JP2014062008A - H2se purification - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of purifying HSe by removing HS and HO.SOLUTION: By passing a HSe-containing gas through an AW-500 molecular sieve, the amount of HS in the HSe-containing gas is reduced to less than 10 ppmv. By passing the HSe-containing gas through a 4A molecular sieve, the amount of HO in the HSe-containing gas is reduced to less than 20 ppmv. The HSe-containing gas is passed through the 4A molecular sieve before passed through the AW-500 molecular sieve.

Description

The present invention relates to the purification of H ₂ Se.

Hydrogen selenide (H ₂ Se) is a gas currently used in the solar cell industry for copper indium gallium selenide (CIGS) thin film solar cells and copper indium gallium selenide sulfide (CIGSS) thin film solar cells. Impurities in the H ₂ Se gas can adversely affect the deposition process of the Se-containing film. Two such impurities include H ₂ O and H ₂ S. H ₂ O can provide oxygen to the metal added to the film and prevent proper deposition. H ₂ S may be added in a controlled manner later in the process. However, sulfur is known to change the band gap structure of the selenium-containing adsorbent layer, and therefore impurities such as H ₂ S in H ₂ Se may affect the performance of the film. The combination of H ₂ S and H ₂ O can cause corrosion of the distribution system and its components, resulting in component / system failure and introduction of metal impurities during the deposition process caused by corrosion of the distribution system. Are known.

Prior art gas purifiers are known in the art. For example, Matheson Tri-Gas Nanochem® C / CL series of gas purifiers, Pall Microelectronics Mini Gasklen® gas purifiers, and SAES Pure Gas, Inc. MC-190 and HP-190 MicroTorr. See purification agents. However, none of these purification agents identify H ₂ Se as the gas to be purified and H ₂ O and H ₂ S as impurities to be removed.

Tom et al., US Pat. No. 5,677,028 discloses a process and composition for purifying H ₂ Se and H ₂ Te to remove moisture and oxidant impurities therefrom. Tom et al. Note that H ₂ Se and H ₂ Te are very difficult to purify due to their high reactivity and toxicity (column 1, lines 35-37). Line). Tom et al. Uses aluminum-containing compounds to remove water and oxidants from H ₂ Se or H ₂ Te (Claim 1). Water and oxidants react with the aluminum-containing compound (column 5, lines 25-30). Tom et al. Does not address the removal of H ₂ S from H ₂ Se.

Patent Document 2 of Taiyo Nippon Sanso Corporation discloses a method for producing H ₂ Se having high purity and having a particularly small water content and H ₂ S amount. Taiyo Nippon Sanso Corporation discloses a reaction of high purity H ₂ with metallic Se and liquefies or solidifies the resulting H ₂ Se product. This process requires a large amount of energy for both this reaction and subsequent liquefaction / solidification.

U.S. Pat. No. 4,797,227 JP 2007-246342 A

There remains a need for an efficient method of removing both H ₂ O and H ₂ S from available H ₂ Se feeds.

A method for purifying H ₂ Se-containing gas is disclosed. By passing the H ₂ Se containing gas through an AW-500 molecular sieve, the amount of H ₂ S in the H ₂ Se containing gas is reduced to less than 10 ppmv. The disclosed methods can further include one or more of the following aspects:
The purified H ₂ Se-containing gas contains less than 5 ppmv of H ₂ S;
Reducing the amount of H ₂ O in the H ₂ Se-containing gas to less than 20 ppmv by passing the H ₂ Se-containing gas through a 4A molecular sieve;
The purified H ₂ Se-containing gas contains less than 1 ppm of H ₂ O;
H ₂ Se containing gas is passed through 4A molecular sieve prior to passing through AW-500 molecular sieve; and H ₂ Se containing gas purified to a cylinder cooled to a temperature in the range of approximately −20 ° C. to approximately −60 ° C. Receive.

