KR101078118B1 - Adsorbent for Producing Ultra-pure Inert Gas - Google Patents

Abstract

The present invention relates to an adsorbent for preparing ultra-high purity inert gas, which includes activated carbon, alumina, synthetic zeolite, natural zeolite, sodium silicate, sodium metasilicate, sodium aluminate, zirconia, titania, talc, silica, inorganic oxide layered compounds, and mixtures thereof. Supporting a certain amount of nickel in the solid carrier, by using at least one compound selected from alkali metals or alkaline earth metal, and coprecipitation in the preparation of the adsorbent to ensure high dispersion of the main active ingredient in the solid carrier, An object of the present invention is to improve the adsorption performance of trace impurities contained, in particular, O ₂ , CO, CO ₂ , H ₂ O, and the like, in comparison with conventional adsorbents.

Solid carrier, nickel, alkali metal, alkaline earth metal, precipitant, high purity inert gas, adsorbent

Description

Adsorbent for Producing Ultra-pure Inert Gas

The present invention relates to an adsorbent for preparing ultra-high purity inert gas, and includes activated carbon, alumina, synthetic zeolite, natural zeolite, sodium silicate, sodium methsilicate, sodium aluminate, zirconia, titania, talc, silica, inorganic oxide layered compounds and their Inert gas by supporting a certain amount of nickel in the mixture solid carrier, additionally using at least one compound selected from alkali metals or alkaline earth metals, and coprecipitation in the preparation of the adsorbent to ensure high dispersion of the main active ingredient in the solid carrier. An object of the present invention is to improve the adsorption performance of trace impurities, especially O ₂ , CO, CO ₂ , H ₂ O and the like, in comparison with conventional adsorbents.

There are several ways to selectively remove certain gases, usually using adsorbents and catalysts.

In order to remove specific gas components at low temperature, it is preferable to use an adsorbent. As the adsorbent, carriers such as activated carbon, zeolite, and layered compounds are commonly used. However, these alone have a limit in the adsorption capacity, the adsorption capacity is reduced or extinguished after a certain time, and also has a disadvantage of one-time because it is not easy to reuse. In order to overcome these disadvantages, various studies have been made on improving the adsorption capacity of a specific gas by administering a certain amount of the active ingredient to a solid carrier, and various examples of regeneration / reuse of the used adsorbent are known.

On the other hand, when using a catalyst has the advantage that can be recycled by introducing a number of active metal to the carrier can be recycled several times, there is a problem that the core technology development is not easy. In order to remove a specific gas using a catalyst, it is necessary to heat it to a temperature of at least 150 ° C. or more, and it is not easy to perform a catalytic reaction at room temperature.

Ultra-high purity gas is an essential material that is directly related to the quality of electronic semiconductor products, and as the demand of high-purity gas for semiconductor manufacturing increases with the development of the electronic industry, it is focusing on gas purity management. Because it is very sensitive to the material (catalyst / adsorbent) and the reaction conditions depending on the concentration, etc., it will be possible to develop the desired technology only by the highly difficult technology.

Inert gases such as nitrogen, argon and helium, which are widely used in the semiconductor manufacturing industry, contain impurities such as ppm, oxygen, carbon monoxide, methane, water vapor and hydrogen, which can reduce their concentration to ppb levels or below. There is an active research on the development of materials.

 Currently, high purity gas is manufactured by applying process technology based on molecular sieve, metal supported catalyst and getter material technology to manufacture high purity inert gas. ① Gas purity (1.0ppb or less), ② Material durability, The core technologies are the molding technology of materials and the recycling / reuse technologies of materials.

As described above, the published literature on the development of an adsorbent that can effectively reduce the concentration of trace impurities contained in an inert gas is as follows.

