吸附步驟的吸附塔51A、 51B的吸附管51c的内部壓力，如上所述為〇〇iMpaG至 IMPaG的範圍；且處於加熱脫附步驟的吸附塔“A、51B的吸附管51 c的内部壓力，如上所述是限於低於吸附步驟中的吸附管51c的内部壓力’而為大氣壓至〇.〇5MPaG的範圍。這樣的構成’是適用於在吸附步驟促進不純物氮吸附至吸附劑、在加熱脫附步驟促進不純物氮從吸附劑脫附的情況。在本發明中’是可以在TSA系統5以冷媒Ml與熱媒 M2不互相混在一起的方式使這些冷媒Ml及熱媒M2在TSA 裝置50内巡迴。也就是對冷媒Ml而言，可以避免因熱媒 Μ 2的混入而使溫度不當地上升的情況；另外，對熱媒μ2 而言’可以避免因冷媒Ml的混入而使冷媒Ml溫度不當地下降的情況。這樣的構成，是適用於有效率地使用冷媒M i 及熱媒M2。在本方法中，是在PSA系統3而如上所述，從處於脫附步驟（第一脫附步驟、第二脫附步驟）的吸附塔31A、31B、 31C持續導出的氣體（廢氣）之中’將氬氣濃度相對較高的廢氣（氣體h)導入緩衝槽1 〇，將此廢氣供作使用PSA法的 201043571 再次的氬的富化。這樣的構成，是有助於以高產率取得高純度氬。在本方法中，是在PSA系統3而如上所述，從處於清潔步驟（第一清潔步驟、第二清潔步驟）的吸附塔31a、31b、 31C持續導出的氣體（沖洗用氣體）之中，將氬氣濃度相對較向的沖洗用氣體（氣體Gs，導入緩衝槽丨〇，將此沖洗用氣體供作使用PSA法的氬氣的富化。這樣的構成，是有助於以高產率取得高純度氬。 D 【實施例】使用弟1圖至第3圖所示的氩ι氣精製裝置γ，而從既疋的原料氣體G。將氬濃縮分離。在本實施例中的原料氣體，疋從單晶矽拉晶爐排出的使用完畢的氣氛氣體，其含有作為主成分的氬氣。此原料氣體G。的的規格，是揭露於第22圖的表格。在本實施例中’在貯留系統1中，將原料氣體G。收進〇緩衝槽10，並同時從緩衝槽1 〇向著後段（前處理系統2、 PSA系3)持續供應氣體Gi，而針對氣體Gi，是藉由升壓吹風器12及流量控制部14，將壓力控制在〇. ιMpa、且將流里控制在20Nm3/h〇在本實施例中，是在前處理系統2中，以以下的條件對乳體Gl進行前處理。使用鉑系觸媒來作為前處理槽20A 内的觸媒°針對導入至前處理槽20A之前的氣體G!，是添相對於一氧化碳為既定的過剩量的氧，使得在前處理槽 2〇A充分地除去—氧化碳。在前處理槽20A的反應溫度是 43 201043571 控制在2 3 0 °C。使用鉑系觸媒作為前處理槽2 〇 B内的觸媒。針對導入至前處理槽20B之前的氣體Gl，是添加既定量的氧’而使在前處理槽20B除去一部分的氫。在前處理槽2 〇B 的反應溫度是控制在2 5 0 °C。使用鉑系觸媒作為前處理槽 2 0C内的觸媒。針對導入至前處理槽20C之前的氣體G!，是添加既定量的氧’而使經過前處理槽2〇c後實質上除去氫及氧。在前處理槽20C的反應溫度是控制在23〇t。在前處理槽20C之後的冷卻器22C中，將氣體G!冷卻至30 °C。在本實施例中，是在PSA系統3或PSA裝置30中，藉由升壓機32將氣體G1升壓至〇.8MPa為止，並同時如第7 圖至第9圖所示在吸附塔31A、31B、31C中重複由吸附步驟、第一減壓步驟、第二減壓步驟、第一脫附步驟、第二脫附步驟、第一清潔步驟、第二清潔步驟、第一升壓步驟、及第二升壓步驟所構成的一個循環。在本實施例中所使用的PSA裝置30的吸附塔31A、31B、31C是各自具有圓筒形狀（内徑100mm、内圍高度18〇〇mm)。在各吸附塔内，是充填CaA式沸石來作為吸附劑。另外在本實施例中，在吸附塔31A、31B、31C的各自之中，吸附步驟是進行33〇秒、第一減壓步驟是進行12〇秒、第二減壓步驟是進行秒、第一脫附步驟是進行6 〇秒、第二脫附步驟是進行1 2 〇秒、第一清潔步驟是進行7〇秒、第二清潔步驟是進行5〇秒' 第一升壓步驟是進行3〇秒、及第二升壓步驟是進行秒。以吸附步驟中的吸附塔31A、31B、31C的内部的最高 44 201043571 壓力為80OkPaG，而以脫附步驟（第一脫附步驟、第二脫附步驟）中的吸附塔31A ' 31B ' 31C的内部的最低壓力為 2 0kPaG。另外，以第一減壓步驟的終了時間點中的吸附塔 31A、31B、31C的内部的壓力（第一中間壓力）為4〇〇kpaG，並以第二減壓步驟的終了時間點中的吸附塔31A、31B、31C 的内部的壓力（第二中間壓力）是2〇〇kPaG。關於以這樣的 G2，其規格條件所實行的本實施例中所取得的準精製氣體是揭露於第22圖的表格。 ΟUsing gas as the method used in the TSA method, the liquid refrigerant Μ1 is used to cool the adsorbent to a desired temperature, and the refrigerant M1 in the present method is used as a medium for cooling by the argon gas. The aqueous solution and the parent unit time are about 7 times higher than the fourth case of the thermal connection of the adsorbent. Therefore, it is possible to end the cooling step in the fourth case. Cooling step The industrial time is shortened. The method is applicable to the use of the argon-refining TSA method according to the present invention, which is suitable for the purpose of the TSA operation, to obtain high-purity argon in a high yield, and the time is shortened. ^ /... "The 吸叼 · · 酿酿酿 ' ' ' ' — — — — rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc. In order to cool the refrigerant enthalpy, the process of the adsorption temperature as low as -50 C can be realized by a cooler or the like which is relatively easy to write 201043571. The method is heated in the heating desorption step of the TSA system 5. The temperature of the moisture absorbent is 'up to 5 如上 as described above. The heating medium M2 is heated to the extent that the heating temperature of 50 ° C at the end of the heating desorption step is the electroheat that can be easily obtained. The internal pressure of the adsorption tube 51c of the adsorption towers 51A, 51B of the TSA system 5 in the adsorption step of the present method is as described above in the range of 〇〇iMpaG to IMPaG; and adsorption in the heating desorption step The internal pressure of the adsorption tube 51c of the column "A, 51B is limited to a range lower than the internal pressure of the adsorption tube 51c in the adsorption step as described above, and is in the range of atmospheric pressure to 〇.〇5 MPaG. Such a constitution is applicable to Promote adsorption of impurity nitrogen to adsorption in the adsorption step In the heating desorption step, the removal of the impurity nitrogen from the adsorbent is promoted. In the present invention, it is possible to make the refrigerant M1 and the heat medium M2 in the TSA system 5 such that the refrigerant M1 and the heat medium M2 are not mixed with each other. In the TSA device 50, the refrigerant M1 can avoid the temperature rising improperly due to the mixing of the heat medium 2, and the heat medium μ2 can be prevented from being mixed by the refrigerant M1. The temperature of the refrigerant M1 is not properly lowered. Such a configuration is suitable for the efficient use of the refrigerant M i and the heat medium M2. In the present method, the PSA system 3 is as described above, and is in the desorption step (the In the gas (exhaust gas) continuously derived from the adsorption towers 31A, 31B, and 31C of the desorption step and the second desorption step, 'the exhaust gas (gas h) having a relatively high argon gas concentration is introduced into the buffer tank 1 〇, and this is The exhaust gas is used for the enrichment of argon again using the PSA method of 201043571. Such a configuration is to contribute to high purity argon in high yield. In the present method, in the PSA system 3 as described above, from the cleaning step (first cleaning step In the gas (flushing gas) continuously derived from the adsorption towers 31a, 31b, and 31C in the second cleaning step, the rinsing gas (gas Gs is introduced into the buffer tank) for the flushing. The gas is supplied as an enrichment of argon gas using the PSA method. Such a configuration contributes to obtaining high-purity argon in a high yield. D [Examples] The argon gas refining device shown in Fig. 1 to Fig. 3 is used. γ is obtained by concentrating and separating argon from the raw material gas G. The raw material gas in the present embodiment, the used atmosphere gas discharged from the single crystal germanium crystal pulling furnace, contains argon as a main component. This material gas G. The specifications are disclosed in the table in Figure 22. In the present embodiment, in the storage system 1, the material gas G is used. The buffer tank 10 is received, and the gas Gi is continuously supplied from the buffer tank 1 to the rear stage (pretreatment system 2, PSA system 3), and the gas Gi is controlled by the booster blower 12 and the flow rate control unit 14, The pressure was controlled to ι. ιMpa, and the flow was controlled at 20 Nm 3 /h. In the present embodiment, in the pretreatment system 2, the milk G1 was pretreated under the following conditions. The platinum-based catalyst is used as the catalyst in the pretreatment tank 20A. For the gas G! before the introduction into the pretreatment tank 20A, oxygen is added to a predetermined excess amount of carbon monoxide, so that the pretreatment tank 2A Fully remove carbon monoxide. The reaction temperature in the pretreatment tank 20A is 43 201043571 controlled at 2 30 °C. A platinum-based catalyst is used as a catalyst in the pretreatment tank 2 〇 B. With respect to the gas G1 before being introduced into the pretreatment tank 20B, a predetermined amount of oxygen is added to remove a part of the hydrogen in the pretreatment tank 20B. The reaction temperature in the pretreatment tank 2 〇B is controlled at 250 °C. A platinum-based catalyst was used as a catalyst in the pretreatment tank 20C. With respect to the gas G! before the introduction into the pretreatment tank 20C, a predetermined amount of oxygen is added, and hydrogen and oxygen are substantially removed after passing through the pretreatment tank 2〇c. The reaction temperature in the pretreatment tank 20C is controlled at 23 〇t. In the cooler 22C after the pretreatment tank 20C, the gas G! was cooled to 30 °C. In the present embodiment, in the PSA system 3 or the PSA device 30, the gas G1 is boosted to 〇.8 MPa by the booster 32, and at the same time as shown in Figs. 7 to 9 in the adsorption tower 31A. And 31B, 31C repeating the adsorption step, the first depressurization step, the second decompression step, the first desorption step, the second desorption step, the first cleaning step, the second cleaning step, the first step of stepping, And a cycle formed by the second step of boosting. The adsorption towers 31A, 31B, and 31C of the PSA unit 30 used in the present embodiment each have a cylindrical shape (inner diameter: 100 mm, inner circumference height: 18 mm). In each adsorption column, CaA zeolite is filled as an adsorbent. Further, in the present embodiment, among the adsorption towers 31A, 31B, and 31C, the adsorption step is performed for 33 sec seconds, the first depressurization step is performed for 12 sec seconds, and the second decompression step is performed for seconds, first. The desorption step is 6 sec., the second desorption step is 1 2 sec., the first cleaning step is 7 sec, and the second cleaning step is 5 sec. The first step is 3 进行. The second and second boosting steps are performed in seconds. The highest internal pressure of the adsorption towers 31A, 31B, and 31C in the adsorption step is 44,000,571,571, and the pressure is 80 kPaG, and the adsorption tower 31A '31B '31C in the desorption step (first desorption step, second desorption step) The internal minimum pressure is 20 kPaG. Further, the internal pressure (first intermediate pressure) of the adsorption towers 31A, 31B, 31C in the end time point of the first depressurization step is 4 〇〇 kpaG, and is at the end time point of the second decompression step. The pressure inside the adsorption towers 31A, 31B, and 31C (second intermediate pressure) is 2 kPa. The quasi-refined gas obtained in the present embodiment, which is carried out under the specifications of G2, is disclosed in the table of Fig. 22. Ο

