CO2 and O2 remover

Abstract

The present invention relates to a CO2 and O2 removing agent, which comprises 65 to 85 wt% nickel oxide (NiO) and 5 to 20 wt% magnesium oxide (MgO), with the weight ratio of the nickel oxide to the magnesium oxide (NiO / MgO) being 4 to 11, and the weight percentages are based on the weight of the CO2 and O2 removing agent.

Description

[Technical Field]

[0001] The present invention relates to a CO2 and O2 (CO2 / O2) removing agent and a method for producing the same. [Background technology]

[0002] CO2 / O2 scavengers are needed in semiconductor manufacturing processes that use inert gas atmospheres containing, for example, nitrogen, helium, or argon. Active gases such as CO2 / O2 must be removed to make the atmosphere inert.

[0003] WO2013109895 discloses a CO2 adsorbent comprising (i) a magnesium salt, and (ii) at least one salt of a Group IA element, wherein (i) the magnesium salt and (ii) the Group IA element salt are present in a molar ratio of about 8:1 to 3:1. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2013109895 Summary of the Invention [Problem to be solved by the invention]

[0005] The objective is to provide a CO2 / O2 remover that effectively removes CO2 and O2 from the gas. [Means for solving the problem]

[0006] One aspect of the present invention is a CO2 and O2 removing agent comprising 65 to 85 wt% nickel oxide (NiO) and 5 to 20 wt% magnesium oxide (MgO), wherein the weight ratio of the nickel oxide to the magnesium oxide (NiO / MgO) is 4 to 11, and the weight percentages are based on the weight of the CO2 and O2 removing agent. CO contained in inert gases 2 and O 2 For removing Regarding CO2 and O2 removers.

[0007] Another aspect of the present invention relates to a method for producing a CO2 and O2 removing agent, comprising mixing a nickel compound and a magnesium compound, and calcining the mixture to form a CO2 and O2 removing agent, wherein the CO2 and O2 removing agent comprises 65 to 85 wt. % nickel oxide (NiO) and 5 to 20 wt. % magnesium oxide (MgO), wherein the weight ratio of the nickel oxide to the magnesium oxide (NiO / MgO) is 4 to 11, and the weight percentages are based on the weight of the CO2 and O2 removing agent.

[0008] Another aspect of the invention involves the steps of disposing a CO2 and O2 removing agent in a container, wherein the CO2 and O2 removing agent comprises 65-85 wt% nickel oxide (NiO) and 5-20 wt% magnesium oxide (MgO), wherein the weight ratio of the nickel oxide to the magnesium oxide (NiO / MgO) is 4-11, the weight percentages being based on the weight of the CO2 and O2 removing agent; and Inert gas The container The CO contained in the inert gas 2 and O 2 Remove process, including inert gas This invention relates to a method for removing CO2 and O2 from [Effects of the Invention]

[0009] CO2 and O2 can be effectively removed from the gas by the present invention. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 shows an example of a cylindrical CO2 / O2 removal agent 10 having a circular cross section. [Figure 2] FIG. 2 shows an example of a cylindrical CO2 / O2 remover 20 having a tri-lobe cross section. DETAILED DESCRIPTION OF THE INVENTION

[0011] The CO2 / O2 remover and its manufacturing method are described below. The CO2 / O2 remover contains 65 to 85 wt % of nickel oxide (NiO) and 5 to 20 wt % of magnesium oxide (MgO) based on the weight of the CO2 / O2 remover.

[0012] In one embodiment, the NiO content is 66.5 wt% or more, in another embodiment, 67.5 wt% or more, in another embodiment, 68.5 wt% or more, in another embodiment, 69 wt% or more, in another embodiment, 70.5 wt% or more, and in another embodiment, 71.2 wt% or more, based on the weight of the CO2 / O2 removing agent. In one embodiment, the NiO content is 83.5 wt% or less, in another embodiment, 82.1 wt% or less, in another embodiment, 80.5 wt% or less, in another embodiment, 78.6 wt% or less, in another embodiment, 76 wt% or less, and in another embodiment, 74.5 wt% or less, based on the weight of the CO2 / O2 removing agent.

