METHOD FOR REFINING ARGON GAS AND RECOVERING AND REFINING APPARATUS FOR ARGON GAS

Abstract

A method is provided for refining an argon gas, in which oxygen is added to the argon gas containing hydrogen, carbon monoxide(CO), and oxygen as impurities so that the hydrogen and the CO are converted into water and carbon dioxide in a catalyst tower, or hydrogen is added to the argon gas so that the oxygen is converted into the water; the method including: monitoring the hydrogen, the CO, and the oxygen on an outlet side of the catalyst tower; and at least one of adding the oxygen to the argon gas when any one of the hydrogen and the CO is detected on the outlet side of the catalyst tower, and adding the hydrogen when the oxygen is detected, wherein the oxygen or the hydrogen to be added is intermittently added to the catalyst tower relative to continuous supply of the argon gas to the catalyst tower.

Claims

1-10. (canceled)

11. A method for refining an argon gas, in which oxygen is added to the argon gas containing at least one of hydrogen, carbon monoxide, and oxygen as impurities so that the hydrogen and the carbon monoxide contained in the argon gas are converted into water and carbon dioxide by using a catalytic reaction in a catalyst tower, or hydrogen is added to the argon gas so that the oxygen contained in the argon gas is converted into the water by using a catalyst reaction in the catalyst tower, and at least one of the hydrogen, the carbon monoxide, and the oxygen is thereby removed from the argon gas, the method comprising the steps of: monitoring at least one of the hydrogen, the carbon monoxide, and the oxygen on an outlet side of the catalyst tower; and at least one of adding the oxygen to the argon gas on an inlet side of the catalyst tower when any one of the hydrogen and the carbon monoxide is detected on the outlet side of the catalyst tower, and adding the hydrogen to the argon gas on the inlet side of the catalyst tower when the oxygen is detected on the outlet side of the catalyst tower, wherein the oxygen or the hydrogen to be added is intermittently added to the catalyst tower relative to continuous supply of the argon gas to the catalyst tower, and at least one of the hydrogen, the carbon monoxide, and the oxygen contained in the argon gas is thereby removed.

12. The method for refining an argon gas according to claim 11, wherein the method comprises none of the steps of, on a downstream side of the catalyst tower, removing oxygen, which is surplus due to the catalytic reaction, by an oxidative reaction with a metal, and removing hydrogen, which is surplus due to the catalytic reaction, by a reductive reaction with a metal.

13. The method for refining an argon gas according to claim 11, wherein a total amount of the hydrogen and the carbon monoxide contained in the argon gas to be refined is compared with an amount of the oxygen contained in the argon gas to be refined, a gas to be added is the oxygen when the total amount of the hydrogen and the carbon monoxide exceeds a double of the amount of the oxygen in terms of a mole equivalent ratio, and a gas to be added is the hydrogen when the same is less than the double.

14. The method for refining an argon gas according to claim 12, wherein a total amount of the hydrogen and the carbon monoxide contained in the argon gas to be refined is compared with an amount of the oxygen contained in the argon gas to be refined, a gas to be added is the oxygen when the total amount of the hydrogen and the carbon monoxide exceeds a double of the amount of the oxygen in terms of a mole equivalent ratio, and a gas to be added is the hydrogen when the same is less than the double.

15. The method for refining an argon gas according to claim 11, wherein the argon gas to be refined is a waste argon gas which is discharged from a silicon single crystal manufacturing apparatus.

16. The method for refining an argon gas according to claim 12, wherein the argon gas to be refined is a waste argon gas which is discharged from a silicon single crystal manufacturing apparatus.

17. The method for refining an argon gas according to claim 13, wherein the argon gas to be refined is a waste argon gas which is discharged from a silicon single crystal manufacturing apparatus.

18. The method for refining an argon gas according to claim 14, wherein the argon gas to be refined is a waste argon gas which is discharged from a silicon single crystal manufacturing apparatus.

19. The method for refining an argon gas according to claim 11, wherein an amount of the oxygen or the hydrogen which is intermittently added is equalized with a stoichiometric amount of oxygen or hydrogen which is insufficient due to the catalytic reaction during a time when the oxygen and the hydrogen are not added.