Japanese Patent JP 1996-217422 relates to "Method and Apparatus for Manufacturing High Purity Nitrogen Gas," which is a high-purity nitrogen gas in which impurities such as O ₂ , CO, CO ₂ , hydrocarbon, H _2, and water vapor are reduced to 1 ppb or less. It is an object of the present invention to provide a method and apparatus for manufacturing the same, which are manufactured through the following four steps.

That is, (A) PSA method is used to convert air into nitrogen containing 1000 ppm of oxygen using carbon having a pore size of 3 kPa, and (B) the reaction temperature is 250 to 400 ° C. using Pd (2wt%) / alumina. Hydrogen is oxidized in carbon monoxide, hydrocarbon, oxygen at 1000ppm atmosphere and converted to carbon dioxide and water. (C) Adsorption and removal of carbon dioxide and water at below 60 ℃ using Ni (60wt%) / silica-alumina. The hydrogen released in the process (C) by (2 wt%) / alumina is removed at 40 ° C. or lower.

However, the material (catalyst and adsorbent) and the method of removing impurities presented in the cited invention are different from the present invention. In addition, the method proposed in the cited invention is a multi-stage process, and there is an uneconomic problem because the materials used in each step are also various.

U.S. Patent (US 5902561) “Low temperature inert gas purifier” impurity O ₂ , CO, CO ₂ , CH ₄ , H ₂ and 99.999% nitrogen or argon gas contained at 0 to 60 ° C. using a two-stage catalyst process. Removes water (impurity concentration: maximum 10ppm), below 1ppb, using Ni / alumina and / or silica in the first stage and getter alloy in the second stage (Zr (80%): Fe (18%) : Sn (2%)) is used to remove the total impurities below 1ppb. If excess carbon dioxide and water are present, first remove them using molecular sieve.

However, there is no description of the preparation method for the nickel-containing catalyst presented in the cited invention, the difference from the present invention is not known.

U.S. Patent (US 4713224) discloses CO, CO using a getter alloy and molecular sieve consisting of 5 wt% Ni-supported porous material (alumina-silica), Zr (80%): Fe (18%): Sn (2%) ₂ , O ₂ , H ₂ , H ₂ O, etc. can be removed up to 0.1 ~ 1.0ppm, CH ₄ can not be removed, the high purity gas for the semiconductor industry that the concentration should be 1.0ppb or less after reducing impurities Does not meet the specifications.

In US Patent (US 5536302) “Adsorbent for removal of trace oxygen from inert gases” is a catalyst / adsorbent (CsO, K / activated carbon or Ni / Al ₂ O _3, etc.) in which an inexpensive oxide, alkali or alkaline earth metal is supported on a reduced support. ) Is used to reduce oxygen (concentration of 10ppm level) as an impurity to ppb level.

In the US patent (US 5110569) “Low temperature purification of gases”, we developed a technique that uses adsorbents and catalysts and removes CO, H ₂ O, CO ₂ , H ₂ below 1ppm through PSA and TSA technologies. The material (adsorbent / catalyst) uses activated alumina, hopcallite (mixture of CuO and MnO), nickel oxide, Pd / alumina, etc., which is different from the material proposed in the present invention.

The Korean patent (Patent No. 10-2005-00230327) developed the "nitrogen gas purification device and its purification method". The high-purity nitrogen gas produced from the air separation device was separated into three purification layers, activated alumina, Ni (50-60wt %) / Silica and zeolite were used to remove various impurities such as O ₂ , CO ₂ , H ₂ , H ₂ O below 5ppb, but there are no specific references to catalysts and adsorbents. The difference with the adsorbent developed in the invention can not be found, and in the present invention, even if one material is used, impurities can be removed at a concentration of 1.0 ppb or less, which is superior to the material of the present invention.