在本貫施例中，疋在TSA系統5或PSA裳置50中，如第12圖至第21圖所示在吸附塔51A、51B中各自重複由吸附步驟、冷媒抽出步驟、加熱脫附步驟、熱媒抽出步驟、冷卻步驟、及蓄壓步驟所構成的一個循環。在本實施例中所使用的TSA裝置50的吸附塔51A、51B是各自具有圓筒形狀（内检20 0mm、内圍高度15〇〇mm)。吸附塔51Α、是各自在内部具有圓筒形狀（内徑20〇mm)的7根吸附管51c。在各吸附塔内’疋充填GaX式彿石來作為吸附劑。使用⑽ 的乙醇水溶液來作為冷媒Ml及熱媒M2。針對導入至PSA 袭置50的準精製In the present embodiment, the crucible is in the TSA system 5 or the PSA skirt 50, and the adsorption step, the refrigerant extraction step, and the heating desorption step are repeated in the adsorption towers 51A, 51B as shown in Figs. 12 to 21, respectively. A cycle consisting of a heat medium extraction step, a cooling step, and a pressure accumulation step. The adsorption towers 51A and 51B of the TSA unit 50 used in the present embodiment each have a cylindrical shape (inner inspection 20 mm, inner circumference height 15 mm). The adsorption tower 51A is seven adsorption tubes 51c each having a cylindrical shape (inner diameter: 20 mm) inside. In each of the adsorption towers, a GaX-type Fossil was filled as an adsorbent. The aqueous solution of ethanol (10) was used as the refrigerant M1 and the heat medium M2. Quasi-refining for introduction to PSA

表轧體G2，疋在熱交換器52A冷卻至-2(TC 為止、在冷卻器52B冷:丨 *The watch body G2, 疋 is cooled to -2 (TC until the heat exchanger 52A, and is cooled in the cooler 52B: 丨 *

d々部至—35 c為止。在鹽水冷卻器52E 中，疋將冷媒Μ1冷卻5 4 η。广 l , ^评至-40C為止。在熱媒槽52F，是將熱媒M2加熱至50Τ'盔 C為止並維持此溫度。在本實施例中，在吸附塔51A、51B的夂ό々士、幻谷自之中，吸附步驟是進行3小時、冷媒抽出步驟是進行〇 9 .Ζ小時、加熱脫附步驟是進行1小時、熱媒抽出步驟县；隹Λ Ω 進仃0 · 2小時、冷卻步驟是進行〗.4 45 201043571 小時、及蓄壓步驟是進行0. 2小時（一個循環的時間是6小時）。另外，以吸附步驟中的吸附塔51A、51B的内部的最終到達吸附壓力（最高壓力）為700kPaG，而以加熱脫附步驟中的吸附塔51A、51B的内部的最終到達脫附壓力（最低壓力）為20kPaG。在本實施例中’是在一個循環的過程中測定吸附管51 c内的吸附計的溫度’其結果示於第圖的曲線圖。在第23圖的曲線圖中，橫軸是表示TSA循環時門 (h)、縱軸是表示吸附劑的溫度（°c )。如第23圖的曲線圖所表’吸附管51c内的吸附計的温度，在吸附步驟之間是維持在-351：、在加熱脫附步驟則激烈地上升而王 4ϋ C、在冷卻步驟則相當程度極速地下降而至-351。針對進行這樣的條件的本實施例中所取得 u I氣體 7 ’其規格是揭露於第22圖的表格。【圖式簡單說明】第1圖是顯示本發明相關的氬精製裝置的全構。歧概略結第2圖是顯示作為第1圖所示的氬精製裝置的一八之PSA系統的結構。 F刀第3圖是顯示作為箆1〜_ ΛΑ — p F两弟1圖所不的氬氣精製裝署认分之TSA系統的結構。 '—部D々 to -35 c. In the brine cooler 52E, the crucible cools the refrigerant crucible 1 by 5 4 η. Wide l, ^ evaluation until -40C. In the heat medium tank 52F, the heat medium M2 is heated to 50 Τ 'helmet C and maintained at this temperature. In the present embodiment, in the gentlemen and the magic valleys of the adsorption towers 51A and 51B, the adsorption step is performed for 3 hours, the refrigerant extraction step is performed for 9 hours, and the heating and desorption step is performed for 1 hour. The heat medium is taken out in the step county; 隹Λ Ω enters 仃 0 · 2 hours, the cooling step is carried out. 4 45 201043571 hours, and the pressure accumulating step is carried out for 0.2 hours (one cycle time is 6 hours). Further, the final arrival adsorption pressure (highest pressure) inside the adsorption columns 51A, 51B in the adsorption step is 700 kPaG, and the final arrival desorption pressure (minimum pressure) inside the adsorption columns 51A, 51B in the heating desorption step ) is 20 kPaG. In the present embodiment, 'the temperature of the adsorbent in the adsorption tube 51 c is measured in one cycle', and the results are shown in the graph of the figure. In the graph of Fig. 23, the horizontal axis represents the gate (h) during the TSA cycle, and the vertical axis represents the temperature (°c) of the adsorbent. As shown in the graph of Fig. 23, the temperature of the adsorbent in the adsorption tube 51c is maintained at -351 during the adsorption step, and rises violently during the heating and desorption step, and in the cooling step. The speed dropped to -351 to a considerable extent. The specification of the u I gas 7 ' obtained in the present embodiment for carrying out such a condition is disclosed in the table of Fig. 22. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing the structure of an argon refining apparatus according to the present invention. Outline Fig. 2 is a view showing a configuration of a PSA system as an eight-part argon refining device shown in Fig. 1. F knives Fig. 3 shows the structure of the TSA system recognized as the argon refining facility as the 箆1~_ ΛΑ — p F two brothers. '-unit

弟4圖是一表格，的PSA法的步驟1〜5 有第2圖所示的PSAFigure 4 is a table, steps 1 to 5 of the PSA method have the PSA shown in Figure 2.