And passing the H ₂ Se in 4A molecular sieve, by the fact that subsequently pass the _H 2 Se in AW-500 molecular _sieve, a method of purifying the _H 2 Se is disclosed. The disclosed methods can further include one or more of the following aspects:
Purified H ₂ Se contains less than 10 ppmv H ₂ S;
Purified H ₂ Se contains less than 5 ppmv H ₂ S;
Purified H ₂ Se contains less than 20 ppmv H ₂ O;
Purified H ₂ Se contains less than 1 ppm H ₂ O; and receives purified H ₂ Se in a cylinder cooled to a temperature in the range of approximately −20 ° C. to approximately −60 ° C.

  For a further understanding of the nature and objects of the invention, reference should be made to the following detailed description taken together with the accompanying figures.

It is a figure explaining an example refinement | purification container. It is a figure explaining an alternative refinement | purification container. FIG. 2 illustrates an exemplary purification system. It is a figure explaining a 2nd refinement | purification system.

Disclosed is a method for purifying a H ₂ Se containing gas, such as “pure” H ₂ Se gas. Applicants have discovered that the amount of impurities in H ₂ Se may change during use or over time. For example, an H ₂ Se cylinder initially containing 25 ppm H ₂ O contained 600 ppm H ₂ O when the cylinder was almost empty. Of course, these changes will affect the quality of the resulting solar cell product. Thus, H ₂ Se used for CIGS or CIGSS deposition needs to have as high purity as possible.

Because of the reactivity of H ₂ Se and H ₂ Se-containing gases, the disclosed purification methods and any subsequent storage are performed in a system pre-flowed with an inert gas to remove air and moisture. Need to be stored in such a container. Exemplary inert gases include N ₂ , Ar, He, and combinations thereof. In the following example, N ₂ was used. The stainless steel component of the purification system shall undergo complete electropolishing and drying.

In order to prevent further impurity formation in the purified H ₂ Se gas, this gas needs to be stored in a cylinder with a surface on which H ₂ Se does not react. Suitable surfaces are steel, carbon steel with Ni coating, aluminum, stainless steel, glass, quartz, nylon, metal alloy sold under the trademark Monel®, trademark Hastelloy
Metal alloy sold under (registered trademark), fluorine-containing resin sold under the trademark Teflon (registered trademark), synthetic rubber sold under the trademark Kalrez (registered trademark), sold under the trademark Viton (registered trademark) Synthetic rubbers and / or glassware sold under the trademark Pyrex®. Preferably, the purified H ₂ Se is stored in a cylinder made from carbon steel with aluminum or Ni coating.

H ₂ Se-containing gas is commercially available. H ₂ Se, the reaction at elevated temperatures of _{H 2} and molten _{Se [H 2 (g) +} Se ( _{melted) → H 2 Se (g)} ] is most often produced in. This reaction comprises approximately 95% (v / v) to approximately 99.9% (v / v) H ₂ Se, typically approximately 99.5% (v / v) to approximately 99.99% An H ₂ Se-containing gas containing (v / v) H ₂ Se is generated. Impurities H ₂ S in the H ₂ Se-containing gas are produced from sulfur impurities in the selenium used to produce this gas. Although low sulfur selenium is commercially available, removing enough sulfur to be low H ₂ S in a H ₂ Se containing gas is very expensive.

That Applicants have surprisingly _and is flowing through the _H 2 Se-containing gas in the AW-500 molecular _{sieve, H 2} S in _H 2 Se-containing gas has been found to be adsorbed by the AW-500. The result is that was not expected, because, in various molecular sieve having the same pore size as the AW-500 molecular sieve, H _{2 O} or H _{2 S} from the H 2 _{Se-containing} gas is for not removed.