Korea Patent (Patent No. 10-2005-0019092) “Preparation of high purity and ultra-high purity gas” removes trace amounts of CO and H ₂ , H ₂ O, CO ₂ , CH ₄ from air by adsorptive separation and catalyst zeolite (a, X, Y, MOR , SiO 2 / Al 2 O 3 = less than 20) were presented to describe, in particular, techniques for removal of CO, H ₂ selective, Ag +, Au + to CO and H ₂ removal In order to remove H ₂ O, activated alumina, zeolite and 13X zeolite were used to remove CO ₂ , which is different from the material proposed in the present invention.

U.S. Patent (US6511640 B1) relates to the "Purification of gases", which is based on the temperature swing adsorption process to reduce the concentration of impurity components (CO, CO ₂ , moisture, H ₂ ) contained in the air. _It is composed of a catalyst oxidized to ₂ (Pd catalyst), and an adsorbent for removing water and CO ₂ (active alumina, silica gel, zeolite), which is fundamentally different from the impurity removal method and composition of the adsorbent proposed in the present invention.

Japanese Patent Application Laid-Open No. 2006-21935 relates to a method for producing a highly purified gas, which provides a method for removing CO in the presence of water, wherein the copper salt is contained in at least one carrier selected from alumina, silica, zeolite and activated carbon. It introduces a technique for reducing CO in the presence of water by using a CO adsorbent carrying a carbon dioxide and a CO oxidation catalyst loaded with a manganese catalyst on at least one carrier selected from alumina, silica, zeolite and activated carbon. However, the material applied in this technique and the adsorbent of the present invention are fundamentally different.

Republic of Korea Patent (Publication No. 10-2005-0030327) relates to a "nitrogen gas purification device and its purification method", in the patent using a 50-60% by weight of nickel supported on the silica carrier O ₂ , CO, H ₂ Although the concentration of is reduced to 5ppb or less, and the concentration of water vapor is reduced to 5ppb or less by using zeolite, there is no detailed description of the manufacturing method of the material and the performance of removing impurities. This is not only different in the composition of the adsorbent developed in the present invention, but also the performance of the adsorbent is far superior to that of the cited invention.

Therefore, it is easy to manufacture in removing trace impurities (O ₂ , CO, CO ₂ , H ₂ O, etc.) contained in inert gas such as nitrogen, helium, argon, etc., and the concentration of impurities is 1.0 ppb The development of the material which can reduce to the following levels and can maintain activity for a long time is calculated | required continuously.

Accordingly, the present inventors have deeply studied the performance and cost-effectiveness of the conventional adsorbent, and in order to develop a new solid state adsorbent having excellent adsorption capacity for a small amount of impurities contained in an inert gas, particularly O ₂ , CO, CO ₂ , H ₂ O and the like. Research effort.

As a result, a certain amount of nickel is supported on porous alumina, silica, sodium metasilicate, sodium silicate, sodium aluminate, zeolite, talc and mixtures thereof, and an additional one or more compounds selected from alkali metals or alkaline earth metals are used. By using coprecipitation and dispersant in the manufacturing process, the main active ingredient can be highly dispersed in the solid carrier, improving the adsorption performance and adsorption holding capacity for trace impurities, especially O ₂ , CO, CO ₂ , H ₂ O It was found that the performance is significantly improved compared to the prior art to complete the present invention.

Accordingly, an object of the present invention is to provide a method for preparing an adsorbent for removing trace impurities (O ₂ , CO, CO ₂ , H ₂ O, etc.) contained in an inert gas having improved adsorption power, adsorption holding power and economic efficiency. have.

The present invention provides a trace amount of impurities (O ₂₎ contained in an inert gas formed by simultaneously carrying one or more compounds selected from nickel (Ni) metal as a main active ingredient and alkali metal or alkaline earth metal as an auxiliary active ingredient in a porous solid carrier. , CO, CO ₂ , H ₂ O, etc.) is characterized by the adsorbent for removal.

That is, a certain amount of active metal salt (nickel, alkali metal or alkaline earth metal) is dissolved in water of at least 70 ° C. in a porous solid carrier, and then a certain amount of coprecipitation agent such as urea, hydrazine, citric acid, etc. is mixed and aged for a sufficient time. To obtain a mixed metal precipitate.

