JP2005349332A - Method for separating gas and its apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for separating gases and its apparatus which can effectively remove impurities from the exhaust gases discharged from a semiconductor production device using krypton, xenon, and neon as atmospheric gases and can recycle the krypton and other gases for reuse. <P>SOLUTION: In separating and removing impure components in a mixture gas containing at least one type of krypton, xenon and neon, a denitration step for converting nitrogen oxide into nitrogen and steam, a 1st adsorption separation step wherein the gas finished by the denitration step is made to contact with a 1st adsorbent whose readily adsorbable gas components are ammonia and steam thereby to adsorb and separate the ammonia and the water vapor, a 2nd adsorption separation step for bringing the gas finished with the 1st adsorption separation step in contact with a 2nd adsorbent whose readily adsorbable gas components are krypton, xenon and neon thereby to discharge the impurity components difficult for the 2nd adsorbent to adsorb, and a desorption/recovery step for desorbing and recovering the gas components adsorbed by the 2nd adsorbent in the 2nd adsorption separation step from the 2nd adsorbent, are performed. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a gas separation method and apparatus, and more specifically, impurity components in a mixed gas containing at least one of krypton, xenon and neon, particularly nitrogen oxide, ammonia, oxygen, nitrogen, hydrogen, helium, water vapor. It is related with the method and apparatus which remove | eliminate such trace impurities, and isolate | separate and refine | purify the said krypton, xenon, and neon to the state which can be reused.

  In the process of manufacturing a semiconductor product such as a semiconductor integrated circuit, a liquid crystal panel, a solar cell and its panel, a magnetic disk, etc., manufacturing is performed in which plasma is generated in an inert gas atmosphere and the semiconductor product or display device is processed by the plasma. Equipment is widely used. Conventionally, helium or argon has been used as an inert gas in such processing, but in recent years, processing using krypton, xenon, or neon has attracted attention in order to perform more advanced processing.

  Krypton, xenon, and neon are extremely expensive gases (hereinafter, these gases are referred to as high value-added gases) due to the abundance ratio in the air and the complexity of the separation process, and processes using such high value-added gases. In order to establish the economy economically, it is indispensable to separate and purify high value-added gas from used exhaust gas at a high recovery rate and to recycle it. Furthermore, the impurity concentration of the recovered high value-added gas is desired to have a high purity of 100 ppm or less.

  Here, the exhaust gas containing the high value-added gas to be separated and refined is a mixture in which the high-value-added gas, which is an atmospheric gas, and nitrogen or argon introduced into the vacuum exhaust means of the semiconductor manufacturing facility are the main gas components. It is in a gas state. Other components in the exhaust gas include gas components that are added depending on the purpose of manufacturing the semiconductor. For example, oxygen is included in plasma oxidation, and oxygen, nitrogen, hydrogen, ammonia, and nitrogen oxide are included in plasma nitriding and oxynitriding. If helium is used for cooling the substrate, helium is also included.

  Hereinafter, the process of a semiconductor manufacturing apparatus and the gas component discharged | emitted at each process are demonstrated in detail. First, the inside of the chamber before inserting the substrate to be subjected to plasma processing is made a clean nitrogen atmosphere or argon atmosphere by evacuating while purging a purge gas such as nitrogen or argon. The substrate is then inserted into the processing chamber, but nitrogen or argon venting and evacuation is continued to maintain a clean nitrogen or argon atmosphere.

  Next, after the gas flowing in the chamber is switched from nitrogen or argon to an atmosphere gas containing a high value-added gas, and the inside of the processing chamber becomes a high value-added gas atmosphere, plasma processing is started. Therefore, the gas exhausted from the chamber during the plasma processing is mainly occupied by high-value-added gas, but also includes gas components and reaction byproducts added depending on the manufacturing purpose.

  After the plasma processing is completed, the semiconductor manufacturing apparatus stops the plasma by stopping the high frequency application. At this time, the flow gas is switched from the high added value gas to nitrogen or argon, and then the substrate is taken out. Therefore, the gas exhausted during this period may contain nitrogen or argon as a main gas component, but may also include high value-added gas remaining in the system.

  In addition, nitrogen or argon is vented between the processing chamber and the vacuum exhaust system regardless of the process in order to prevent back diffusion of impurities from the vacuum exhaust system. The reverse diffusion preventing nitrogen or argon is exhausted together with the gas exhausted from the processing chamber. Further, nitrogen or argon is also vented to the bearing portion of the vacuum pump for preventing air entrainment. A part of this nitrogen or argon flows into the vacuum exhaust system and is exhausted together with the gas described above.

  A pressure fluctuation adsorption separation (PSA) method is widely known as a method for separating and purifying a target gas component from a mixed gas. For example, when air is used as a raw material to obtain oxygen as a product, zeolite is used as an adsorbent, and air is circulated under pressure to adsorb and fix nitrogen, which is an easily adsorbable gas component, to the adsorbent. Oxygen is collected as a product. Next, if the adsorbent layer is placed under a pressure condition sufficiently lower than the air circulation step (adsorption step), the nitrogen adsorbed on the adsorbent is desorbed. The PSA operation that repeats the adsorption process at a relatively high pressure and the regeneration process at a relatively low pressure is capable of switching between adsorption and regeneration in a short time, so it is easy to increase the amount of product generated per adsorbent. This has the advantage that the device can be easily made compact.

  As a method for removing trace impurities in the source gas, a temperature fluctuation adsorption separation (TSA) method is widely known. For example, in the cryogenic air separation device, a pretreatment device using the TSA method is used to remove moisture and carbon dioxide, which are trace components in the raw material air. In this pretreatment device, impurities such as water and carbon dioxide, which are easily adsorbable gas components, are adsorbed and removed by allowing air to pass through an adsorbent packed bed of activated alumina or zeolite. The adsorbent that has reached adsorption saturation can be easily regenerated by circulating a heated purge gas.