顯示關於實行第2圖所示的pSA裝之在各PSA吸附塔所進行的步驟、裝置的各自動閥及回收線的自動閥 201043571 的開閉狀態》第5圖是一表格，顯示關於實行第2圖所示的PSA裝置的PSA法的步驟6~1〇之在各PSA吸附塔所進行的步驟、還有第2圖所示的PSA裝置的各自動閥及回收線的自動閱的開閉狀態。The opening and closing state of the automatic valve 201043571 which is performed in each PSA adsorption tower and the automatic valve and the recovery line of the apparatus, which is shown in Fig. 2, is shown in the table. In the PSA method of the PSA apparatus shown in the figure, steps 6 to 1 are performed in the respective PSA adsorption towers, and the automatic valves of the PSA apparatus shown in Fig. 2 are automatically opened and closed.

第6圖是一表格’顯示關於實行第4圖所示的PSA裝置的PSA法的步驟11〜15之在各PSA吸附塔所進行的步驟、還有第2圖所示的PSA裝置的各自動閥及回收線的自動閥的開閉狀態。第7圖（a)~(e)是顯示實行第2圖所示的PSA裝置的 PSA法的步騍卜5中的氣體流動狀態。第8圖（a) ~(e)是顯示實行第2圖所示的PSA裝置的 PSA法的步驟6〜1 0中的氣體流動狀態。第9圖（a)〜（e)是顯示實行第2圖所示的PSA裝置的 PSA法的步驟U45中的氣體流動狀態。第1 〇圖是一表格，顯示關於實行第3圖所示的TSA 、SA法的步驟1〜5之在各TSA吸附塔所進行的步驟、 w有第3圖所示的TSA裝置的各自動閥的開閉狀態。第11圖是一表格，顯示關於實行第3圖所示置的 TSA, e J Μ 裝。^去的步驟5〜6之在各TSA吸附塔所進行的步驟、 j 3圖所示的TSA裝置的各自動閥的開閉狀態。第1 2圖是顯示實行第3圖所示的TSA裝置的TSA^ 步驟1 Φ仏A J 1 古的 ♦甲的冷媒流動狀態及氣體流動狀態。Fig. 6 is a table showing the steps performed in the respective PSA adsorption towers in steps 11 to 15 of the PSA method for carrying out the PSA apparatus shown in Fig. 4, and the respective automatics of the PSA apparatus shown in Fig. 2. The opening and closing state of the automatic valve of the valve and the recovery line. Fig. 7 (a) to (e) show the gas flow state in the step 5 of the PSA method for carrying out the PSA apparatus shown in Fig. 2. Fig. 8 (a) to (e) show gas flow states in steps 6 to 10 of the PSA method for carrying out the PSA apparatus shown in Fig. 2. Fig. 9 (a) to (e) show the gas flow state in the step U45 of the PSA method for carrying out the PSA apparatus shown in Fig. 2. The first diagram is a table showing the steps performed in the respective TSA adsorption towers in steps 1 to 5 of the TSA and SA methods shown in Fig. 3, and the automatic operation of the TSA apparatus shown in Fig. 3 The valve is opened and closed. Figure 11 is a table showing the TSA, e J Μ installed in the implementation of Figure 3. The steps of 5 to 6 in the steps of the respective TSA adsorption towers, and the opening and closing states of the automatic valves of the TSA apparatus shown in Fig. 3 are shown. Fig. 1 is a flow chart showing the refrigerant flow state and the gas flow state of the TSA of the TSA device shown in Fig. 3, step 1 Φ 仏 A J 1 .

第1 3圖是顯示實行第3圖所示的TSA裝置的TSA 片的 47 201043571 步驟2中的冷媒流動狀態、熱媒流動狀態、及氣體流動狀態。第1 4圖是顯示實行第3圖所示的TSA裝置的TSA法的步驟3中的冷媒流動狀態、熱媒流動狀態、及氣體流動狀態。第1 5圖是顯示實行第3圖所示的TSA裝置的TSA法的步驟4中的冷媒流動狀態及氣體流動狀態。第1 6圖是顯示實行第3圖所示的TSA裝置的TSA法的步驟5中的冷媒流動狀態及氣體流動狀態。第1 7圖是顯示實行第3圖所示的TSA裝置的TSA法的步驟6中的冷媒流動狀態及氣體流動狀態。第1 8圖是顯示實行第3圖所示的TSA裝置的TSA法的步驟7中的冷媒流動狀態、熱媒流動狀態、及氣體流動狀態。第1 9圖是顯示實行第3圖所示的TSA裝置的TSA法的步驟8中的冷媒流動狀態、熱媒流動狀態、及氣體流動狀態。第20圖是顯示實行第3圖所示的TSA裝置的TSA法的步驟9中的冷媒流動狀態及氣體流動狀態。第21圖是顯示實行第3圖所示的TSA裝置的TSA法的步驟1 0中的冷媒流動狀態及氣體流動狀態。第22圖是一表格，顯示實施例中的原料氣體、準精製氣體、及精製氣體的規格。第23圖是一曲線圖，顯示實施例中的吸附劑溫度。 201043571 【主要元件符號說明】卜貯留系統； 3〜PSA系統； 4a〜自動閥； 1 0〜貯留槽； 12〜升壓吹風器； 14〜流量控制部；〇 20A〜前處理槽； 200前處理槽； 22A〜冷卻器； 220冷卻器； 23B〜氧供應量控制部； 24〜氳供應量控制部； 25B〜溫度計； 2 6〜氫濃度分析計；〇 27A'線； 2 70線； 30〜PSA裝置； 31a〜氣體通過口； 31b〜氣體通過口； 32〜升壓機； 32b〜氣體送出口； 34'線； 2〜前處理系統； 4〜回收線； 5〜T S A系統； 11 ~除塵器； 13〜濃度分析計； 1 5 '線； 20B〜前處理槽； 21〜預熱器； 22B〜冷卻器； 23A〜氧供應量控制部； 230氧供應量控制部； 25A〜溫度計； 250溫度計； 2 7'線； 27B'線； 2 7D'線； 31A〜吸附塔； 31B〜吸附塔； 31C〜吸附塔； 32a~氣體吸入口； 33〜冷卻器； 34’〜主幹路； 49 201043571 34A~分支路； 34B~分支路； 34C~分支路； 3 5'線； 35A~分支路； 3 5 B〜分支路； 350分支路； 3 6'線； 36A~分支路； 36B〜分支路； 3 6 C〜分支路； 3 7〜線； 37A〜分支路； 37B〜分支路； 370分支路； 3 7 d ~自動閥； 51A〜吸附塔； 51B~K附塔； 51〇~吸附管； 5le〜空間部； 52A〜熱交換器； 520冷媒槽； 52E〜鹽水冷卻器； 52G〜熱媒幫浦； 34a~自動閥； 34b〜自動閥； 34c〜自動閥； 35’〜主幹路； 3 5 a〜自動閥； 35b〜自動閥； 35c〜自動閥； 36’〜主幹路； 3 6 a〜自動閥； 36b〜自動閥； 36c~自動閥； 37’〜主幹路； 37a〜自動閥； 37b〜自動閥； 3 7 c ~自動閥； 50~TSA 裝置； 51a〜氣體通過 51b〜氣體通過 5Id〜分隔板； 51 f〜空間部； 52B〜冷卻器； 52D〜冷媒幫浦 52F〜熱媒槽； 5 3 ~ 線； 50 201043571Fig. 1 is a flow chart showing the flow of the refrigerant, the state of the flow of the heat medium, and the state of the gas flow in the step 2 of the 2010 TIA sheet of the TSA sheet of the TSA device shown in Fig. 3. Fig. 14 is a view showing a refrigerant flow state, a heat medium flow state, and a gas flow state in the third step of the TSA method for carrying out the TSA device shown in Fig. 3. Fig. 15 is a view showing the refrigerant flow state and the gas flow state in the step 4 of the TSA method for carrying out the TSA device shown in Fig. 3. Fig. 16 is a view showing the refrigerant flow state and the gas flow state in the step 5 of the TSA method for carrying out the TSA device shown in Fig. 3. Fig. 17 is a view showing the refrigerant flow state and the gas flow state in the step 6 of the TSA method for carrying out the TSA device shown in Fig. 3. Fig. 18 is a view showing the refrigerant flow state, the heat medium flow state, and the gas flow state in the step 7 of the TSA method for carrying out the TSA device shown in Fig. 3. Fig. 19 is a view showing the refrigerant flow state, the heat medium flow state, and the gas flow state in the step 8 of the TSA method for carrying out the TSA device shown in Fig. 3. Fig. 20 is a view showing the refrigerant flow state and the gas flow state in the step 9 of the TSA method for carrying out the TSA device shown in Fig. 3. Fig. 21 is a view showing a refrigerant flow state and a gas flow state in the step 10 of the TSA method for carrying out the TSA apparatus shown in Fig. 3. Fig. 22 is a table showing the specifications of the material gas, the quasi-purified gas, and the purified gas in the examples. Figure 23 is a graph showing the adsorbent temperature in the examples. 