H ₂ Se has a critical diameter of approximately 4 angstroms (146 pm). The critical diameter is the approximate molecular diameter of the molecule. H ₂ S has a critical diameter of 3.6 angstroms (134 pm). H ₂ O has a critical diameter of 3.2 angstroms (95 pm). Based on these sizes, those skilled in the art would expect that having a pore size of approximately 4 angstroms would be the best molecular sieve that captures H ₂ O and H ₂ S without capturing H ₂ Se. I will. However, although AW-500 molecular sieve has a pore size of 5 Angstroms, it is still effectively H ₂ Se, even though both H ₂ Se and H ₂ S molecules are smaller than the pore size of AW-500 molecular sieve. Remove H ₂ S (3.6 Å / 134 pm) from (4 Å / 146 pm). In addition, the polarities of the three molecules are similar (H ₂ Se (0.59D), H ₂ S (0.97D) and H ₂ O (1.85D)), making separation by adsorption techniques difficult. (D = Debye. 1 coulomb meter = 2.999 × 10 ²⁹ D).

The H ₂ Se-containing gas contacts the AW-500 molecular sieve by flowing through the container of the AW-500 molecular sieve. AW-500 molecular sieve is commercially available. Currently, AW-500 is supplied as 1/16 "(inch) or 1/8" (inch) pellets. Any size can be used in the disclosed method. The AW-500 molecular sieve can be placed in a container made from stainless steel. Alternatively, the AW-500 molecular sieves, aluminum, can be placed in a container made from SiH ₄ by passivated stainless steel, or nickel-plated carbon steel. The container shall have an inlet and an outlet. In an alternative represented in FIG. 1A, the inlet 10 and outlet 20 are located at the opposite ends of the container 1 to minimize dead flow zones in the molecular sieve. The arrows in FIG. 1A represent the direction of gas flow through the container 1. However, an alternative, for example, where the inlet 10 is located at one end of the cylindrical container 1 and the outlet 20 is located at the cylindrical surface of the container 1 at the other end of the container 1 It may be desirable to have a common inlet and outlet location. Those skilled in the art will recognize that the shape of the container 1 is not limited to cylinders, but may include spheres, cubes or other polyhedric shapes.

Commercially available AW-500 molecular sieve is provided in its activated state by the manufacturer. However, Applicants have to remove any contaminants that may have been adsorbed during transportation from the manufacturer, from its original container to the purification container, or from the purification container itself. Reactivate the AW-500 molecular sieve before use. Applicants activate the AW-500 molecular sieve by heating the AW-500 molecular sieve to a temperature in the range of about 150 ° C. to about 250 ° C. under inert gas for about 10 hours to about 24 hours. . Inert _gas, N _{2, Ar, He,} or a combination thereof. One skilled in the art will determine the activation time and activation temperature depending on the amount of molecular sieve that is activated, with higher amounts requiring longer or higher temperatures and smaller amounts for shorter times or It will be appreciated that lower temperatures will be required. AW-500 can be activated by heating to as high as 600 ° C. However, heating the AW-500 to such temperatures would require the remaining components in the purification system, such as valves, and would be more expensive. This is because these components are believed to be designed to withstand exposure to such temperatures. As a result, activation at temperatures below 300 ° C. allows the use of less expensive valves in the purification system.

The initial reaction between the H ₂ Se-containing gas and AW-500 molecular sieve, CO ₂ is generated. Therefore, after activation of the AW-500 molecular sieve, the initial H ₂ Se-containing gas flowing through the AW-500 molecular sieve is vented. Applicants calculate the time required to reduce the CO ₂ level caused by the initial contact between the H ₂ Se-containing gas and the AW-500 molecular sieve in relation to the amount of molecular sieve. Not. However, the initial reaction raises the temperature of the AW-500 molecular sieve. In order to produce high purity (ie low CO ₂ content) H ₂ Se gas, Applicants return the temperature of the AW-500 molecular sieve to room temperature (approximately 15 ° C. to approximately 30 ° C.). Until then, H ₂ Se gas was passed through the AW-500 molecular sieve. For approximately 10 kg of AW-500 molecular sieve and H ₂ Se containing gas at a flow rate of approximately 100 cc / min to approximately 1000 cc / min, the average time to reach room temperature was approximately 2 hours. The purified H ₂ Se gas contained approximately less than 3 ppm CO ₂ . One skilled in the art will recognize that longer or shorter vent periods may be required due to differences in the amount of AW-500. In addition, those skilled in the art may find that higher concentrations of CO ₂ may be acceptable for some H ₂ Se applications, resulting in the disclosed purification process requiring little or no vent time. You will recognize that you may not.