In order to reuse the high value-added gas used in a semiconductor manufacturing apparatus or the like, it is necessary to remove unnecessary gas components such as trace impurities, reaction byproducts, and purge gas contained in the collected mixed gas. The removal of unnecessary gas components in the mixed gas can be achieved to some extent even by the combination of the above-described conventional techniques. For example, if it is a trace gas component such as ammonia, nitrogen oxide, moisture (water vapor), it can be adsorbed and removed by the TSA method using an adsorbent such as zeolite (see, for example, Patent Document 1).
JP 2003-342010 A

  However, since it was difficult to separate helium and hydrogen in the conventional combination, in the invention described in Patent Document 1, as a method for removing hydrogen, hydrogen was converted into water vapor by a hydrogen oxidation catalytic reaction in the presence of oxygen. Conversion and then water vapor had to be removed with the adsorbent. However, it is not only necessary to add a catalyst cylinder using a palladium catalyst or the like and only an adsorption cylinder using the TSA method for removing water vapor only to treat hydrogen, but oxygen is supplied from outside the system. There is a problem that the device configuration becomes complicated, such as necessity. As another separation method, it is conceivable to use a membrane separation method, but in any case, the configuration of the apparatus becomes complicated, resulting in an increase in apparatus cost and an increase in installation space.

  Accordingly, the present invention separates and recycles high-value-added gas from exhaust gas discharged from semiconductor product or display device manufacturing equipment that uses at least one kind of high-value-added gas of krypton, xenon, or neon as an atmospheric gas, and recycles it In doing so, it efficiently removes trace impurities such as nitrogen oxides, ammonia, oxygen, nitrogen, hydrogen, helium, and water vapor contained in the exhaust gas, and continuously separates and purifies high value-added gas with high recovery. An object of the present invention is to provide a gas separation method and apparatus that can be recycled and reused.

  To achieve the above object, the gas separation method of the present invention is a gas separation method for separating and removing an impurity component in a mixed gas containing at least one of krypton, xenon, and neon. A denitration step of converting a certain nitrogen oxide into nitrogen and water vapor by a denitration catalytic reaction in the presence of a reducing substance, and a gas after the denitration step to a first adsorbent containing ammonia and water vapor as easily adsorbable gas components The first adsorbing / separating step in which ammonia and water vapor as impurities are adsorbed on the first adsorbent and separated from the gas, and the second adsorbent containing krypton, xenon and neon as easily adsorbable gas components. A second adsorptive separation step of contacting the gas after the first adsorptive separation step and discharging impurity components that are difficult to adsorb to the second adsorbent; In is characterized in that it comprises a desorption recovery step of recovering by desorbing the adsorbed gas components in the second adsorbent from the second adsorbent.

  Furthermore, in the gas separation method of the present invention, the gas recovered in the desorption recovery step is brought into contact with a third adsorbent containing krypton, xenon and neon as difficult adsorbing gas components, A third adsorptive separation step for adsorbing and separating easily adsorbable gas components is performed, and in particular, the gas component adsorbed on the third adsorbent in the third adsorptive separation step is desorbed from the third adsorbent and desorbed. The gas component is circulated and mixed with the gas introduced into the third adsorptive separation step. In addition, at the front stage of the denitration step, ammonia and nitrogen oxide, which are impurity components in the mixed gas, are reacted with a denitration catalyst to be converted into nitrogen and water vapor, whereby at least one of ammonia and nitrogen oxide is obtained. It is characterized by carrying out a catalytic reaction step of removing from the mixed gas.

  Further, the gas separation apparatus of the present invention is a gas separation apparatus for separating and removing an impurity component in a mixed gas containing at least one of krypton, xenon and neon, wherein nitrogen oxides are removed from nitrogen in the presence of a reducing substance. Denitration catalyst reaction means packed with a denitration catalyst that converts it into water and steam, first adsorption separation means filled with a first adsorbent containing ammonia and water vapor as easily adsorbable gas components, and easy adsorption of krypton, xenon and neon A second adsorbing / separating means filled with a second adsorbent as a reactive gas component, a reducing substance addition path connected to the inlet side of the denitration catalyst reaction means, and a gas derived from the outlet side of the denitration catalyst reaction means Is introduced into the inlet side of the first adsorption cylinder, and the gas component not adsorbed on the first adsorbent is led out from the outlet side of the first adsorption cylinder to enter the second adsorption separation means. A first lead-out path and a second lead-in path that are introduced to the side, a second lead-out path that leads out a gas component that has not been adsorbed by the second adsorbent from the outlet side of the second adsorption separation means, and the second adsorbent And a recovery path for recovering from the inlet side of the second adsorption separation means by desorbing the gas component adsorbed on the second adsorbent.

  Further, the gas separation apparatus of the present invention includes a third adsorption separation unit filled with a third adsorbent containing krypton, xenon and neon as a hardly adsorbable gas component, and is provided from the second adsorption separation unit to the recovery path. A third introduction path for introducing the recovered gas to the inlet side of the third adsorption separation means, and a third lead-out path for deriving the gas component not adsorbed by the third adsorbent from the outlet side of the third adsorption cylinder And the third adsorption separation means desorbs the gas component adsorbed on the third adsorbent from the third adsorbent and derives it from the inlet side of the third adsorption cylinder. 3 It is characterized by having a circulation path that circulates and joins the gas introduced into the adsorption separation means. Furthermore, a catalyst reaction means for reacting ammonia and nitrogen oxides, which are impurity components in the mixed gas, with a denitration catalyst and converting them into nitrogen and water vapor is provided upstream of the denitration catalyst reaction means. .

  According to the present invention, impurities such as nitrogen oxide, ammonia, oxygen, nitrogen, hydrogen, helium, and water vapor are efficiently separated and removed from a mixed gas containing at least one kind of high value added gas such as krypton, xenon, and neon. be able to. In addition, the equipment cost and operation cost of the entire separation device can be reduced. In particular, in the present invention, impurity components are extracted from high-value-added gas mixed exhaust gas having various compositions discharged from various processes of a semiconductor process using a high-value-added gas, for example, an oxidation process, a nitriding process, and an oxynitriding process. It can be reliably separated and removed, and the high value-added gas after impurity separation can be recovered in a reusable state as the atmospheric gas of the semiconductor manufacturing apparatus.