20. The method for refining an argon gas according to claim 18, wherein an amount of the oxygen or the hydrogen which is intermittently added is equalized with a stoichiometric amount of oxygen or hydrogen which is insufficient due to the catalytic reaction during a time when the oxygen and the hydrogen are not added.

21. A recovering and refining apparatus for an argon gas which contains at least one of hydrogen, carbon monoxide, and oxygen as impurities, comprising: at least one of a catalyst tower in which oxygen is added to the argon gas so that the hydrogen and the carbon monoxide contained in the argon gas are converted into water and carbon dioxide by a catalytic reaction, and a catalyst tower in which hydrogen is added to the argon gas so that the oxygen contained in the argon gas is converted into the water by a catalytic reaction; detecting means for monitoring at least one of the hydrogen, the carbon monoxide, and the oxygen on an outlet side of the catalyst tower; and at least one of oxygen adding means for adding the oxygen to the argon gas on an inlet side of the catalyst tower when any one of the hydrogen and the carbon monoxide is detected on the outlet side of the catalyst tower, and hydrogen adding means for adding the hydrogen to the argon gas on the inlet side of the catalyst tower when the oxygen is detected on the outlet side of the catalyst tower, wherein the oxygen adding means and the hydrogen adding means intermittently add the oxygen or the hydrogen relative to continuous supply of the argon gas to the catalyst tower.

22. The recovering and refining apparatus for an argon gas according to claim 21, wherein the apparatus comprises none of, on a downstream side of the catalyst tower, a metal tower in which oxygen which is surplus due to the catalytic reaction is removed by an oxidative reaction with a metal, and a metal tower in which hydrogen which is surplus due to the catalytic reaction is removed by a reductive reaction with a metal.

23. The recovering and refining apparatus for an argon gas according to claim 21, wherein a total amount of the hydrogen and the carbon monoxide contained in the argon gas to be refined is compared with an amount of the oxygen contained in the argon gas to be refined, the oxygen is added when the total amount of the hydrogen and the carbon monoxide exceeds a double of the amount of the oxygen in terms of a mole equivalent ratio, and the hydrogen is added when the same is less than the double.

24. The recovering and refining apparatus for an argon gas according to claim 22, wherein a total amount of the hydrogen and the carbon monoxide contained in the argon gas to be refined is compared with an amount of the oxygen contained in the argon gas to be refined, the oxygen is added when the total amount of the hydrogen and the carbon monoxide exceeds a double of the amount of the oxygen in terms of a mole equivalent ratio, and the hydrogen is added when the same is less than the double.

25. The recovering and refining apparatus for an argon gas according to claim 21, wherein the argon gas to be refined is a waste argon gas discharged from a silicon single crystal manufacturing apparatus.

26. The recovering and refining apparatus for an argon gas according to claim 22, wherein the argon gas to be refined is a waste argon gas discharged from a silicon single crystal manufacturing apparatus.

27. The recovering and refining apparatus for an argon gas according to claim 23, wherein the argon gas to be refined is a waste argon gas discharged from a silicon single crystal manufacturing apparatus.

28. The recovering and refining apparatus for an argon gas according to claim 24, wherein the argon gas to be refined is a waste argon gas discharged from a silicon single crystal manufacturing apparatus.

29. The recovering and refining apparatus for an argon gas according to claim 21, wherein an amount of the oxygen or the hydrogen which is intermittently added is equalized with a stoichiometric amount of oxygen or hydrogen which is insufficient due to the catalytic reaction during a time when the oxygen and the hydrogen are not added.

30. The recovering and refining apparatus for an argon gas according to claim 28, wherein an amount of the oxygen or the hydrogen which is intermittently added is equalized with a stoichiometric amount of oxygen or hydrogen which is insufficient due to the catalytic reaction during a time when the oxygen and the hydrogen are not added.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0051] FIG. 1 is a schematic view showing that oxygen is added to a waste argon gas to cause a catalytic reaction;

[0052] FIG. 2 is a schematic view of an oxygen additive flow volume when the oxygen is intermittently added by a method for refining an argon gas according to the present invention;

[0053] FIG. 3 is a schematic view showing an oxygen retaining function on a catalyst surface;