In addition, the adsorbent of the present invention was prepared by washing / filtering / drying the mixed precipitate, and then calcining and pretreatment in a hydrogen atmosphere.

As described above, the adsorbent prepared according to the present invention has excellent fast adsorption performance and excellent retention of adsorption property, and thus includes oxygen, carbon monoxide, methane, and water vapor contained in inert gases such as nitrogen, argon, and helium, which are widely used in the semiconductor manufacturing industry. Hydrogen or the like can be used as a material capable of reducing the concentration of impurities to a level of 1.0 ppb or less.

Hereinafter, the present invention will be described in detail.

The present invention is a novel adsorbent for removing impurities such as traces of O ₂ , CO, CO ₂ , H ₂ O contained in an inert gas at room temperature, the main active ingredient of a specific metal component in a porous solid carrier, a specific auxiliary activity The present invention relates to an adsorbent for removing trace amounts of impurities (O ₂ , CO, CO ₂ , H ₂ O, etc.) contained in an inert gas by simultaneously carrying the components.

That is, a certain amount of active metal salt is supported on the porous solid carrier, and the active metal salt is made of nickel, alkali metal or alkaline earth metal.

The adsorbent for removing trace impurities (O ₂ , CO, CO ₂ , H ₂ O, etc.) contained in the inert gas according to the present invention will be described in more detail.

The porous carrier is generally used in the manufacture of adsorbents in the art, but is not particularly limited, and specifically, for example, activated carbon, alumina, synthetic zeolite, natural zeolite, zirconia, titania, talc, silica, sodium metasilicate, silicic acid Sodium, sodium aluminate, inorganic oxide layered compounds and mixtures thereof may be used.

In the present invention, (1) a specific main active ingredient and auxiliary active ingredient are mixed and used as the active ingredient supported on the porous solid carrier, (2) the main active ingredient and the precipitant are used in a certain component ratio when preparing the adsorbent, and (3 Specific post-treatment features to optimize the activity of the manufactured adsorbents.

The main active ingredient is nickel (Ni) which can easily adsorb / remove the impurity gas existing in the inert gas, among metal components generally used in the art.

As the auxiliary active ingredient, the main active ingredient can be highly dispersed in the solid carrier, and thus the adsorption performance can be improved. Among the water-soluble alkali metal salts or water-soluble alkaline earth metal salts exhibiting synergistic effects with the main active ingredient, One or more compounds selected are selected and used.

The molar ratio of the auxiliary active ingredient to the main active ingredient is maintained in the range of 0.5 to 5.0, and when the content of the auxiliary active ingredient is out of the range, there is a problem in that the adsorption capacity is low.

Such active ingredients are supported by 30.0 to 70.0% by weight with respect to the final adsorbent. If the supported amount is less than 30.0% by weight, the adsorption capacity is low and when the content exceeds 70.0% by weight, the technique of high dispersion of the active ingredient is not only easy. Economical and consequently affect the adsorption capacity.

Meanwhile, a method of preparing a new adsorbent for removing impurities such as trace amounts of O ₂ , CO, CO ₂ , and H ₂ O contained in an inert gas according to the present invention at room temperature will be described in detail.

First, impurities, dust and the like present in the solid carrier are removed. This is not particularly limited to conventional methods, but in the present invention, the solid carrier is washed with distilled water once or twice and dried for about 24 hours at a temperature of 100 to 120 ° C., or about 4 to 5 hours at a temperature of 300 to 400 ° C. Fires.

Next, the main active metal raw material and the auxiliary active metal raw material are dissolved in water having a weight of 50 to 100 times higher than that of the solid carrier, and then a predetermined amount of precipitant is mixed and stirred at 60 to 90 ° C. for about 10 to 24 hours, at the same temperature. Aged for 3 to 10 hours, the precipitate is washed / filtered, dried at 100 to 120 ° C. for about 8 to 10 hours and then calcined at 500 ° C. in an oxygen atmosphere for 4 to 5 hours.