  FIG. 1 is a system diagram showing an embodiment of the gas separation apparatus of the present invention, and FIG. 2 is a system diagram showing an example of a semiconductor manufacturing apparatus. This gas separation apparatus separates and removes impurity components contained in the exhaust gas discharged from the semiconductor manufacturing apparatus 11 that uses at least one of krypton, xenon, and neon as an atmospheric gas, and can be reused as an atmospheric gas. It is formed so that the mixed gas purified can be recovered.

  As main equipment in this gas separation device, a denitration catalyst reaction means 21 that performs a denitration process in order from the upstream side of the gas flow, and a first adsorption separation that performs a first adsorption separation process that mainly adsorbs and separates ammonia and water vapor. Means 31 and second adsorptive separation means 41 for performing a second adsorptive separation step of adsorbing krypton, xenon and neon to separate hydrogen and helium are provided.

  Further, a third adsorption separation means 51 for performing a third adsorption separation step for further purifying the gas recovered by the second adsorption separation means 41 is provided at the subsequent stage of the second adsorption separation means 41, and the denitration catalyst reaction means 21 In the previous stage, a catalytic reaction means 61 for performing a catalytic reaction step for removing ammonia or nitrogen oxide is provided.

  As shown in FIG. 2, the semiconductor manufacturing apparatus 11 supplies a predetermined gas into the processing chamber 14 from the gas panel 12 through the gas supply path 13, and processes the substrate with the processing chamber 14 in a predetermined atmosphere. Thus, as described above, exhaust gas having a composition corresponding to the processing state is discharged to the exhaust path 15 of the processing chamber 14. In the exhaust path 15, a booster pump 16 for sucking gas from the processing chamber 14, a recovery back pump 17 for sending exhaust gas discharged from the booster pump 16 to the gas separation device, and exhaust gas discharged from the booster pump 16 An exhaust-side back pump 18 is provided for discharging the gas from the system.

  The pumps 16, 17 and 18 are provided with seal gas introduction portions 16a, 17a and 18a for introducing a seal gas for preventing back diffusion of impurities and entrainment of the atmosphere, respectively, and the gas introduction portions 16a and 17a. Nitrogen or argon is introduced from the gas, and nitrogen is introduced from the gas introduction part 18a.

  Exhaust gas sucked into the recovery back pump 17, that is, at least one of krypton, xenon and neon used as the atmospheric gas, nitrogen or argon used as the purge gas, nitrogen or argon introduced into the pump Gases added for substrate processing and gases generated by reaction or decomposition during processing, for example, mixed gas containing nitrogen oxide, ammonia, hydrogen, oxygen, nitrogen, water vapor, carbon dioxide, helium, etc. as impurities The exhaust gas consisting of is introduced from the recovery back pump 17 through the exhaust gas recovery path 19 into the gas separation device.

  As the atmospheric gas, a high value-added gas such as krypton, xenon, or neon may be used alone, or a mixed gas thereof or a gas obtained by mixing these with argon at a predetermined ratio may be used. In the present invention, when a high value-added gas and argon are mixed and used as an atmospheric gas, the mixed gas of the high value-added gas and argon is also regarded as a high value-added gas. When an atmosphere gas in which a high value-added gas and argon are mixed is used, a considerable amount of argon is contained in the exhaust gas. In addition, when nitrogen is introduced as a sealing gas into each pump 16, 17, and 18, a considerable amount of nitrogen is also included.

  The exhaust gas introduced into the gas separation device is first introduced into the catalytic reaction means 61 to perform the catalytic reaction step. The catalyst reaction means 61 is a reactor in which a denitration catalyst is filled in a reaction cylinder 62. By contacting exhaust gas with the denitration catalyst, nitrogen oxide and ammonia contained in the exhaust gas are reacted to at least these. Either one is removed from the exhaust gas. A commercially available catalyst can be used as the denitration catalyst, and the reaction temperature depends on various operating conditions such as the type and amount of catalyst used, the concentration of nitrogen oxides and ammonia, and the flow rate of exhaust gas. However, it is usually 250 ° C. or higher, preferably about 300 ° C. For heating to the catalytic reaction temperature, a heater may be provided at the inlet of the reaction tube 62 to heat the exhaust gas flowing into the tube, and the reaction tube 62 may be provided with heating means such as a heater. Also good.

Nitrogen oxides and ammonia coexisting in the exhaust gas flowing into the reaction cylinder 62 come into contact with the denitration catalyst at a predetermined temperature, so that the nitrogen oxides are dinitrogen monoxide (N ₂ O) and nitrogen monoxide (NO ), Nitrogen dioxide (NO ₂ ) and ammonia react to convert to nitrogen and water vapor, respectively.

3N ₂ O + 2NH ₃ → 4N ₂ + 3H ₂ O
6NO + 4NH ₃ → 5N ₂ + 6H ₂ O
6NO ₂ + 8NH ₃ → 7N ₂ + 12H ₂ O

  At this time, when ammonia and oxygen coexist in the exhaust gas, a reaction between ammonia and oxygen also occurs at the same time and is converted into nitrogen and water vapor.

3O ₂ + 4NH ₃ → 2N ₂ + 6H ₂ O

  Further, when the nitrogen oxide and ammonia react to generate ammonium nitrate before flowing into the catalyst reaction means 61, the ammonium nitrate is finally converted into nitrogen and water vapor.

NH ₄ NO ₃ + NO → NO ₂ + N ₂ + 2H ₂ O
NO + NH ₃ → N ₂ + 2 / 3H ₂ O
NO + NO ₂ + 2NH ₃ → N ₂ + 3H ₂ O

  These catalytic reactions satisfy at least one of the conditions when nitrogen oxides and ammonia coexist in the exhaust gas, when ammonium nitrate is already formed, and when ammonia and oxygen coexist. For example, when ammonia is not included in the exhaust gas, ammonium nitrate is not generated. Therefore, these catalytic reactions do not occur and are unnecessary steps, but the processing in the semiconductor manufacturing apparatus 11 is specified. If not, nitrogen oxides and ammonia may coexist in the exhaust gas, so it is preferable to provide them at the most upstream part of the apparatus.