[0054] FIG. 4 is a schematic view showing that the oxygen retained on the catalyst surface reacts with hydrogen and carbon monoxide in the argon gas to be converted into water and carbon dioxide;

[0055] FIG. 5 is a schematic view showing an example of a refining flow of the waste argon gas from a silicon single crystal manufacturing apparatus according to the present invention;

[0056] FIG. 6 is a schematic view showing an example of a refining flow of the waste argon gas from the silicon single crystal manufacturing apparatus according to a conventional technology (Patent Literature 1); and

[0057] FIG. 7 is a schematic view showing an example of a refining flow of the waste argon gas from the silicon single crystal manufacturing apparatus according to a conventional technology (Patent Literature 2).

BEST MODE(S) FOR CARRYING OUT THE INVENTION

[0058] As described above, a recovering and refining apparatus for an argon gas and a method for refining an argon gas which realize a low apparatus cost, a stable operation, and a low energy cost have been demanded.

[0059] In refinement of a waste argon gas from a silicon single crystal manufacturing apparatus or the like, the present inventors have paid attention to the point that there is a time lag between amounts of added hydrogen and oxygen and amounts of surplus hydrogen and surplus oxygen flowing from a catalyst tower when the hydrogen and the oxygen are added to the hydrogen, the oxygen, and carbon monoxide in the waste argon gas to cause a catalytic reaction.

[0060] For example, it has been revealed that, in a case where hydrogen concentration on an inlet side of the catalyst tower is constant, when an oxygen flow volume to be added is first maintained constant and then the added oxygen flow volume is suddenly increased to a stoichiometric ratio or more, there is a time lag of several minutes to several tens of minutes after the increase in oxygen flow volume at the inlet until surplus oxygen appears on an outlet side of the catalyst tower.

[0061] Further, it has been also revealed that, in a case where oxygen concentration on the inlet side of the catalyst tower is constant and hydrogen is added, there is likewise a time lag of several minutes to several tens of minutes after starting excessive addition of the hydrogen until the hydrogen appears on the outlet side of the catalyst tower. This leads to a supposition that the catalyst tower has an oxygen and hydrogen retaining function.

[0062] As a result of conducting the earnest examinations to achieve the objects, the present inventors have found out that a metal tower adopted in conventional examples can be eliminated by applying the oxygen and hydrogen retaining function of a catalyst to intermittently add the oxygen and the hydrogen to the catalyst tower, and brought the present invention to completion. That is, the present invention eliminates a metal tower provided, on a post stage of the catalyst tower, which removes the surplus hydrogen or the surplus oxygen, and enables a reduction in equipment cost, energy saving, and a decrease in frequency of occurrence of apparatus failures.

[0063] An embodiment of the present invention will now be described in detail hereinafter with reference to the drawings, but the present invention is not restricted thereto.

[Recovering and Refining Apparatus for Argon Gas]

[0064] A recovering and refining apparatus for an argon gas will now be described hereinafter with reference to FIG. 1 to FIG. 5.

[0065] FIG. 1 is a schematic view showing that oxygen is added to a waste argon gas to cause a catalytic reaction, and it is a view when the oxygen is added or injected on an inlet side of a catalyst tower. The waste argon gas contains at least one of hydrogen, carbon monoxide, and oxygen as an impurity. In this case, when the oxygen is intermittently added or injected, the added oxygen must be sufficiently uniformly mixed in the waste argon gas by the time that it reaches a surface of a catalyst.

[0066] FIG. 2 is a schematic view of oxygen additive flow volumes when the oxygen is intermittently added according to the present invention. The additive flow volume must be an amount which is greatly beyond a stoichiometric ratio and falls below an oxygen retaining amount of the catalyst so that the oxygen does not flow to a downstream side of the catalyst tower. Thus, a relationship between an amount of the catalyst and an oxygen retainable amount of the catalyst must be checked by conducting a test in advance. When the amount of the catalyst is too small, an oxidative reaction becomes insufficient or oxygen addition intervals are too short and unrealistic in some cases, and hence attention is required.