In order to reduce the amount of _{H 2} S in H ₂ Se-containing _gas, the _H 2 Se-containing gas to flow through the AW-500 molecular sieve prepared according to the above paragraph. The H ₂ Se-containing gas shall remain in contact with the AW-500 molecular sieve for approximately 0.5 seconds to approximately 100 seconds, preferably approximately 2 seconds to approximately 40 seconds. This process may be performed at room temperature (approximately 15 ° C. to approximately 30 ° C.). Alternatively, the process may be performed at a temperature in the range of approximately 0 ° C to approximately 35 ° C. However, as shown in the following example, more H ₂ S is adsorbed on the AW-500 molecular sieve in the room temperature process than in the lower temperature process.

Resulting _H 2 Se-containing gas, _H 2 S of less than 10 ppmv, preferably has a _{H 2} S of less than 5 ppmv, about 99.995% of (v / v) ~ about 99.999% (v / v) Contains H ₂ Se.

Water (H ₂ O) is also preferably removed from the H ₂ Se-containing gas. The presence of moisture can contribute to corrosion of piping and gas distribution systems, even at very low concentrations. H
₂ O can be removed by passing H ₂ Se-containing gas through a 4A molecular sieve. 4A molecular sieve is commercially available. Currently, 4A molecular sieves are supplied as 14 × 30 granules, 10 × 20 beads, 8 × 12 beads, 4 × 8 beads, 1/16 ″ pellets, and 1/8 ″ pellets. Any of these sizes can be used in the disclosed method. Similar to the AW-500 molecular sieve, the 4A molecular sieve can be stored in a stainless steel container. Alternatively, 4A molecular sieves can be placed in containers made from aluminum, SiH ₄ passivated stainless steel, or nickel plated carbon steel. Similar to the container for AW-500 molecular sieve, the container for 4A molecular sieve shall have an inlet and an outlet. In an alternative represented in FIG. 1A, the inlet 10 and outlet 20 are located at the opposite ends of the container 1 to minimize dead flow zones in the molecular sieve. The arrows in FIG. 1A represent the direction of gas flow through the container 1. However, for example, as shown in FIG. 1B, the inlet 10 is located at one end of the cylindrical container 1, and the outlet 20 is the cylindrical surface of the container 1 at the other end of the container 1. In some cases, alternative inlet and outlet locations are desirable, such as Those skilled in the art will recognize that the shape of the container 1 is not limited to cylinders, but may include spheres, cubes or other polyhedral shapes.

Prior to use, the 4A molecular sieve is activated by heating the 4A molecular sieve under inert gas to a temperature in the range of about 150 ° C to about 250 ° C for about 10 hours to about 24 hours. Inert _gas, N _{2, Ar, He,} or a combination thereof. N ₂ is adsorbed on 4A molecular sieves at these temperatures. Therefore, in order to produce purified H ₂ Se gas with a low amount of N ₂ , a ° C He purge should be performed after activation of 4A molecular sieves under N ₂ atmosphere. For every 500 g of 4A molecular sieve, the flow rate of the inert gas is proportional to approximately 100 cc / min (ie, 500 g = 100 cc / min, 1 kg = 200 cc / min, etc.). After approximately 8 hours of He purge, purification of the H ₂ Se containing gas can begin. One skilled in the art will recognize that longer or shorter activation periods may be required depending on the amount of 4A.