  When nitrogen oxides and ammonia coexist in the exhaust gas, the catalytic reaction ends when one of them disappears due to the catalytic reaction. For example, when nitrogen oxide is contained in a larger amount than ammonia, the catalytic reaction ends with the excess nitrogen oxide remaining when ammonia disappears. Further, when ammonia is contained in a larger amount than nitrogen oxide, the catalytic reaction is completed with excess ammonia remaining when the nitrogen oxide disappears. However, even if ammonia and oxygen coexist in the exhaust gas even when the exhaust gas does not contain any nitrogen oxides, both reactions occur. Note that when oxygen and hydrogen coexist in the exhaust gas, water vapor is generated by the reaction of oxygen and hydrogen.

  By providing such a catalyst reaction means 61 and performing a catalyst reaction step of removing at least one of nitrogen oxide and ammonia in the exhaust gas, nitrogen oxide and ammonia react on the downstream side of the catalyst reaction means 61. Thus, ammonium nitrate can be prevented from being produced.

  That is, when nitrogen oxides, particularly nitrogen dioxide and ammonia coexist in the exhaust gas discharged from the semiconductor manufacturing apparatus 11, the nitrogen dioxide and ammonia react in the pipe through which the exhaust gas flows to produce ammonium nitrate, There is a risk of depositing and accumulating as solid matter on the inner wall of equipment such as piping wall surfaces and valves, which may block the exhaust gas piping or hinder the operation of the equipment.

  For this reason, conventionally, piping and equipment are heated to 170 ° C. or higher, which exceeds the liquefying point of ammonium nitrate, or 210 ° C. or higher, which is the decomposition temperature of ammonium nitrate, to prevent clogging of exhaust gas piping and malfunction of equipment. It was. However, not only the entire exhaust gas piping system, including valves and instruments, need to be always heated, but the valves, etc. must also be heat-resistant, and the equipment cost and There was a problem that the operating cost increased significantly.

  On the other hand, by installing the catalyst reaction means 61 in the exhaust gas recovery path 19 and removing at least one of nitrogen oxides and ammonia, ammonium nitrate may be generated in the piping system downstream from the catalyst reaction means 61. This eliminates the need to heat piping and equipment. In particular, by providing the reaction cylinder 62 as close to the semiconductor manufacturing apparatus 11 as possible, even when nitrogen oxides and ammonia coexist in the exhaust gas, heating is performed in order to avoid inconvenience due to the generation of ammonium nitrate. It is possible to shorten the required exhaust gas recovery path 19 or to omit or simplify the heating means, and it is possible to minimize the cost increase required for heating the piping system.

  The exhaust gas led out from the catalyst reaction means 61 to the outlet path 63 passes through the inlet path 22 of the denitration catalyst reaction means 21 and is reduced through the reducing substance addition path 23 connected to the inlet side of the denitration catalyst reaction means 21. The denitration catalyst reaction means 21 is introduced in the state of being mixed with an active substance such as hydrogen or ammonia, and the denitration process is performed. The inlet path 22 is provided with a flow meter (mass flow meter) 22F to measure the flow rate, and the reducing substance addition path 23 is provided with a flow rate controller (mass flow controller) 23F to reduce the flow rate of the reducing substance ( The amount of reducing substance added is sufficient to convert and remove nitrogen oxides.

The denitration catalyst reaction means 21 is a denitration catalyst reaction cylinder 24 filled with a denitration catalyst, and the same denitration catalyst as that used in the reaction cylinder 62 can be used in the same manner as the denitration catalyst. Heating can be done in the same way. When hydrogen is added to the exhaust gas as a reducing substance, dinitrogen monoxide (N ₂ O), nitrogen monoxide (NO), and nitrogen dioxide (NO ₂ ) contained in the exhaust gas are removed by the denitration catalytic reaction shown below. Converted to nitrogen and water vapor, respectively. In addition, when oxygen is contained, a reaction between oxygen and hydrogen occurs simultaneously.

2NO + 2H ₂ → N ₂ + 2H ₂ O
2NO ₂ + 4H ₂ → N ₂ + 4H ₂ O
N ₂ O + H ₂ → N ₂ + H ₂ O
O ₂ + 2H ₂ → 2H ₂ O

  The denitration process by the denitration catalyst reaction means 21 is an unnecessary process when the nitrogen gas is not included in the exhaust gas, but the process in the semiconductor manufacturing apparatus 11 is not specified as described above. In some cases, nitrogen oxides may be contained in the exhaust gas, and it is difficult to separate and remove nitrogen oxides from the exhaust gas by ordinary adsorption separation. Therefore, it is necessary to provide it upstream of the separation device.

  Nitrogen oxides are removed by the denitration catalyst reaction means 21, and when oxygen is contained, the exhaust gas led to the denitration cylinder outlet path 25 in a state where oxygen is also removed to some extent is removed by the first compressor 25C. The first adsorption separation means 31 is sent to the first introduction path 32 and is introduced into the first adsorption separation means 31 through the first introduction path 32, and the first adsorption separation means 31 removes ammonia and water vapor. A separation step is performed.

  The first adsorbing / separating means 31 fills a pair of first adsorbing cylinders 33a and 33b with a first adsorbent containing ammonia and water vapor as easily adsorbing gas components, and separates and removes ammonia and water vapor by TSA operation. In the adsorption process performed at a relatively low temperature, ammonia and water vapor are removed from the exhaust gas by adsorbing ammonia and water vapor to the first adsorbent, and the first adsorption is performed in a regeneration process performed at a relatively high temperature. The first adsorbent is regenerated by desorbing ammonia and water vapor adsorbed on the adsorbent from the first adsorbent. When carbon dioxide is contained in the exhaust gas, the carbon dioxide is also adsorbed on the first adsorbent and simultaneously separated and removed from the exhaust gas.

  The first adsorption cylinders 33a and 33b include an inlet side path 34a and 34b, an outlet side path 35a and 35b, and a regeneration path 36a for switching the first adsorption cylinders 33a and 33b between the adsorption process and the regeneration process. , 36b are provided. Further, the inlet-side paths 34a and 34b are provided with an exhaust path 37 for exhausting gas discharged during the regeneration process of the first adsorption cylinders 33a and 33b to the outside of the system, and the outlet-side paths 35a and 35b have The first deriving path 38 for deriving the gas component that has not been adsorbed by the first adsorbent in the adsorption process is provided, and the regeneration gas introduction path for introducing the regeneration gas used in the regeneration process is provided in the regeneration paths 36a and 36b. 39 is provided. Although not shown in the drawing, each path of the first adsorption separation means 31 is provided with a valve for alternately switching the first adsorption cylinders 33a and 33b between the adsorption process and the regeneration process.