201043571 [Main component symbol description] Bu storage system; 3~PSA system; 4a~automatic valve; 1 0~reservoir; 12~boost hair dryer; 14~flow control unit; 〇20A~pre-treatment tank; 200 pre-treatment Tank; 22A~cooler; 220 cooler; 23B~ oxygen supply control unit; 24~氲 supply control unit; 25B~ thermometer; 2 6~ hydrogen concentration analyzer; 〇27A' line; 2 70 line; 30~ PSA device; 31a~ gas passage port; 31b~ gas passage port; 32~ booster; 32b~ gas delivery port; 34' line; 2~ pretreatment system; 4~ recycling line; 5~TSA system; 13~concentration analyzer; 1 5 'line; 20B~ pre-treatment tank; 21~ preheater; 22B~ cooler; 23A~ oxygen supply control unit; 230 oxygen supply control unit; 25A~ thermometer; Thermometer; 2 7' line; 27B' line; 2 7D' line; 31A~ adsorption tower; 31B~ adsorption tower; 31C~ adsorption tower; 32a~ gas suction port; 33~ cooler; 34'~ trunk road; 49 201043571 34A~ branch road; 34B~ branch road; 34C~ branch road; 3 5' line; 35A~ branch Road; 3 5 B~ branch road; 350 branch road; 3 6' line; 36A~ branch road; 36B~ branch road; 3 6 C~ branch road; 3 7~ line; 37A~ branch road; 37B~ branch road; 370 branch road; 3 7 d ~ automatic valve; 51A ~ adsorption tower; 51B ~ K attached tower; 51 〇 ~ adsorption tube; 5le ~ space part; 52A ~ heat exchanger; 520 refrigerant tank; 52E ~ brine cooler; 52G ~ Heat medium pump; 34a ~ automatic valve; 34b ~ automatic valve; 34c ~ automatic valve; 35' ~ trunk road; 3 5 a ~ automatic valve; 35b ~ automatic valve; 35c ~ automatic valve; 36' ~ trunk road; 3 6 a~ automatic valve; 36b~ automatic valve; 36c~ automatic valve; 37'~ trunk road; 37a~ automatic valve; 37b~ automatic valve; 3 7 c ~ automatic valve; 50~TSA device; 51a~ gas through 51b ~ gas through 5Id ~ partition plate; 51 f ~ space portion; 52B ~ cooler; 52D ~ refrigerant pump 52F ~ heat medium tank; 5 3 ~ line; 50 201043571

53’〜主幹路； 53a〜自動閥； 5 3 b〜自動閥； 54’ ~主幹路； 54a〜自動閥； 54b〜自動閥； 5 6'線； 56A〜分支路； 56B〜分支路； 5 6 c〜自動閥； 57’〜主幹路； 57a〜自動閥； 5 7 b ~自動閥； 58’〜主幹路； 5 8 a〜自動閥； 5 8 b ~自動閥； 5 9 b '線； 59d'線； 59f'線； E2〜精製氣體導出端； GO〜原料氣體； 53八~分支路； 536~分支路； 5 4'線； 54A〜分支路； 54B〜分支路； 5 5'線； 56’〜主幹路； 56a〜自動閥； 56b〜自動閥； 5 7'線； 57A〜分支路； 57B〜分支路； 5 8'線； 58A〜分支路； 58B〜分支路； 5 9a'線； 5 9c'線； 5 9e'線； E1〜原料氣體導入端 E3〜精製氣體導出端 G1〜氣體； G2〜準精製氣體； G3〜氣體； G3’〜氣體； G3’ ’〜氣體； G4〜氣體； G5〜氣體； 51 201043571 G6〜氣體； G7~精製氣體； G7’〜氣體； Μ卜冷媒； M2〜熱媒； Υ〜氬氣精製裝置。53'~ trunk road; 53a~ automatic valve; 5 3 b~ automatic valve; 54' ~ trunk road; 54a~ automatic valve; 54b~ automatic valve; 5 6' line; 56A~ branch road; 56B~ branch road; 6 c~automatic valve; 57'~ trunk road; 57a~ automatic valve; 5 7 b ~ automatic valve; 58'~ trunk road; 5 8 a~ automatic valve; 5 8 b ~ automatic valve; 5 9 b 'line; 59d' line; 59f' line; E2~ refined gas export end; GO~ material gas; 53-8~ branch road; 536~ branch road; 5 4' line; 54A~ branch road; 54B~ branch road; 5 5' line 56'~ trunk road; 56a~ automatic valve; 56b~ automatic valve; 5 7' line; 57A~ branch road; 57B~ branch road; 5 8' line; 58A~ branch road; 58B~ branch road; 5 9a' Line; 5 9c' line; 5 9e' line; E1 ~ raw material gas introduction end E3 ~ refined gas derivation end G1 ~ gas; G2 ~ quasi-refined gas; G3 ~ gas; G3' ~ gas; G3' '~ gas; G4 ~ gas; G5 ~ gas; 51 201043571 G6 ~ gas; G7 ~ refined gas; G7 '~ gas; Μ 冷 refrigerant; M2 ~ heat medium; Υ ~ argon refining device.

Claims

201043571 VII. Patent application scope: 1. An argon refining method comprising: collecting a mixed gas containing argon into a storage tank; supplying the mixed gas from the storage tank to a TSA adsorption tower, the tsa adsorption tower containing a packed adsorbent a sorbent tube; and repeating a cycle comprising the following steps in the TSA adsorption column: an adsorption step of introducing the mixed gas into the state in which the adsorbent in the adsorption tube is at a relatively low temperature for adsorption. a tube' causes the adsorbent to adsorb impurities in the mixed gas, and the argon-rich purified gas is led out from the adsorption tube; a heating desorption step causes the adsorbent in the adsorption tube to warm up to a relative a temperature that simultaneously desorbs the impurities from the adsorbent; and a cooling step to cool the adsorbent in the adsorbent tube; wherein in the heating and desorbing step, a liquid heat medium is used to heat the adsorbent Q tube The adsorbent is introduced into the adsorption tube and at the same time, the exhaust gas (of f gas) is extracted from the adsorption tube to introduce the exhaust gas The storage tank; and in the cooling step' is to use a liquid refrigerant to cool the adsorbent in the adsorption tube. 2. An argon purification method comprising: charging an argon-containing mixed gas into a storage tank; supplying the mixed gas from the storage tank to a TSA adsorption tower selected from a plurality of TSA adsorption towers, wherein the TSA adsorption towers are filled Adsorbent 53 201043571 adsorption tube; and in the above plurality of TSA adsorption