The molar ratio of the auxiliary active ingredient to the main active ingredient is in the range of 0.5 to 5.0, and the molar ratio of the main active ingredient to the precipitant is in the range of 0.5 to 5.0.

In order to maximize the adsorption performance of the calcined product, it is characterized by performing at least 500 ° C. for 3 hours or more in a 5% H 2 atmosphere.

The active ingredient is preferably loaded with the main active ingredient, auxiliary active ingredient and precipitant sequentially in the solid carrier, if the order is changed, there is a problem that the chemical structure of the main active ingredient is altered and the adsorption power is weakened. It is desirable to maintain the same order.

In addition, the precipitant used in the present invention is a co-precipitation agent that plays a role of co-precipitation of the active ingredient and the auxiliary active ingredient dissolved in the aqueous solution at the same time, by simply increasing the pH of the solution to induce coprecipitation of the main active ingredient and auxiliary active ingredient It is not desirable to do so.

The adsorbent prepared in this way is highly dispersed in the carrier and the main active ingredient and the auxiliary active ingredient to effectively remove impurities such as traces of O ₂ , CO, CO ₂ and H ₂ O contained in the inert gas at room temperature. Do.

Hereinafter, the present invention will be described in more detail with reference to the following examples, which are not intended to limit the present invention.

Example 1

After dissolving 16.3g of Ni (NO ₃ ) ₂ -6H ₂ O in distilled water at 90 ° C, 2g of Na ₂ SiO ₃ -nH ₂ O, 10g of urea, and 0.15g Mg (NO ₃ ) ₂ -6H ₂ O were mixed for 24 hours. After stirring, the stirring is stopped and aged at the same temperature for 4 hours. The obtained product was washed / filtered, dried at 110 ° C., calcined at 500 ° C. for 5 hours in an oxygen atmosphere, and pretreated at 500 ° C. for 5 hours with 5% H ₂ to prepare an adsorbent.

Example 2

Dissolve 16.3g of Ni (NO ₃ ) ₂ -6H ₂ O in distilled water at 90 ° C, mix 2g of SiO ₂ with 10g of urea (100%), 0.19g Mg (NO ₃ ) ₂ -6H ₂ O, and stir for 24 hours. The stirring is then stopped and aged at the same temperature for 4 hours. The obtained product was washed / filtered, dried at 110 ° C., calcined at 500 ° C. for 5 hours in an oxygen atmosphere, and pretreated at 500 ° C. for 5 hours with 5% H ₂ to prepare an adsorbent.

Example 3

16.3g of Ni (NO ₃ ) ₂ -6H ₂ O was dissolved in distilled water at 90 ° C, and then 2g of NaAlO ₂ -nH ₂ O, 10g of urea (110%) and 0.12g Mg (NO ₃ ) ₂ -6H ₂ O were mixed. After stirring for 24 hours, the stirring was stopped and aged at the same temperature for 4 hours. The obtained product was washed / filtered, dried at 110 ° C., calcined at 500 ° C. for 5 hours in an oxygen atmosphere, and pretreated at 500 ° C. for 5 hours with 5% H ₂ to prepare an adsorbent.

Example 4

After dissolving 16.3 g of Ni (NO ₃ ) ₂ -6H ₂ O in distilled water at 90 ° C, 2 g of Al ₂ O ₃ -SiO ₂ (15-85%) and 10 g of urea (100%), 0.14 g Mg (NO ₃ ) ₂ thereby mixing -6H ₂ O and aged at the same temperature to stop the stirring for 24 hours, then stirred for 4 hours. The obtained product was washed / filtered, dried at 110 ° C., calcined at 500 ° C. for 5 hours in an oxygen atmosphere, and pretreated at 500 ° C. for 5 hours with 5% H ₂ to prepare an adsorbent.