  As the first adsorbent, activated carbon, silica gel, various zeolites and the like can be used. In particular, potassium ion exchange type A zeolite has the ability to sufficiently adsorb not only water vapor and ammonia but also carbon dioxide. However, since it has the property of hardly adsorbing the high value-added gas, the high value-added gas can be recovered more efficiently by adopting this as an adsorbent.

  In the first adsorption / separation means 31, for example, when the first adsorption cylinder 33a on the left side in FIG. 1 is performing the adsorption process, the first adsorption / separation means 31 is led out to the denitration cylinder outlet path 25 and sent out from the first compressor 25C. The exhaust gas is introduced from the first introduction path 32 through the inlet side path 34a into the first adsorption cylinder 33a, and water vapor, ammonia, and carbon dioxide in the exhaust gas are adsorbed by the first adsorbent and separated and removed. The exhaust gas from which water vapor, ammonia, and carbon dioxide have been removed is led out to the first lead-out path 38 from the outlet side path 35a.

  The regeneration process is performed in the other first adsorption cylinder 33b, and the regeneration gas heated to a predetermined temperature is introduced from the regeneration gas introduction path 39 into the first adsorption cylinder 33b through the regeneration path 36b, and the first adsorbent. Is heated to desorb water vapor, ammonia and carbon dioxide, and are discharged out of the system from the inlet side passage 34b through the exhaust passage 37. Both the first adsorption cylinders 33a and 33b are alternately switched between the adsorption process and the regeneration process by opening and closing the valves provided in the respective paths at a preset timing, and thereby the water vapor, ammonia, dioxide in the exhaust gas. Continuous adsorption and removal of carbon.

  The exhaust gas from which water vapor, ammonia, and carbon dioxide have been removed by the first adsorptive separation means 31 includes hydrogen added in the exhaust gas as impurities and helium in addition to hydrogen added in the denitration step, Nitrogen and argon used as the gas, argon as an atmospheric gas component other than the high value-added gas, and the like are included.

  The exhaust gas led out to the first lead-out path 38 in the adsorption step of the first adsorption separation means 31 flows into the second introduction path 42 of the second adsorption separation means 41 via the first buffer tank 38B, and the second compressor 42C and the 2nd buffer tank 42B are introduced into the 2nd adsorption separation means 41, and the 2nd adsorption separation process including a desorption recovery process is performed.

  The second adsorption separation means 41 fills a pair of second adsorption cylinders 43a and 43b with a second adsorbent containing a high value-added gas (krypton, xenon and neon) as an easily adsorbable gas component. Hydrogen and helium, which are difficult-to-adsorb components with respect to the adsorbent, are separated and removed by PSA operation. In the adsorption process performed at a relatively high pressure, the second adsorbent adsorbs the high value-added gas, (2) Hydrogen and helium that have not been adsorbed by the adsorbent are removed from the exhaust gas by discharging from the adsorption cylinder, and the high value-added gas adsorbed by the second adsorbent is desorbed in a regeneration process performed at a relatively low pressure. In addition, the purge gas is introduced into the adsorption cylinders 43a and 43b from the outlet side to collect the high added value gas and to regenerate the second adsorbent.

  The second adsorption cylinders 43a and 43b include an inlet side path 44a and 44b, an outlet side path 45a and 45b, and a purge gas inlet path for switching the second adsorption cylinders 43a and 43b between the adsorption process and the regeneration process. 46a and 46b are provided. Further, the inlet-side paths 44a and 44b include a recovery path 47 for recovering the high value-added gas discharged during the regeneration process of the second adsorption cylinders and a first circulation path for circulating it to the first buffer tank 38B. 48 is provided, and hydrogen and helium that have not been adsorbed by the first adsorbent in the adsorption process are discharged from the third buffer tank 49B through the flow rate controller (mass flow controller) 49F to the outlet-side paths 45a and 45b. A second lead-out path 49 and a purge gas introduction path 50 for introducing purge gas used in the regeneration process into the third buffer tank 49B via a flow rate controller (mass flow controller) 50F are provided. Although not shown, each path of the second adsorption / separation means 41 is provided with a valve for alternately switching both the second adsorption cylinders 43a and 43b between the adsorption process and the regeneration process.

  For the second adsorbent, it is preferable to use activated carbon which is an equilibrium separation type adsorbent. This activated carbon has a large amount of high value-added gas adsorption (easy adsorption), a small amount of nitrogen adsorption (difficult adsorption), hydrogen as an equilibrium adsorption amount under relatively high pressure as in the adsorption process of PSA operation, hydrogen In addition, it has the property of hardly adsorbing helium, and is optimal for separating and removing hydrogen, helium and nitrogen in the exhaust gas.

  The purge gas introduced from the purge gas introduction path 50 is a gas that does not contain hydrogen and helium, or a gas that can be easily separated by the third adsorption separation means 51 in the subsequent stage and has few impurities to be removed, such as high-purity argon or high-purity nitrogen. High-purity oxygen or the like can be used, but usually a gas present in a relatively large amount in the gas to be treated by the second adsorptive separation means 41, for example, a mixture of a high value-added gas and argon as an atmospheric gas When using gas, it is preferable to use high purity argon. By appropriately setting the PSA operation, it is possible to use a gas not corresponding to the above conditions as a purge gas, but the recovery efficiency of the final high value-added gas is reduced or impurities are mixed. This is not preferable.

  In the second adsorption / separation means 41, for example, when one of the second adsorption cylinders 43a on the left side in FIG. 1 is performing an adsorption process, the exhaust gas led out from the first adsorption / separation means 31 to the first lead-out path 38 is The pressure is increased to a predetermined adsorption process pressure by the second compressor 42C of the second introduction path 42, and is introduced from the second buffer tank 42B through the inlet-side path 44a into the one second adsorption cylinder 43a, and in the exhaust gas. High value-added gas is adsorbed by the second adsorbent and held in the cylinder, and hydrogen and helium that have not been adsorbed by the second adsorbent, and nitrogen and argon that are difficult to adsorb by the second adsorbent are led out from the outlet side passage 45a. Then, the gas is discharged from the second lead-out path 49 through the third buffer tank 49B and the flow rate controller 49F.