towers, each of which repeats a cycle comprising the following steps: an adsorption step in which the adsorbent in the adsorption tube is in a relatively low temperature adsorption temperature state Introducing the mixed gas into the adsorption tube, causing the adsorbent to adsorb the impurities in the mixed gas, and deriving the argon-rich purified gas from the adsorption tube; and heating desorption step to make the adsorption tube The adsorbent is heated to a relatively high temperature and simultaneously desorbs the impurities from the adsorbent; and a cooling step is performed to cool the adsorbent in the adsorbent tube; wherein in the heating desorption step, liquid heat is used The medium heats the adsorbent in the adsorption tube, and introduces the refined gas into the adsorption tube and simultaneously extracts the exhaust gas from the adsorption tube Off gas), the exhaust gas is introduced into the storage tank; and the refined gas introduced into the adsorption tube of the TSA adsorption column in the heating desorption step is a purified gas derived from the adsorption tube of the TSA adsorption column in the adsorption step; In the & step, the liquid refrigerant is used to cool the adsorbent in the adsorption tube. 3. The argon refining method according to claim 2, wherein in the two steps, 'the refined gas is introduced into the adsorption tube and the exhaust gas is simultaneously withdrawn from the adsorption tube, and the exhaust gas is introduced into the storage tank. The purified gas of the adsorption tube of the TSA adsorption tower of the 忒 cooling step is obtained from the (four)° and the adsorption tube of the attached TSA adsorption tower. 4. The argon refining method according to any one of claims 1 to 3, wherein in the adsorbing step, the liquid refrigerant is used to continue cooling the adsorbent in the adsorption tube. The argon refining method according to any one of claims 1 to 3, wherein the adsorption temperature is -50. The argon purification method according to any one of the above claims 1 to 3, wherein the temperature of the adsorbent heated in the heat desorption step is as high as 50 ° C. The argon purification method according to any one of claims 1 to 3, wherein a first internal pressure of the adsorption tube of the TSA adsorption column in the adsorption step is in a range of 0.01 MPaG to 1 MPaG; and the heating is desorbed. The second internal pressure of the adsorption tube of the TSA adsorption tower of the step is, in the case of being lower than the first internal pressure, the range of atmospheric pressure to 〇〇5 MPaG. 8. If the scope of the patent application is 1-3 An argon refining method according to any one of the preceding claims, wherein a portion of the impurities contained in the mixed gas is removed by a psA method before the mixed gas is supplied to the TSA adsorption column. 9. As described in claim 8 An argon refining method, wherein in the PSA method, the mixed gas is supplied to a PSA adsorption column selected from a plurality of PSA adsorption columns packed with a PSA adsorbent; and in each of the plurality of PSA adsorption columns, each of which is repeatedly carried out Dilution step Ring: Adsorption step 'In the state where the PSA adsorption column is relatively high pressure 55 201043571, the mixed gas is introduced into the PSA adsorption column, so that the PSA adsorbent adsorbs the impurities in the mixed gas, and the argon gas is rich. a quasi-refining gas derived from the PSA adsorption column; and a desorbing step of depressurizing the PSA adsorption column to desorb the impurities from the PSA adsorbent, and extracting gas from the PSA adsorption column; The desorption step includes a first desorption step of deriving a first gas from the PSA adsorption column during the start of the desorption step, and a second gas deriving from the PSA adsorption column after the first desorption step The second desorption step, and the first gas is introduced into the storage tank. The argon refining method according to claim 8, wherein in the PSA method, the PSA adsorbent is filled. a plurality of adsorption towers selected from the pSA adsorption tower to supply the mixed gas; and in each of the plurality of adsorption towers, each of which repeats a cycle comprising the following steps: an adsorption step, adsorption at the PSA The tower is relatively high-pressure, and the mixture is introduced into the adsorption tower, so that the PSA adsorbent adsorbs the impurities in the mixed gas, and the argon-rich quasi-refined gas is led out from the PSA adsorption tower; a step of depressurizing the PSA adsorption column to conduct the gas from the PSA adsorption column; a desorbing step of depressurizing the PSA adsorption column to desorb the impurity from the PSA adsorbent, and deriving from the psA adsorption column Gas. 56 201043571 - a cleaning step of introducing a cleaning gas into the PSA adsorption column and deriving the gas from the psA adsorption column; and a step of increasing the pressure in the PSA adsorption column; wherein the cleaning gas of the cleaning step is from a gas derived from the adsorption column of the depressurization step; and the cleaning step includes a first cleaning step of deriving