[0067] FIG. 3 is a schematic view showing an image of the oxygen retaining function on a catalyst surface, which is assumed by the present inventors. Since how the oxygen is retained on the catalyst surface is unknown, the retained oxygen is tentatively represented by a symbol O. An amount of the oxygen to be intermittently added or injected must not exceed an amount of the oxygen which can be retained on the catalyst surface. Furthermore, when a hydrogen densitometer and a carbon monoxide densitometer (detecting means) to monitor surplus (unreacted) hydrogen and surplus (unreacted) carbon monoxide which appear on an outlet side of the catalyst tower are installed in the middle of the catalyst tower or when the catalyst towers are installed on two stages and these densitometers are installed between them, it is possible to cope with leakage of a hydrogen component from the catalyst tower or delay times of the densitometers on the outlet side of the catalyst tower.

[0068] FIG. 4 is a schematic view showing an image of a reaction of the oxygen retained on the catalyst surface and the hydrogen and the carbon monoxide in the argon gas when the hydrogen, the carbon monoxide, and the oxygen are contained in the argon gas, which is assumed by the present inventors. The oxygen present in the argon gas in advance is temporarily retained on the catalyst surface. Additionally, like the oxygen already retained on the catalyst surface, it reacts with the hydrogen and the carbon monoxide in the argon gas, and water and carbon dioxide are thereby generated.

[0069] It is to be noted that the description using FIG. 3 and FIG. 4 expresses the assumption of the present inventors to explain a phenomenon which occurs in the catalyst tower in an easy-to-understand manner. Whether this assumption is right or wrong does not affect the effectiveness of the present invention.

[0070] Further, when this state continues, the oxygen retained on the catalyst surface is all consumed by the reaction, the oxygen becomes insufficient, and unreacted hydrogen and unreacted carbon monoxide appear on an outlet side of the catalyst tower. In such a state, the oxygen is again intermittently added or injected so that the oxygen is retained on the catalyst surface. This operation is repeatedly performed.

[0071] FIG. 5 is a schematic view showing an example of a refining flow of the waste argon gas from a silicon single crystal manufacturing apparatus, and a metal tower, which is present in a recovering and refining apparatus for an argon gas according to conventional technologies (FIG. 6 and FIG. 7), on a downstream side of the catalyst tower is not required. In FIG. 5, a part surrounded by a broken line corresponds to the recovering and refining apparatus for the waste argon gas. The waste argon gas discharged from the single-crystal manufacturing apparatus is pressurized to a predetermined pressure by a pressurizing apparatus, and then supplied to the recovering and refining apparatus 10 for the waste argon gas. The recovering and refining apparatus for the waste argon gas according to the present invention has at least one of the catalyst tower where oxygen is added to the argon gas so that the hydrogen and the carbon monoxide contained in the argon gas are converted into the water and the carbon dioxide by the catalytic reaction, and the catalyst tower where hydrogen is added to the argon gas so that the oxygen contained in the argon gas is converted into the water by the catalytic reaction. However, FIG. 5 shows an example where the apparatus has only the catalyst tower where oxygen is added to the hydrogen and the carbon monoxide to convert them into the water and the carbon dioxide.

[0072] The recovering and refining apparatus for the waste argon gas according to the present invention is provided with detecting means for monitoring at least one of the hydrogen, the carbon monoxide, and the oxygen on an outlet side of the catalyst tower. A recovering and refining apparatus 10 for a waste argon gas shown in FIG. 5 is provided with detecting means for the hydrogen and the carbon monoxide.

[0073] Further, the recovering and refining apparatus for the waste argon gas according to the present invention includes at least one of oxygen adding means for adding the oxygen to the argon gas on an inlet side of the catalyst tower when one of the hydrogen and the carbon monoxide is detected on the outlet side of the catalyst tower, and hydrogen adding means for adding the hydrogen to the argon gas on the inlet side of the catalyst tower when the oxygen is detected on the outlet side of the catalyst tower. There is shown an example where the recovering and refining apparatus 10 for the waste argon gas in FIG. 5 includes the oxygen adding means.

[0074] When either the hydrogen or the carbon monoxide is detected by the detecting means, a predetermined large flow volume of the oxygen is immediately added into the catalyst tower for a short time by the oxygen adding means. Consequently, the oxygen is again retained by the catalyst in the catalyst tower.