[0013] In one embodiment, the MgO content is 5.5 wt% or more, in another embodiment, 6.2 wt% or more, in another embodiment, 7.5 wt% or more, in another embodiment, 7.9 wt% or more, in another embodiment, 8.9 wt% or more, in another embodiment, 9.9 wt% or more, and in another embodiment, 10.5 wt% or more, based on the weight of the CO2 / O2 removing agent. In one embodiment, the MgO content is 19.2 wt% or less, in another embodiment, 18.1 wt% or less, in another embodiment, 17.5 wt% or less, in another embodiment, 16.3 wt% or less, in another embodiment, 15.5 wt% or less, in another embodiment, 14.8 wt% or less, in another embodiment, 13.2 wt% or less, in another embodiment, 12.5 wt% or less, in another embodiment, 11.1 wt% or less, and in another embodiment, 9.9 wt% or less, based on the weight of the CO2 / O2 removing agent.

[0014] The weight ratio of NiO to MgO (NiO / MgO) is 4 to 11. In one embodiment, the weight ratio of NiO to MgO (NiO / MgO) is 4.5 or more, in another embodiment, 5.1 or more, in another embodiment, 5.7 or more, in another embodiment, 6.1 or more, in another embodiment, 6.9 or more, in another embodiment, 7.5 or more, and in another embodiment, 8.1 or more. In another embodiment, the weight ratio of NiO to MgO (NiO / MgO) is 10.5 or less, in another embodiment, 9.8 or less, in another embodiment, 5.7 or less, in another embodiment, 9 or less, in another embodiment, 8.2 or less, in another embodiment, 7.5 or less, and in another embodiment, 6.8 or less. A CO2 / O2 removing agent containing NiO and MgO in the above weight ratio can sufficiently remove both CO2 and O2.

[0015] In one embodiment, the CO2 / O2 removing agent further comprises one or more other metal oxides selected from the group consisting of silicon oxide (SiO2), aluminum oxide (Al2O3), sodium oxide (Na2O), and mixtures thereof. In another embodiment, the CO2 / O2 removing agent further comprises one or more other metal oxides selected from the group consisting of silicon oxide (SiO2), aluminum oxide (Al2O3), and mixtures thereof.

[0016] In another embodiment, the CO2 / O2 removing agent contains SiO2 in addition to NiO and MgO. The SiO2 content is, based on the weight of the CO2 / O2 removing agent, 1 wt% or more in one embodiment, 2.2 wt% or more in another embodiment, 2.9 wt% or more in another embodiment, 3.6 wt% or more in another embodiment, 4.5 wt% or more in another embodiment, 5.2 wt% or more in another embodiment, and 6.9 wt% or more in another embodiment. The SiO2 content is, based on the weight of the CO2 / O2 removing agent, 20 wt% or less in one embodiment, 17.2 wt% or less in another embodiment, 13.5 wt% or less in another embodiment, 10.3 wt% or less in another embodiment, 8.5 wt% or less in another embodiment, 6.4 wt% or less in another embodiment, and 5.2 wt% or less in another embodiment.

[0017] In one embodiment, the CO2 / O2 removing agent contains Al2O3 in addition to NiO and MgO. The Al2O3 content is, based on the weight of the CO2 / O2 removing agent, 1 wt% or more in one embodiment, 3.2 wt% or more in another embodiment, 5.9 wt% or more in another embodiment, 7.2 wt% or more in another embodiment, 9.5 wt% or more in another embodiment, 10.1 wt% or more in another embodiment, and 11.2 wt% or more in another embodiment. The Al2O3 content is, based on the weight of the CO2 / O2 removing agent, 30 wt% or less in one embodiment, 26.3 wt% or less in another embodiment, 22.5 wt% or less in another embodiment, 18.3 wt% or less in another embodiment, 15.5 wt% or less in another embodiment, 12.8 wt% or less in another embodiment, and 11.6 wt% or less in another embodiment.

[0018] In one embodiment, the CO2 / O2 removing agent contains an alkali metal oxide in addition to NiO and MgO. In another embodiment, the alkali metal oxide is selected from the group consisting of sodium oxide (Na2O), potassium oxide (KO), lithium oxide (Li2O), and combinations thereof. In another embodiment, the alkali metal oxide includes sodium oxide (Na2O). The alkali metal oxide is present in an amount of 0.01 wt% or more, 0.05 wt% or more, 0.09 wt% or more, 0.1 wt% or more, 0.24 wt% or more, 0.33 wt% or more, or 0.42 wt% or more, based on the weight of the CO2 / O2 removing agent. In one embodiment, the alkali metal oxide is present in an amount of 2 wt% or less, 1.9 wt% or less, 1.2 wt% or less, 0.8 wt% or less, or 0.6 wt% or less, based on the weight of the CO2 / O2 removing agent. The CO2 / O2 removal agent may, in another embodiment, not include alkali metal oxides or Na2O.