the first gas from the PSA adsorption column during the start of the cleaning step, and adsorbing from the PSA after the first cleaning step The tower derives a second cleaning step of the second gas and directs the second gas to the storage tank. 11. The argon refining method according to claim 10, wherein the desorption step comprises a first desorption step of deriving a third gas from the pSA adsorption column during the start of the desorption step, and The second desorption step of deriving the fourth gas from the PSA adsorption column after the first desorption step, and introducing the third gas into the storage tank. 12. The argon gas purification method according to any one of claims 8 to 11, wherein the mixing gas is supplied from the storage tank before the mixed gas is supplied to the TSA adsorption column or the PSA adsorption column. The gas is treated beforehand, and the purpose of the pretreatment is to remove or change at least a portion of the impurities contained in the mixed gas. 13. An argon refining apparatus comprising: - a TSA adsorption tower having a first gas passage opening and a second gas passage opening, and having an adsorption tube, the adsorption tube and the first and second gas passage openings Connected and filled with an adsorbent; a storage tank for storing the mixed gas before supplying the mixed oxygen containing argon to the TSA suction 57 201043571; a refrigerant storage tank to cool the adsorbent in the adsorption tube For the purpose of storing the liquid refrigerant supplied to the TSA adsorption tower; a heat medium storage tank for heating the adsorbent in the adsorption tube for storing the liquid heat medium supplied to the TSA adsorption tower; a first gas line connecting the storage tank and the TSA adsorption tower, wherein the mixed gas is supplied from the storage tank to the first gas passage port side of the TSA adsorption tower; a second gas line is connected Between the TSA adsorption tower and the storage tank, a gas derived from the first gas passing through the port side of the TSA adsorption tower is supplied to the storage tank; a first refrigerant line for discharging the refrigerant from the refrigerant Storage tank Supplying to the TSA adsorption tower; a second refrigerant line for returning the refrigerant from the TSA adsorption tower to the refrigerant storage tank; - a first heat medium for supplying the heat medium from the heat medium storage tank to the a TSA adsorption tower; and a second heat medium for returning the heat medium from the TSA adsorption tower to the heat medium storage tank. 14·—A argon refining device, comprising: a plurality of TSA adsorption towers, wherein a _ , , /, negative scorpion body passage port and a first gas passage port have a _ adsorption tube, and the order is π ΐ & The 尨 adsorption tube is in communication with the first and first gas passage ports and is filled with the adsorbent; a storage tank for supplying the α 虱 body which will be rushed, s human> μ 虱 to the TSAs 58 201043571 Before the adsorption tower, the mixed gas is stored; a refrigerant storage tank is used for cooling the adsorbent in the adsorption tube for storing the liquid refrigerant supplied to the TSA adsorption tower; and a heat medium storage tank for heating the adsorption tube The adsorbent is for the purpose of storing the liquid heat medium supplied to the TSA adsorption tower; a first gas line is connected between the storage tank and each of the TSA adsorption towers, and the mixed gas is taken from the storage tank The first gas supplied to the respective TSA adsorption towers passes through the mouth side; [) a second gas line having a trunk road and a plurality of branch roads, the branch roads being disposed in each of the above-mentioned TSA adsorption towers and connected thereto The suction of the tsa adsorption tower The second gas of the attached pipe passes through the mouth side; the second gas line has a main road and a plurality of branch roads, the main road is connected to the storage tank, and the branch roads are disposed in each of the TSA adsorption towers and a first gas passing through the port side of the adsorption tube connecting the TSA adsorption tower; a first refrigerant line 'for supplying the refrigerant from the refrigerant storage tank to the TSA adsorption tower of the adsorbent cooling target; - a first refrigerant line 'for returning the refrigerant from the TSA adsorption tower to the refrigerant storage tank; a first heat medium line for supplying the heat medium from the heat medium storage tank to the TSA adsorption tower of the adsorbent heating object; and - second A heat medium wire for returning the heat medium from the TSA adsorption tower to the heat medium storage tank. 15. The argon refining apparatus of claim 13 or 14, further comprising a PSA system having a PM adsorption column for removing a portion of the impurities contained in the mixed gas by the psA method. 16. The argon refining apparatus according to claim 15, wherein a pretreatment system for performing a pretreatment is provided on the first gas line, and the purpose of the pretreatment is to supply the mixed gas to the TSA. At least a portion of the impurities contained in the mixed gas are removed or altered prior to the adsorption column or the PSA adsorption column. 