Comparative Example 1

The adsorbent was prepared in the same manner as in Example 2 but washed / filtered and dried at 110 ° C., calcined at 500 ° C. for 5 hours in an oxygen atmosphere, and pretreated at 300 ° C. for 5 hours using 5% H ₂ . It was.

Comparative Example 2

Dissolve 16.3g of Ni (NO ₃ ) ₂ -6H ₂ O in distilled water at 90 ° C, mix 10g of urea (100%) and 0.15g Mg (NO ₃ ) ₂ -6H ₂ O, stir for 24 hours, and then stir. Stop and mature at the same temperature for 4 hours. The obtained product was washed / filtered, dried at 110 ° C., calcined at 500 ° C. for 5 hours in an oxygen atmosphere, and pretreated at 500 ° C. for 5 hours with 5% H ₂ to prepare an adsorbent.

Comparative Example 3

After dissolving 16.3 g of Ni (NO ₃ ) ₂ -6H ₂ O in distilled water at 90 ° C., ₂ g of Na ₂ SiO ₃ , 610 mL of 0.3M NH ₄ OH, and 0.15 g Mg (NO ₃ ) ₂ were mixed and stirred for 24 hours. The stirring is stopped and aged at the same temperature for 4 hours. The obtained product was washed / filtered, dried at 110 ° C., calcined at 500 ° C. for 5 hours in an oxygen atmosphere, and pretreated at 500 ° C. for 5 hours with 5% H ₂ to prepare an adsorbent.

Comparative Example 4

After dissolving 16.3 g of Ni (NO3) 2-6H2O in 200 mL of distilled water at 90 ° C, 2 g of Na2SiO3, 40 g of urea, and 0.15 g Mg (NO3) 2-6H2O were mixed and stirred for 24 hours, and then the stirring was stopped and the mixture was stirred at the same temperature for 4 hours. Mature. The obtained product was washed / filtered, dried at 110 ° C., calcined at 500 ° C. for 5 hours in an oxygen atmosphere, and pretreated at 500 ° C. for 5 hours with 5% H ₂ to prepare an adsorbent.

In order to measure the activity of the adsorbent prepared by the above production method, it was measured by the performance evaluation apparatus of FIG. The catalytic activity measuring device is configured by organically connecting three parts such as an impurity gas supply device such as O ₂ , CO, a vertical reaction vessel, and a concentration measuring device.

In FIG. 1, impurity gases such as O ₂ and CO supplied from the gas cylinders 1 and 2 are respectively flowed to flow directly through the flow regulator 3 to the fixed bed reactors 5 and 6 equipped with the adsorbent. It is constructed, and 5% H ₂ supplied from the gas cylinder (4) is flowed to enable the post-treatment of the adsorbent.

At this time, the amount and speed of each gas used for the performance evaluation of the adsorbent was controlled by the flow controller (3), the fixed bed reactor (5) was made of Pyrex glass 50 cm in length, 1.6 cm in diameter.

The adsorbent was mounted in the middle of the reactor in the form of granules, and impurity gases (O ₂ , CO) were adsorbed by the active ingredients supported on the carrier while passing through the mounted adsorbent layer, and then quantified by a detector.

At this time, impurity gas (O ₂ , CO) concentration was quantified using a gas chromatograph.

Experimental Example 1

In order to evaluate the performance of the adsorbents prepared in Examples 1 to 4 and Comparative Examples 1 to 4, the adsorption performance was measured using the activity measuring device shown in FIG.

The amount of adsorbent used for measuring the adsorption performance of the material was filled with 1 g each, the gas flow rate was 250 cc / min, the adsorption reaction was carried out at 20 ~ 25 ℃. Concentrations of impurity gas used were 54ppm O ₂ and 32ppm CO (bottom gas He), the detector was micro TCD (Valco Instrument Co), column packing material MS-5A, column oven temperature was performed at 110 ℃.