  In the other second adsorption cylinder 43b, a regeneration process including a desorption recovery process is performed, and the high value added that the inside of the second adsorption cylinder 43b is reduced to a predetermined regeneration process pressure and adsorbed on the second adsorbent. While the gas is desorbed, a part of the gas in the third buffer tank 49B is introduced into the second adsorption cylinder 43b from the purge gas inlet path 46b as the purge gas, and the high added value gas desorbed from the second adsorbent is introduced into the inlet side path. 44b. At this time, a gas not containing hydrogen or helium is introduced into the third buffer tank 49B from the purge gas introduction path 50 via the flow rate controller 50F, and is led out from one second adsorption cylinder 43a in the adsorption process. A gas having a lower hydrogen or helium content than the gas is introduced into the other second adsorption cylinder 43b as a purge gas.

  In this regeneration process, immediately after the start of the regeneration process, a gas that is not adsorbed by the second adsorbent in the second adsorption cylinder 43b, that is, a non-adsorptive gas other than a high value-added gas such as hydrogen, helium, and nitrogen Since the extracted gas is led out from the second adsorption cylinder 43b to the inlet side path 44b, the gas led out at this time is circulated through the first circulation path 48 to the first buffer tank 38B having a low pressure. Further, the gas led out from the second adsorption cylinder 43b to the inlet side path 44b immediately before the end of the regeneration process is also high when the purge gas introduced from the third buffer tank 49B to the second adsorption cylinder 43b is desorbed from the second adsorbent. Since there is a possibility that the gas is led to the inlet side path 44b together with the added value gas, the gas led to the inlet side path 44b at this time is also circulated to the first buffer tank 38B through the first circulation path 48.

  In this way, the gas led out to the inlet side path 44b immediately after the start of the regeneration process and just before the end is circulated to the first buffer tank 38B, and only the gas led out to the inlet side path 44b in the intermediate desorption recovery process is recovered. By collecting in the path 47, a gas containing impurity components such as hydrogen, helium, nitrogen, etc. is circulated to the first buffer tank 38B, merged with the exhaust gas, and processed again by the second adsorption separation means 41. The recovery rate and purity of the added value gas can be improved.

  Both the second adsorption cylinders 43a and 43b are alternately switched between the adsorption process and the regeneration process by opening and closing the valves provided in the respective paths at a preset timing, and hydrogen, helium, nitrogen in the exhaust gas. Are continuously removed. The composition of the exhaust gas led to the recovery path 47 in the intermediate stage in the regeneration process of the second adsorption separation means 41 is in a state where nitrogen or argon used as the purge gas is mixed with the high value-added gas, and other gas components Is almost removed. The exhaust gas is recovered from the recovery path 47 to the fourth buffer tank 47B, and passes through the third introduction path 52, the third compressor 52C, and the fifth buffer tank 52B of the third adsorption / separation means 51. And the third adsorptive separation step is performed.

  The third adsorption / separation means 51 fills a pair of third adsorption cylinders 53a and 53b with a third adsorbent having a high added value gas as a hardly adsorbable gas component and nitrogen or oxygen as a hardly adsorbable gas component. , Nitrogen and oxygen which are easily adsorbable gas components to the third adsorbent are separated and removed by PSA operation, and nitrogen and oxygen are converted into the third adsorbent in an adsorption process performed at a relatively high pressure. The high value-added gas that has not been adsorbed by the third adsorbent is recovered from the third adsorption cylinders 53a and 53b by separating the high value-added gas from nitrogen and oxygen, and is performed at a relatively low pressure. The third adsorbent is regenerated by desorbing nitrogen and oxygen adsorbed on the third adsorbent in the regeneration step.

  In the third adsorption cylinders 53a and 53b, the inlet side paths 54a and 54b, the outlet side paths 55a and 55b, and the purge gas inlet path 56a for switching and using the third adsorption cylinders 53a and 53b between the adsorption process and the regeneration process. , 56b, respectively. Further, the inlet-side paths 54a and 54b are provided with exhaust circulation paths 57 and 57a for exhausting or circulating the gas derived during the regeneration process of the third adsorption cylinders 53a and 53b to the fourth buffer tank 47B. The outlet-side passages 55a and 55b are provided with a third lead-out route 58 for leading the gas that has not been adsorbed by the third adsorbent in the adsorption step, that is, the high value-added gas through the sixth buffer tank 58B. Yes. Although not shown, each path of the third adsorption separation means 51 is provided with a valve for alternately switching the third adsorption cylinders 53a and 53b between the adsorption process and the regeneration process.

  Further, the fourth buffer tank 47B has a high-value-added gas introduction path 72 for introducing the high-value-added gas from the high-value-added gas introduction source 71 to the fourth buffer tank 47B via the introduction valve 72V, and a third compression. A part of the gas discharged from the machine 52C is extracted and circulated to the fourth buffer tank 47B, and a part of the gas in the sixth buffer tank 58B is extracted and circulated to the fourth buffer tank 47B. The second analysis path 74 is provided, and the first analysis path 73 and the second analysis path 74 are provided with a first analyzer 73A and a second analyzer 74A, respectively, and are based on the analysis result of the first analyzer 73A. The inlet valve 72V is controlled to open and close.

  As the third adsorbent used in the third adsorptive separation means 51, it is preferable to use zeolite 4A (Na-A type zeolite) which is a speed separation type adsorbent. This zeolite 4A has a characteristic that it easily adsorbs nitrogen and oxygen having a molecular diameter smaller than that of a high value-added gas as compared with a high value-added gas having a relatively large molecular diameter. This characteristic is a separation characteristic generally referred to as a speed separation type. If an appropriate adsorption time is selected, it is possible to selectively adsorb nitrogen and oxygen while preventing high value-added gas from being adsorbed. .