In order to reduce the amount of of H _{2 O} H 2 _{Se-containing} gas, the H 2 _{Se-containing} gas, is passed through a 4A molecular sieve prepared according to the above paragraph. The H ₂ Se-containing gas shall remain in contact with the 4A molecular sieve for approximately 0.5 seconds to approximately 100 seconds, preferably approximately 2 seconds to approximately 40 seconds. This process may be performed at room temperature (approximately 15 ° C. to approximately 30 ° C.). Alternatively, the process may be performed at a temperature in the range of approximately 0 ° C to approximately 35 ° C.

Resulting _H 2 Se-containing gas is, of _H 2 O less than 20 ppmv, preferably having of _{H 2} O of less than 1 ppmv, about 99.995% of (v / v) ~ about 99.999% (v / v) Contains H ₂ Se.

The water removal step using 4A molecular sieve may be performed before or after the H ₂ S removal step using AW-500 molecular sieve. When the water removal step is performed after the H ₂ S removal step, Applicants believe that 4A molecular sieve helps to reduce the CO ₂ produced by the reaction of H ₂ Se and AW-500 molecular sieve. ing. When performing the H ₂ S removal step after water removal, Applicants have reduced the water content in the H ₂ Se-containing gas, resulting in a reaction between H ₂ Se and AW-500 molecular sieves. We believe that little or no CO ₂ will be lost. In another alternative, to store both the AW-500 molecular sieve and 4A molecular sieves in the same _container, H 2 S, it is possible to simultaneously remove the _{H 2} O and CO _2.

After purification, the purified gas can be transferred to a suitable cylinder at a temperature in the range of approximately −20 ° C. to approximately −60 ° C. In order to prevent the cylinder from being overfilled with H ₂ Se, the cylinder may be located on the meter.

One exemplary purification system is depicted in FIG. H ₂ Se containing gas is contained in a cylinder labeled H ₂ Se (source). Open the cylinder valve (not shown) and valve V1 to remove H ₂ O or H ₂ S from the H ₂ Se containing gas in a container-1 containing one of the disclosed molecular sieves with H ₂ Let the Se-containing gas flow in. The pressure sensor P1 displays the pressure of the H ₂ Se supply cylinder. The pressure sensor P1 can be a pressure gauge or a pressure transducer. The valve V2 is opened, and the H ₂ Se-containing gas is caused to flow into the container-2 containing a molecular sieve different from that contained in the container-1. For example, when container-1 contains AW-500, container-2 contains 4A. Alternatively, if container-1 contains 4A, container-2 contains AW-500. In another alternative, both container-1 and container-2 may contain both AW-500 and 4A. Thereafter (when the cylinder valve (not shown) opens), the purified H ₂ Se flows through the valve V3 and enters the cylinder labeled H ₂ Se (after purification). Pressure sensor P2 is believed to indicate any unexpected drop in pressure on Container-1 or Container-2. Pressure sensor P2 also indicates that H ₂ Se gas is flowing into the H ₂ Se purified product cylinder. The pressure sensor P2 can also be a pressure gauge or a pressure transducer. When inspection of the container-1 is necessary, the valve V1 and the valve V2 can be closed. When inspection of the container-2 is necessary, the valve V2 and the valve V3 can be closed.

A second exemplary purification system is depicted in FIG. H ₂ Se containing gas is contained in a cylinder labeled H ₂ Se (source). Valve V9 is removed from the entire system by circulating between (a) pressurization of purge gas (eg, N ₂ , He, Ar, or other inert gas) and (b) generation of vacuum in the system. Use to properly purge any contaminants. It is believed that purge / vacuum circulation is used to maintain the purity of the H ₂ Se purification system whenever a source or product cylinder is connected to or disconnected from the system. This procedure will also prevent any H ₂ Se from being expelled from the system, exposing workers, and preventing air and other impurities from entering the system.