The performance of the adsorbents prepared in Examples 1 to 4 and Comparative Examples 1 to 4 was measured, and the results are shown in Table 1 below.

Breakthrough time (hr) O ₂ CO Example 1 23 6.0 Example 2 22 4.5 Example 3 20 7.0 Example 4 22 4.0 Comparative Example 1 2.5 1.5 Comparative Example 2 0.4 0.3 Comparative Example 3 7.0 3.0 Comparative Example 4 1.0 0.5

As shown in Table 1, it was confirmed that the adsorbents of Examples 1 to 4 prepared according to the present invention have superior impurity gas adsorption performances, such as CO and O ₂ , compared to Comparative Examples 1 to 4. Specifically, in Examples 1 to 4, 100% adsorption performance was maintained for 20 to 23 hours for CO ₂ and 4.0 to 7.0 hours for CO ₂ .

On the other hand, in Comparative Examples 1 to 4, (1) conditions for post-treatment of the calcined adsorbent (Comparative Example 1), (2) adsorbent presentation, when a specific carrier did not coexist (Comparative Example 2), (3) adsorbent preparation When inducing coprecipitation of the main active ingredient and auxiliary active ingredient by simply increasing the pH of the aqueous solution (Comparative Example 3), (4) When the molar ratio of the main active ingredient and the precipitant is out of a specific composition (Comparative Example 4), etc. The adsorbents prepared in the state of not satisfying the various conditions presented in the present invention were observed to have excellent initial adsorption performance, but they quickly disappeared and were also undesirable in terms of maintaining the adsorption performance. It is not satisfied.

In the present invention, by using the granular adsorbent as a starting material to prepare a molded body having a certain shape and size to evaluate the performance of removing impurity gas (O ₂ , CO, CO ₂ , H ₂ O) contained in the actual inert gas It was.

Example 5

The adsorbent prepared in Example 1 was used to make cylindrical pellets having a diameter of 5 mm and a height of 3 mm using a molding machine to evaluate the performance of the adsorbent to measure the concentrations of O ₂ , CO, CO ₂ , and H ₂ O.

Comparative Example 5

The adsorbent prepared in Comparative Example 2 was used to make cylindrical pellets having a diameter of 5 mm and a height of 3 mm using a molding machine to evaluate the performance of the adsorbent, and to measure concentrations of O ₂ , CO, CO ₂ , and H ₂ O.

Comparative Example 6

The adsorbent prepared in Comparative Example 3 was used to make cylindrical pellets having a diameter of 5 mm and a height of 3 mm using a molding machine to evaluate the performance of the adsorbent to measure concentrations of O ₂ , CO, CO ₂ , and H ₂ O.

Experimental Example 2

The performance of the adsorbents prepared in Example 5 and Comparative Examples 5 to 6 was evaluated by the following method.

After configuring the line as shown in Figure 2, Hitachi's API-MS (Atmospheric pressure ionization-Mass) was measured using a calibration curve method to measure the concentration of CO ₂ , H ₂ O, O ₂ H ₂ and CO concentration of Trace Analytical Measured by RGA3 (Reduction Gas Analyzer).

Example 5, Comparative Example 5

Activated adsorbent is filled with 60g of adsorbent in SUS Tube (SUS 316L 3/4 "), and then purged for 2 hours using purified N ₂ , and the filling column is heated to 250 ℃ (actual temperature 280 ℃) and hydrogen 40L (actual 18L) ) Was injected for 30 minutes to activate the adsorbent.

End the hydrogen injection PN ₂ (pure N ₂₎ was substituted in a state in which a temperature is maintained in the PN ₂ 1 hour conducted Purge operation and after lowering the temperature to 20 ~ 25 ℃ using the API-MS impurities PN ₂ The concentration was measured (obtained values of 0.5 ppb or less for N ₂ CO ₂ , O ₂ , and H ₂ O).