  In the third adsorption separation means 51, for example, when the one third adsorption cylinder 53a on the left side in FIG. 1 is performing an adsorption process, the gas led out from the second adsorption separation means 41 to the recovery path 47 is The pressure is increased to a predetermined adsorption process pressure by the third compressor 52C in the third introduction path 52, introduced into the third adsorption cylinder 53a from the fifth buffer tank 52B through the inlet-side path 54a, Oxygen is adsorbed by the third adsorbent and held in the cylinder, and the high value-added gas that has not been adsorbed by the third adsorbent is led to the sixth buffer tank 58B from the outlet side passage 55a.

  In the other third adsorption cylinder 53b, a regeneration process is performed. The inside of the third adsorption cylinder 53b is reduced to a predetermined regeneration process pressure to desorb nitrogen and oxygen adsorbed on the third adsorbent, 6 A part of the high added value gas in the buffer tank 58 is introduced as a purge gas from the purge gas inlet path 56b, and nitrogen and oxygen desorbed from the third adsorbent are led to the exhaust circulation path 57 through the inlet side path 54b.

  In this regeneration process, immediately after the start of the regeneration process, a gas that is not adsorbed by the third adsorbent in the third adsorption cylinder 53b, that is, a gas containing a large amount of high value-added gas is led to the exhaust circulation path 57. Therefore, the gas derived at this time is circulated and collected in the fourth buffer tank 47B. Further, the gas led out from the third adsorption cylinder 53b to the exhaust circulation path 57 just before the end of the regeneration process is also the nitrogen in which the purge gas introduced from the sixth buffer tank 58B to the third adsorption cylinder 53b is desorbed from the third adsorbent. Since there is a possibility of being led to the exhaust circulation path 57 together with oxygen, the gas led to the exhaust circulation path 57 at this time is also circulated and collected in the fourth buffer tank 47B.

  In this way, the high value-added gas-containing gas led out to the exhaust circulation path 57 immediately after the start of the regeneration process and immediately before the end is circulated and recovered in the fourth buffer tank 47B and reprocessed. By discharging the derived gas out of the system from the path 57a, it is possible to improve the recovery rate of the high value-added gas.

  Both third adsorption cylinders 53a and 53b are alternately switched between an adsorption process and a regeneration process by opening and closing valves provided in the respective paths at a preset timing, and adsorb nitrogen and oxygen in the gas. Removal is performed continuously. The gas led to the sixth buffer tank 58B in the adsorption process of the third adsorption cylinders 53a and 53b is nitrogen oxide, ammonia, hydrogen, oxygen, nitrogen, water vapor, carbon dioxide, Impurities such as helium are removed to 100 ppm or less, and it is a high value-added gas that can be used as an atmospheric gas.

  When a mixed gas of high value-added gas and argon is used as the atmospheric gas, the gas in the sixth buffer tank 58B is changed to high value-added gas by using argon as the purge gas of the second adsorption separation means 41. It can be a mixed gas with argon. At this time, the composition ratio between the high value-added gas and argon can be adjusted to a predetermined composition ratio by controlling the amount of high value-added gas introduced from the high value-added gas introduction path 72.

  A part of the gas (high value-added gas) in the sixth buffer tank 58B is extracted to the second analysis path 74 for analysis and subjected to composition analysis by the second analyzer 74A. Circulates to 4 buffer tank 47B. The high value-added gas led out from the sixth buffer tank 58B to the third lead-out path 58 is flow-regulated by a flow rate controller (mass flow controller) 58F and introduced into the purifier 75, and further refined by the purifier 75. Then, the gas is supplied from the gas panel 12 to the semiconductor manufacturing apparatus 11 and recycled.

  Further, during the standby period when the high-value-added gas is not supplied to the semiconductor manufacturing apparatus 11, the high-value-added gas is added to the first buffer tank 38B and the fourth buffer tank 47B from the flow controller 76F through the high-value-added gas circulation path 76 The value gas is circulated.

  For the purifier 75, a getter type purifier using a metal or an alloy such as titanium, vanadium, zirconium, iron, nickel, or the like is preferably used. The concentration of impurities remaining in a trace amount in the value gas can be further reduced.

  As shown in this embodiment, the catalyst reaction means 61, the denitration catalyst reaction means 21, the first adsorption separation means 31, the second adsorption separation means 41, and the third adsorption separation means 51 are arranged in this order, and the catalyst reaction step, the denitration process, The mixed gas discharged from the semiconductor manufacturing apparatus 11 that performs processing such as plasma oxidation, plasma nitridation, and plasma oxynitridation by sequentially performing the steps, the first adsorption separation step, the second adsorption separation step, and the third adsorption separation step. Efficient high value-added gas by removing impurities such as nitrogen oxides, ammonia, hydrogen, oxygen, nitrogen, water vapor, carbon dioxide, helium, etc. It can be separated and recovered well.

  Therefore, in the separation apparatus shown in this embodiment, when one process for oxidizing, nitriding, and oxynitriding is performed in one semiconductor manufacturing apparatus, each process for oxidizing, nitriding, and oxynitriding is a separate semiconductor. Although it is performed by the manufacturing equipment, it is possible to deal with exhaust gas being discharged together, even if only one of the oxidation, nitriding, and oxynitriding processes is performed, a gas separation device of this configuration is installed. Therefore, it is possible to directly cope with the addition or change of the processing steps in the semiconductor manufacturing apparatus.

  When there is no possibility that nitrogen oxides and ammonia coexist in the exhaust gas, the catalytic reaction means 61 can be omitted. In addition, a mixed gas of high-value-added gas and argon is used as the atmospheric gas, and argon is used as a seal gas for each pump and a purge gas for the second adsorption / separation means 41 to denitrify impurity oxygen and impurity nitrogen in the exhaust gas. When the catalyst reaction means 21, the first adsorption separation means 31 and the second adsorption separation means 41 can separate and remove, the third adsorption separation means 51 can be omitted.