Close all valves before operating the purification system. Open the valve (not shown) of the H ₂ Se source cylinder, and then open valve V1, valve V2, valve V4, valve V5, valve V6, valve V7 and valve V8. Container 1 may contain molecular sieve 4A, and container 2 may contain molecular sieve AW-500. Alternatively, container 1 may contain molecular sieve AW-500 and container 2 may contain molecular sieve 4A. In another alternative, both container 1 and container 2 may include both molecular sieve AW-500 and molecular sieve 4A. The pressure sensor P1 displays the pressure of the H ₂ Se supply cylinder. The filter 1 and the filter 2 are used to prevent fine particles from being discharged from the container 1 and the container 2 and entering the cylinder of the purified H ₂ Se product. The pressure sensor P2 is believed to indicate any unexpected drop in pressure on the container 1, container 2, filter 1 or filter 2. The pressure sensor P2 also indicates that H ₂ Se gas is flowing into the H ₂ Se product cylinder.

Use V10, to H 2 _Se to determine whether it has the appropriate qualities to fill in H ₂ Se product cylinder, can be to the analytical instrument sends the H ₂ Se sample. If the quality of H ₂ Se is at the required level, a cooling means with a thermocouple TC is used on the H ₂ Se product cylinder to reduce the cylinder pressure and the pressure between the source cylinder and the product cylinder. The difference can be maintained. Suitable cooling means include liquid baths capable of cooling the H ₂ Se product cylinder to temperatures as low as −60 ° C., such as liquid nitrogen, dry ice, acetone, isopropanol, and other known heat transfer liquids. Is mentioned. The cooling means and TC act as a temperature controller that cools the product cylinder. _Thus, the pressure difference which allows the flow of _H 2 Se to _H 2 Se products from _H 2 Se source occurs. Opening a H ₂ Se product cylinder valve (not shown), high purity _H 2 Se _is, it will flow from the _H 2 Se source cylinder to the _H 2 Se product cylinder. The meter 1 may display the amount of product discharged from the H ₂ Se source cylinder, and the meter 2 will display the amount of product filled in the H ₂ Se product cylinder. If inspection of the purification agent 1 and / or the filter 1 is necessary, the valve V4 and the valve V5 can be closed. If inspection of the purification agent 2 and / or the filter 2 is necessary, the valve V6 and the valve V7 can be closed. Filter 3 is the last filter used to keep particles out of the H ₂ Se product. If purification of the H ₂ Se source is not required, valve V2 and valve V8 can be closed and valve V1 and valve V3 can be opened.

  The following non-limiting examples are presented to further illustrate embodiments of the present invention. However, this example is not intended to be all-inclusive and is not intended to limit the scope of the invention described herein.

Example 1
The following series of molecular sieves and catalysts were screened.

Level of _{H 2} O loading and _{H 2} S loading in the _table, the amount of _{H 2} O and _{H 2} S which is present in the _H 2 Se source (unit: ppmv) represents a. The H ₂ O removal and H ₂ S removal columns indicate the percent (v / v) of each removed from H ₂ Se.

Analysis of H ₂ O loading and H ₂ O removal was performed by Meeco's Aquavolt + equipped with a P ₂ O ₅ electrolyte H ₂ O analyzer. However, Se was deposited on the P ₂ O ₅ electrolyte. In addition, the response time was very slow. As a result, H ₂ O analysis was not performed in all of the tests in the table above. Further H ₂ O analysis was performed using a HALO H ₂ O analyzer.

Analysis of H ₂ S loading and H ₂ S removal was performed by GC HP 5890 / PDHID. A Restek GC column capable of detecting N ₂ , O ₂ , CO ₂ , CH ₄ and H ₂ S in the H ₂ Se containing gas was utilized. The GC was calibrated using gas standards containing 30 ppm and 100 ppm of each of these impurities. The detection limit was about 0.1 ppm (3 × S / N).