[0075] As an adsorption tower installed at the rear of this catalyst tower, one which can adsorb and remove the water and the carbon dioxide generated by the catalyst tower, and nitrogen can suffice, and the same adsorption tower as those in conventional examples may be used, or any other type may be used. In the example of the recovering and refining apparatus for an argon gas according to the present invention shown in FIG. 5, like the conventional techniques shown in FIG. 6 and FIG. 7, the water and the carbon dioxide are adsorbed and removed in a first adsorption tower, and the nitrogen is adsorbed in a second adsorption tower. As adsorbents for the water and the carbon dioxide, and the nitrogen, for example, zeolite and mordenite type zeolite are disclosed, respectively, in Patent Literature 1, and these materials can be used.

[0076] The modes described above all correspond to a case where an impurity amount in the waste argon gas stoichiometrically meets (a total amount of the hydrogen and the carbon monoxide)>(an amount of the oxygen), adding the oxygen alone before the catalyst tower can suffice, and this is an example where hydrogen adding means is not provided. According to a result of a test conducted by the present inventors, since a hydrogen retaining function on the catalyst surface is also present like the case of the oxygen, when the impurity amount in the waste argon gas stoichiometrically meets (the total amount of the hydrogen+the carbon monoxide)<(the amount of the oxygen), the gas to be added or injected is changed to the hydrogen, and the same apparatus structure can be adopted. A difference from the recovering and refining apparatus 10 for an argon gas shown in FIG. 5 lies in that the hydrogen adding means is provided in place of the oxygen adding means and the gas to be detected is the oxygen.

[0077] It is to be noted that, in case of using an mole equivalent, it can be said that the oxygen is added by the oxygen adding means when the total amount of the hydrogen and the oxygen monoxide in the waste argon gas exceeds a double of the amount of the oxygen in a mole equivalent ratio, or that the hydrogen is added by the hydrogen adding means when the same is less than the double.

[0078] Furthermore, when concentration of the impurities in the waste argon gas fluctuates with time and the gas to be added must be changed, it is preferable to include both the oxygen adding means and the hydrogen adding means.

[0079] In the recovering and refining apparatus for the waste argon gas according to the present invention, the same amount of the oxygen or the hydrogen, as a stoichiometric amount of the oxygen or the hydrogen which lacks due to the catalytic reaction in the catalyst tower during a time when the oxygen or the hydrogen is not added, is added, and hence the surplus oxygen or hydrogen can be prevented from being produced.

[Refining Method for Argon Gas]

[0080] A method for refining an argon gas using the recovering and refining apparatus for an argon gas shown in FIG. 5 will now be described hereinafter.

[0081] First, in such refinement of the waste argon gas as shown in FIG. 1, in case of converting the hydrogen and the carbon monoxide into the water and the carbon dioxide by additive oxygen with the use of the catalyst tower, the additive oxygen is added or injected excessively for a stoichiometric ratio in a short time (in terms of a peak), and the oxygen is thereby retained in the catalyst tower. On the outlet side of the catalyst tower, the hydrogen and the carbon monoxide are continuously monitored. Then, the hydrogen and the carbon monoxide react with the oxygen held in the catalyst tower and thus the water and the carbon dioxide are generated until the hydrogen or the carbon monoxide appears on the outlet side of the catalyst tower. Moreover, when the hydrogen or the carbon monoxide is detected on the outlet side of the catalyst tower, an operation to inject (add) the oxygen which is excessive for the stoichiometric ratio is again performed. This situation means that the stoichiometric amount of the oxygen is added as a whole by intermittently injecting the excessive oxygen for a short time as shown in FIG. 2, and the refinement of the waste argon gas can be continuously advanced.

[0082] Additionally, when the concentrations of the hydrogen and the carbon monoxide contained in the waste argon gas have changed, intervals of short-time injection alone are changed as a consequence. Namely, time intervals of appearance of the hydrogen and the carbon monoxide on the outlet side of the catalyst tower are shortened when the concentrations of the hydrogen and the carbon monoxide are increased, or the time intervals of appearance of the hydrogen and the carbon monoxide on the outlet side of the catalyst tower are just prolonged when the concentrations are lowered. Therefore, troublesome adjustment concerning an additive amount of the oxygen does not have to be carried out, and automatic control can be simply realized.