17. A method of purifying a gas comprising: supplying a mixed gas containing a target gas to a TSA adsorption column, the tsa adsorption column comprising a adsorption tube filled with an adsorbent; and repeating a cycle including the following steps in the TSA adsorption column : an adsorption (adsorpt i on) step of introducing the mixed gas into the adsorption tube while the adsorbent in the adsorption tube is in a relatively low temperature adsorption temperature, so that the adsorbent adsorbs impurities in the mixed gas, And purifying the refined gas after the target gas is enriched from the adsorption tube; heating the desorption step, heating the adsorbent in the adsorption tube to a relatively high temperature and simultaneously desorbing the impurities from the adsorbent; And cooling step 'cooling the adsorbent in the adsorption tube; wherein in the heating desorption step, 'using a liquid heat medium to heat the adsorbent in the adsorption tube; and in the cooling step' is to use a liquid The refrigerant cools the adsorbent in the adsorption tube. 18. A method for purifying a gas, comprising: 60 201043571 • supplying a mixed gas containing a target gas to a TSA adsorption tower selected from a plurality of TSA adsorption towers, wherein the TSA adsorption tower comprises a adsorption tube filled with an adsorbent; Each of the plurality of TSA adsorption towers is repeatedly subjected to a cycle comprising the following steps: an adsorption step of introducing the mixed gas into the adsorption tube while the adsorbent in the adsorption tube is at a relatively low temperature for adsorption. And causing the adsorbent to adsorb the impurities in the mixed gas, and deriving the refined gas after the target gas is enriched from the adsorption tube; and heating desorption step, heating the adsorbent in the adsorption tube to relative The temperature of the south temperature simultaneously desorbs the impurities from the adsorbent; and the cooling step lowers the adsorbent in the adsorption tube; wherein in the heating desorption step, the liquid heat medium is used to heat the adsorption tube The adsorbent; and Q in the cooling step, using a liquid refrigerant to cool the adsorption in the adsorption tube Agent. 19. The objective gas refining method according to claim 17 or claim 18, wherein in the adsorbing step, the liquid refrigerant is used to continue cooling the adsorbent in the adsorption tube. The target gas refining method according to claim 17 or 18, wherein the adsorption temperature is -50X: or more. The object gas refining method according to claim 17 or 18, wherein the temperature of the adsorbent heated in the heat desorption step is 61 201043571 up to 50 °C. 22. The gas refining device of the invention comprises: a TSA adsorption tower having a first gas passage opening and a second gas passage opening, and having an adsorption tube, the adsorption tube and the first and second gases passing through The port is connected and filled with an adsorbent; a refrigerant storage tank for cooling the adsorbent in the adsorption tube for storing the liquid refrigerant supplied to the TSA adsorption tower; and a heat medium storage tank for heating the adsorption tube The adsorbent is for storing the liquid heat medium supplied to the TSA adsorption tower; a first refrigerant line for supplying the refrigerant from the refrigerant storage tank to the TSA adsorption tower; and a second refrigerant line for Returning the refrigerant from the TSA adsorption tower to the refrigerant storage tank; a first heat medium line for supplying the heat medium from the heat medium storage tank to the TSA adsorption tower; and a second heat medium line for The heat medium is returned from the TSA adsorption tower to the heat medium storage tank. 23. The gas refining device of the invention, comprising: a plurality of TSA adsorption towers having a first gas passage opening and a first gas passage opening, and having an adsorption tube, the first and first oxygen The body is connected through the port and filled with the adsorbent; the refrigerant storage tank 'for the purpose of cooling the adsorbent in the adsorption tube for storing the liquid refrigerant supplied to the TSA adsorption tower; a heat medium storage tank 'heating the adsorption tube For the purpose of the adsorbent, 62 201043571 . A liquid heat medium for storing the enemy to the TSA adsorption tower; a gas line having a main road and a plurality of branch roads, the branches being placed on one of the above-mentioned TSA adsorption towers The second gas passing through the adsorption tube of the tsa adsorption tower passes through the mouth side; the first refrigerant line is used to supply the refrigerant from the refrigerant storage tank to the TSA adsorption tower of the adsorbent cooling target; Returning the refrigerant from the TSA adsorption tower to the refrigerant storage tank; Ο a first heat medium line for supplying the heat medium from the heat medium storage tank to the TSA adsorption tower of the adsorbent heating object; HTM lines for the heating medium of the heat medium storage tank back to the adsorption tower from the TSA. ❹ 63