After changing PN ₂ to GN ₂ (General N ₂ ), we confirmed the column's ability to remove impurities. The experimental results were obtained as shown in Table 2. The concentrations of impurities in GN ₂ after reacting with catalyst are shown in Table 2.

The performance of the molded adsorbents prepared in Example 5 and Comparative Example 5 was measured and the results are shown in Table 2 below.

Impurity Gas Concentration (ppb) Before the reaction After the reaction Impurity Gas Name CO CO ₂ H ₂ O O ₂ CO CO ₂ H ₂ O O ₂ Example 5 Mi measurement 100 1000 1000 Mi measurement 0.04 0.5 0.15 Comparative Example 5 Mi measurement 100 1000 1000 Mi measurement 1.5 0.7 0.07

The present invention is not limited to the above-described embodiments, and as can be seen in the appended claims, those skilled in the art can make modifications without departing from the spirit of the present invention, and such modifications are possible. Belongs to the scope of.

1 is a block diagram showing an apparatus for evaluating the performance of a material according to the present invention; And

2 is a flowchart illustrating a process for measuring activity.

<Explanation of Signs of Major Parts of Drawings>

1: O ₂ gas cylinder 2: CO gas cylinder

3: MFC 4: H2 Gas Cylinder

5, 6: constant temperature fixed bed reactor 7: gas chromatograph

Claims (9)

In the ultrahigh purity inert gas manufacturing adsorbent containing a porous solid carrier, active metal salt and co-precipitation agent, Melting the porous solid carrier and the active metal salt dispersed in the porous solid carrier in water at 70 ° C .; Mixing and aging a co-precipitation agent for precipitating the active metal salt with the molten porous solid carrier and the active metal salt to form a mixed metal precipitate; Filtering, washing, drying and calcining the mixed metal precipitate; And The calcined mixed metal precipitate is prepared by a method comprising the step of heat treatment in a hydrogen atmosphere, The porous solid carrier is selected from the group consisting of activated carbon, alumina, synthetic zeolite, natural zeolite, sodium silicate, sodium metasilicate, sodium aluminate, zirconia, titania, talc, silica, inorganic oxide layered compounds, and mixtures thereof , The active metal salt is a salt of a metal selected from the group consisting of nickel, alkali metals and alkaline earth metals (salt). delete The method of claim 1, The active ingredient of the active metal salt is an adsorbent for ultrapure inert gas production, characterized in that derived from nitrate, sulfate, hydrochloride or acetate of each metal. The method of claim 1, An adsorbent for preparing ultra-high purity inert gas, wherein the molar ratio of the co-precipitant to the nickel raw material is 1: 0.5 to 5.0 when the adsorbent is manufactured. The method of claim 1, The active metal salt is, 30 to 70% by weight of the nickel is supported, An adsorbent for producing ultra-high purity inert gas, wherein the molar ratio of the mole ratio of the nickel component to the alkali metal or alkaline earth metal is from 0.5 to 5.O: 1. The method of claim 1, The alkali metal is selected from the group consisting of Li, Na, K, Rb and Cs, The alkaline earth metal is selected from the group consisting of Mg, Ca, Sr and Ba adsorbent for ultra-high purity inert gas production. The method of claim 1, The heat treatment step, Adsorbent for preparing ultra-high purity inert gas, characterized in that performed for 5 hours at 500 ℃ in a 5% H ₂ atmosphere. The method of claim 1, The co-precipitation agent, Adsorbent for ultrapure inert gas production, characterized in that it is selected from the group consisting of citric acid, urea, ammonia water, caustic soda, sodium carbonate and hydrazine. An ultra-high purity inert gas adsorbent according to any one of claims 1 and 3 to 8, Adsorbent for producing ultra high purity inert gas, characterized in that the concentration of O ₂ , CO, CO ₂ and H ₂ O contained in the inert gas is reduced to a level of 1.0 ppb or less.

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