[0083] As to the oxygen contained in the waste argon gas, when the addition of the oxygen is changed to the addition of the hydrogen and the appearance of the oxygen is monitored, the same refining method can be applied.

[0084] As described above, in a case where gases to be removed are the hydrogen, the carbon monoxide, and the oxygen, since two types of gases are added, the catalysts must be independently provided on two stages (a catalyst to remove the hydrogen and the carbon monoxide and a catalyst to remove the oxygen) if concentrations of the gases to be removed greatly change. However, in case of the waste argon gas from the normal silicon single crystal manufacturing apparatus, it is often the case that a magnitude correlation of a total amount of the hydrogen and the carbon monoxide and an amount of oxygen is fixed, a smaller amount gas is used by a larger amount gas for the catalytic reaction, and hence installing either the oxygen adding means or the hydrogen adding means can usually suffice.

Examples

[0085] Although the present invention will now be more specifically described hereinafter with reference to examples, but the present invention is not restricted thereto.

Examples

[0086] A waste argon gas from a silicon single crystal manufacturing apparatus (a CZ apparatus) was refined by a recovering and refining apparatus for an argon gas and a method for refining an argon gas according to the present invention (based on the refining flow shown in FIG. 5.).

[0087] Apparatus operating conditions of the recovering and refining apparatus 10 for an argon gas are as described below. [0088] Waste argon gas flow volume: 500 Nm.sup.3/h [0089] Impurity concentrations in the waste argon gas [0090] Hydrogen: 5 to 20 mole ppm [0091] Oxygen: 20 to 30 mole ppm [0092] Carbon monoxide: 60 to 100 mole ppm [0093] Nitrogen: 50 to 100 mole ppm

[0094] It is to be noted that this waste argon gas constantly stoichiometrically met (a total amount of the hydrogen and the carbon monoxide)>(an amount of the oxygen). [0095] Catalyst: Pt catalyst [0096] Added gas: Oxygen (4 NL of oxygen was injected per one intermittent injection)

[0097] An intermittent injection amount of 4 NL was obtained by actually measuring a holding capability of the catalyst in advance.

[0098] Table 1 shows values obtained by converting respective concentrations, i.e., minimum (Min) values, average (Ave) values, and maximum (Max) values of the concentrations of the impurities (the hydrogen, the oxygen, and the carbon monoxide) in the waste argon gas into flow volumes by a calculation, and results of obtaining intermittent addition intervals with the use of these values. Further, impurity flow volumes and intermittent addition intervals when a waste argon gas flow volume is 487 Nm.sup.3/h, hydrogen concentration is 7 mole ppm, oxygen concentration is 23 mole ppm, and oxygen monoxide concentration is 65 mole ppm (Example 1) and when a waste argon gas flow volume is 498 Nm.sup.3/h, hydrogen concentration is 3 mole ppm, oxygen concentration is 27 mole ppm, and oxygen monoxide concentration is 95 mole ppm (Example 2) were also obtained by a calculation, and results are shown in Table 1.

TABLE-US-00001 TABLE 1 Range of operating conditions Examples Unit Min Ave Max Example 1 Example 2 Waste argon Nm3/hr 500 500 500 487 498 gas flow volume Hydrogen Mole 5 10 20 7 3 concentration ppm Oxygen Mole 20 25 30 23 27 concentration ppm Carbon Mole 60 80 100 65 95 monoxide ppm concentration Difference in Mole 25 40 60 26 44 waste argon ppm gas Intermittent NL 4.0 4.0 4.0 4.0 4.0 oxygen injection amount Hydrogen flow NL/min 0.04167 0.08333 0.16667 0.05682 0.02490 volume Oxygen flow NL/min 0.16667 0.20833 0.25000 0.18668 0.22410 volume Carbon NL/min 0.50000 0.66667 0.83333 0.52758 0.78850 monoxide flow volume Intermittent min 38.4 24.0 16.0 37.9 21.9 addition interval Difference NL 0.000 0.000 0.000 0.000 0.000 after catalytic reaction

[0099] The calculated values in Table 1 will now be described with reference to a column of the minimum values (Min) of the concentrations as an example.