In addition to measuring the removal of impurities H ₂ S and H ₂ O, the generation of other impurities upon contact with H ₂ Se was analyzed.

ZnO successfully removed H ₂ S, but appeared to produce other impurities that have not yet been identified.

Molecular sieve 5A did not remove H ₂ O or H ₂ S. This may be a result of H ₂ Se adsorption in 5 angstrom pores.

AW-500 is to remove _{H 2} S while releasing some degree of CO _2. Surprisingly, AW-500, despite having a pore size of the same 5 angstroms as molecular sieve 5A, AW-500 was removed _{H 2} S from the _H 2 Se. Capacity of AW-500 molecular sieves for _{H 2} S in H ₂ Se were found to exceed _1% (g H 2 S / g AW -500).

The capacity of 4A molecular sieve relative to H ₂ O in H ₂ Se was found to be 2.4% (g H ₂ O / g 4A).

Example 2
One container containing a 4A molecular sieve, 72 ° F, particularly used for removing _{H 2} O from about 110 psig _H 2 Se. Containing AW-500 molecular sieve, a second container was first container series, 72 ° F, was used from about 110 psig _H 2 Se in order to remove the _{H 2} S. An analytical facility capable of measuring both H ₂ S concentration and H ₂ O concentration in H ₂ Se was positioned downstream of the vessel. The measured value of the level of H ₂ O in H ₂ Se was less than 1 ppm, and the measured value of the level of H ₂ S in H ₂ Se was less than 5 ppm. At these levels, the possibility of reaction with H ₂ O or H ₂ Se in the process is very low.

  Many further modifications in the details, materials, processes, and arrangements of components described and illustrated herein to illustrate the nature of the invention will be described in the appended claims. It is understood that those skilled in the art can do within the principles and scope. Accordingly, the present invention is not intended to be limited to the specific embodiments in the examples and / or the accompanying drawings listed above.

Claims (13)

A method of purifying a H ₂ Se-containing gas to reduce the _H 2 Se-containing gas by passing the AW-500 molecular sieve, the amount of _{H 2} S in the _H 2 Se-containing gas to below 10ppmv A method for purifying an H ₂ Se-containing gas. The method of claim 1, wherein the purified H ₂ Se-containing gas contains less than 5 ppmv H ₂ S. The method of claim 1, further comprising reducing the amount of H ₂ O in the H ₂ Se-containing gas to less than 20 ppmv by passing the H ₂ Se-containing gas through a 4A molecular sieve. _H 2 Se-containing gas the purified contains of _{H 2} O of less than 1 ppm, The method according to claim 3. Wherein the H ₂ Se-containing gas is passed through the 4A molecular sieve prior to passing to the AW-500 molecular sieve, the method according to claim 3. The method of claim 1, further comprising receiving the purified H ₂ Se-containing gas in a cylinder cooled to a temperature in the range of approximately −20 ° C. to approximately −60 ° C. To a temperature in the range of about -20 ° C. ~ about -60 ° C. further comprises receiving the H ₂ Se-containing gas the purified cooled cylinders, the method according to claim 3. A method for purifying H ₂ Se, comprising:
Passing H ₂ Se through a 4A molecular sieve;
A method for purifying H ₂ Se, comprising subsequently passing H ₂ Se through an AW-500 molecular sieve. The purified _H 2 Se contains _{H 2} S of less than 10 ppmv, The method of claim 8. The method of claim 9, wherein the purified H ₂ Se contains less than 5 ppmv H ₂ S. The purified _H 2 Se contains of _{H 2} O of less than 20 ppmv, The method of claim 8. The method of claim 11, wherein the purified H ₂ Se contains less than 1 ppm of H ₂ O. The method of claim 8, further comprising receiving the purified H ₂ Se in a cylinder cooled to a temperature in the range of approximately −20 ° C. to approximately −60 ° C.