It is a systematic diagram which shows one example of the gas separation apparatus of this invention. It is a systematic diagram which shows an example of a semiconductor manufacturing apparatus.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 11 ... Semiconductor manufacturing apparatus, 12 ... Gas panel, 13 ... Gas supply path, 14 ... Processing chamber, 15 ... Exhaust path, 16 ... Booster pump, 17 ... Collection | recovery back pump, 18 ... Exhaust side back pump, 16a, 17a, 18a ... seal gas introduction part, 19 ... exhaust gas recovery route, 21 ... denitration catalyst reaction means, 22 ... inlet route, 22F ... flow meter (mass flow meter), 23 ... reducing substance addition route, 23F ... flow rate controller (mass flow controller) ), 24 ... Denitration catalyst reaction cylinder, 25 ... Denitration cylinder outlet path, 25C ... First compressor, 31 ... First adsorption separation means, 32 ... First introduction path, 33a, 33b ... First adsorption cylinder, 34a, 34b ... Inlet side path, 35a, 35b ... Outlet side path, 36a, 36b ... Regeneration path, 37 ... Exhaust path, 38 ... First lead-out path, 38B ... First buffer tank 39 ... regeneration gas introduction path, 41 ... second adsorption separation means, 42 ... second introduction path, 42B ... second buffer tank, 42C ... second compressor, 43a, 43b ... second adsorption cylinder, 44a, 44b ... Inlet side path, 45a, 45b ... Outlet side path, 46a, 46b ... Purge gas inlet path, 47 ... Recovery path, 47B ... Fourth buffer tank, 48 ... First circulation path, 49 ... Second outlet path, 49B ... Third Buffer tank, 49F ... flow rate controller (mass flow controller), 50 ... purge gas introduction path, 50F ... flow rate controller (mass flow controller), 51 ... third adsorption separation means, 52 ... third introduction path, 52B ... fifth buffer tank , 52C ... third compressor, 53a, 53b ... third adsorption cylinder, 54a, 54b ... inlet side path, 55a, 55b ... outlet side path, 56a, 56b ... Gas gas inlet path, 57, 57a ... exhaust circulation path, 58 ... third outlet path, 58B ... sixth buffer tank, 58F ... flow rate controller (mass flow controller), 61 ... catalytic reaction means, 62 ... reactor cylinder, 63 ... outlet 71: High value-added gas introduction source, 72 ... High value-added gas introduction path, 72V ... Introduction valve, 73 ... First analysis path, 73A ... First analyzer, 74 ... Second analysis path, 74A ... Second Analyzer, 75 ... Purifier, 76 ... High value-added gas circulation path, 76F ... Flow controller (mass flow controller)

Claims (8)

  In a gas separation method for separating and removing an impurity component in a mixed gas containing at least one of krypton, xenon, and neon, nitrogen oxides that are impurity components in the mixed gas are subjected to a denitration catalytic reaction in the presence of a reducing substance. A denitration step for converting nitrogen and water vapor, and a first adsorbent containing ammonia and water vapor as easily adsorbing gas components are brought into contact with the gas after the denitration step so that ammonia and water vapor as impurities are brought into the first adsorbent. A first adsorptive separation step of adsorbing and separating from the gas; a gas after the first adsorptive separation step is brought into contact with a second adsorbent containing krypton, xenon and neon as easily adsorbable gas components; A second adsorptive separation step for discharging impurity components that are difficult to adsorb to the adsorbent; and a gas component adsorbed on the second adsorbent in the second adsorptive separation step. The method of separating gases, characterized in that it comprises a desorption recovery step of recovering by al desorption.   The gas recovered in the desorption recovery step is brought into contact with a third adsorbent containing krypton, xenon and neon as hardly adsorbable gas components, and an easily adsorbable gas component is adsorbed and separated from the third adsorbent. The gas separation method according to claim 1, wherein three adsorption separation steps are performed.   The gas component adsorbed on the third adsorbent in the third adsorption separation step is desorbed from the third adsorbent, and the desorbed gas component is circulated and mixed with the gas introduced into the third adsorption separation step. The gas separation method according to claim 2.   Prior to the denitration step, ammonia and nitrogen oxide, which are impurity components in the mixed gas, are reacted with a denitration catalyst and converted into nitrogen and water vapor, whereby at least one of ammonia and nitrogen oxide is mixed gas The gas separation device according to any one of claims 1 to 3, wherein a catalytic reaction step of removing the catalyst from the inside is performed.   In a gas separation apparatus for separating and removing impurity components in a mixed gas containing at least one of krypton, xenon and neon, a denitration catalyst for converting nitrogen oxides into nitrogen and water vapor in the presence of a reducing substance is packed. Denitration catalyst reaction means, first adsorption separation means filled with a first adsorbent containing ammonia and water vapor as easily adsorbing gas components, and a second adsorbent containing krypton, xenon and neon as easily adsorbing gas components The second adsorbing / separating means, the reducing substance addition path connected to the inlet side of the denitration catalyst reaction means, and the gas led out from the outlet side of the denitration catalyst reaction means are introduced to the inlet side of the first adsorption cylinder. A first introduction path, a first extraction path for introducing a gas component that has not been adsorbed by the first adsorbent from the outlet side of the first adsorption cylinder, and introducing the gas component to the inlet side of the second adsorption separation unit; An introduction path, a second lead-out path for deriving a gas component not adsorbed on the second adsorbent from the outlet side of the second adsorption separation means, and a gas component adsorbed on the second adsorbent from the second adsorbent A gas separation device comprising a recovery path that is desorbed and recovered from the inlet side of the second adsorption separation means.   A third adsorbing / separating means filled with a third adsorbent containing krypton, xenon and neon as difficult adsorbing gas components; A third introduction path for introducing the gas component that has not been adsorbed by the third adsorbent from the outlet side of the third adsorption cylinder. The gas separation device according to claim 5.   The third adsorptive separation means desorbs the gas component adsorbed on the third adsorbent from the third adsorbent, leads out from the inlet side of the third adsorption cylinder, and supplies the gas introduced into the third adsorptive separation means. The gas separation device according to claim 6, further comprising a circulation path for circulating and joining.   2. The catalyst reaction means for reacting ammonia and nitrogen oxide, which are impurity components in the mixed gas, with a denitration catalyst and converting them into nitrogen and water vapor in a stage preceding the denitration catalyst reaction means. The gas separator according to any one of 5 to 7.

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