[0100] Since the concentration of the hydrogen is 5 mole ppm, the flow volume of the same is 0.04167 NL/min (=500 Nm.sup.3/h5 mole ppm=0.0025 Nm.sup.3/h=0.04167 NL/min).

[0101] Based on the same calculation, the flow volume of the oxygen is 0.16667 NL/min since the concentration of the same is 20 mole ppm, and the flow volume of the carbon monoxide is 0.50000 NL/min since the concentration of the same is 60 mole ppm.

[0102] The difference in waste argon gas shown in Table 1 represents concentrations of gases which remain as a result of the catalytic reaction in the catalytic tower when no gas is added. The hydrogen and the carbon monoxide can be treated in terms of a total amount without being discriminated. The difference in waste argon gas is calculated by the following expression.

Difference in waste argon gas=Hydrogen concentration+Carbon monoxide concentration2Oxygen concentration(6)

In case of the minimum values of the concentration, based on Expression (6), the difference in the waste argon gas is 25 mole ppm (=5+60220).

[0103] Furthermore, the intermittent addition interval shown in Table 1 is calculated by the following expression.

Intermittent addition interval=Intermittent oxygen injection amount{()(Hydrogen flow volume+Carbon monoxide flow volume)Oxygen flow volume} (7)

[0104] In case of the minimum values of the concentrations, based on Expression (7), the intermittent addition interval is 38.4 min (=4{0.5(0.04167+0.50000)0.16667}). The flow volumes of the impurities and the intermittent addition intervals in other cases can be calculated in the same manner.

[0105] In all calculation results shown in Table 1, the difference after the catalytic reaction (a total amount of the surplus hydrogen and carbon monoxide or an amount of the surplus oxygen) is zero.

[0106] In case of the waste argon gas in each of Example 1 and Example 2 shown in Table 1, flow volumes of the impurities obtained by a calculation, an actually measured intermittent addition interval and an actually measured difference after a catalytic reaction when the refinement was performed by using the recovering and refining apparatus 10 for an argon gas according to the present invention shown in FIG. 5 are shown in Table 2. The oxygen is surplus when the difference after the catalytic reaction has a positive sign, and a total amount of the hydrogen and the carbon monoxide is surplus when the same has a negative sign.

TABLE-US-00002 TABLE 2 Unit Example 1 Example 2 Waste argon gas Nm3/hr 487 498 flow volume Hydrogen Mole ppm 7 3 concentration Oxygen Mole ppm 23 27 concentration Carbon monoxide Mole ppm 65 95 concentration Difference in Mole ppm 26 44 waste argon gas Intermittent NL 4.0 4.0 oxygen injection amount Hydrogen flow NL/min 0.05682 0.02500 volume Oxygen flow NL/min 0.18668 0.22500 volume Carbon monoxide NL/min 0.52758 0.79167 flow volume Intermittent min 36.1 23.2 addition interval Difference after NL 0.382 0.507 catalytic reaction

[0107] Next, impurity concentrations in the argon gas after the refinement of the waste argon gas shown in the columns of Example 1 and Example 2 in Table 2 were measured, and results are as described below. [0108] Impurity concentrations in the refined argon gas [0109] Hydrogen<1 mole ppm [0110] Oxygen<1 mole ppm [0111] Carbon monoxide<1 mole ppm [0112] Carbon dioxide<1 mole ppm [0113] Nitrogen<2 mole ppm

[0114] In this manner, the refined argon gas had the purity which is sufficient for reuse in the silicon single crystal manufacturing apparatus.

[0115] As described above, the recovering and refining apparatus for an argon gas and the method for refining an argon gas according to the present invention are configured to recover, refine, and reuse the argon gas as a furnace atmospheric gas in the silicon single crystal manufacturing apparatus (the CZ apparatus or the FZ apparatus), costs of the recovering and refining apparatus can be reduced, the apparatus can be stably operated, and contribution to energy saving can be achieved.

[0116] It is to be noted that the present invention is not restricted to the embodiment. The embodiment is an illustrative example, and any example which has substantially the same configuration and exerts the same functions and effects as the technical concept described in claims of the present invention is included in the technical scope of the present invention.