[0019] The CO2 / O2 removing agent compositions described herein include, but are not limited to, those listed in Table I, and those skilled in the art of chemistry can make minor substitutions or additions without substantially changing the desired properties of the CO2 / O2 removing agent. For example, substitution of 0.001 to 3.0 wt. % of oxides of iron (Fe), calcium (Ca), titanium (Ti), cerium (Ce), zinc (Zn), and zirconium (Zr), alone or in combination, based on the weight of the CO2 / O2 removing agent, can be made to achieve similar performance. The composition of the CO2 / O2 removing agent can be determined by performing ultraviolet analysis (XRF analysis) on the CO2 / O2 removing agent.

[0020] The shape of the CO2 / O2 removing agent is not limited. The CO2 / O2 removing agent can be in any shape as long as it has sufficient removal capacity and strength as a CO2 / O2 removing agent. In one embodiment, the CO2 / O2 removing agent is granular. In another embodiment, the CO2 / O2 removing agent is cylindrical or spherical. In one embodiment, the cross section of the cylindrical CO2 / O2 removing agent is selected from the group consisting of circular, elliptical, polygonal, rectangular, and polylobal. In another embodiment, the cross section of the cylindrical CO2 / O2 removing agent is circular, elliptical, or polylobal, in another embodiment, polylobal, or trilobal.

[0021] FIG. 1 shows an example of a cylindrical CO2 / O2 remover 10 having a circular cross section. The diameter 12 of the cylindrical CO2 / O2 remover 10 is 0.5 to 10 mm in one embodiment, 0.8 to 8.7 mm in another embodiment, 1 to 5.7 mm in another embodiment, and 1.2 to 3.3 mm in another embodiment. The length 13 of the cylindrical CO2 / O2 remover 10 is 0.5 to 30 mm in one embodiment, 1.2 to 21 mm in another embodiment, 2.5 to 16 mm in another embodiment, and 3.2 to 10 mm in another embodiment. When the cross section is elliptical or rectangular, the diameter refers to the major axis. When the cross section is polylobal or polygonal, the diameter refers to the diameter of the circumscribed circle. FIG. 2 shows an example of a cylindrical CO2 / O2 remover 20 having a trilobal cross section.

[0022] This is the diameter of a circumscribing circle 21 of the trilobe cross section of cylindrical CO2 / O2 remover 20. Diameter 22 of trilobe CO2 / O2 remover 20 is 0.5 to 10 mm in one embodiment, 0.8 to 8.7 mm in another embodiment, 1 to 5.7 mm in another embodiment, and 1.2 to 3.3 mm in another embodiment. Length 23 of trilobe CO2 / O2 remover 20 is 0.5 to 30 mm in one embodiment, 1.2 to 21 mm in another embodiment, 2.5 to 16 mm in another embodiment, and 3.2 to 10 mm in another embodiment.

[0023] In one embodiment, the CO / O removal agent is porous. In one embodiment, the pore volume is 0.05 mm 3 / g~5.0mm 3 / g. The pore volume can be measured using an automatic pore size distribution analyzer such as the BELSORP-mini-II from MicrotracBEL Corporation. The specific surface area (S BET ) is 10 to 1000 m in one embodiment. 2 / g, in another embodiment, 32 to 800 m 2 / g, in another embodiment, 58 to 645 m 2 / g, in another embodiment, 68 to 500 m 2 / g, in another embodiment, 80 to 320 m 2 / g, in another embodiment, 85 to 240 m 2 / g, in another embodiment, 100 to 200 m 2 The specific surface area is / g. The specific surface area can be measured by the BET single-point method, which involves N2 gas adsorption at liquid nitrogen temperature. A specific surface area analyzer such as the Macsorb Model 1210 from MOUNTECH can be used.

[0024] In one embodiment, the CO2 / O2 removing agent is made by a precipitation method or a drying method. A Ni compound, an Mg compound, and optionally a Si compound, an Al compound, and / or a Na compound are prepared. The compounds are mixed and calcined to form the CO2 / O2 removing agent. In one embodiment, the Al compound can be added to the mixture of the Ni compound and the Mg compound before or after the calcination step.

[0025] For the source of the CO2 / O2 removal agent, such as compounds of Ni, Mg, Al, Si and Na, any compound that provides the oxides of those metals after calcination can be used.

[0026] The Ni compound may be an oxide, a salt, or a mixture thereof. In one embodiment, the Ni compound may be selected from the group consisting of nickel oxide, nickel nitrate, nickel nitrite, nickel sulfate, and combinations thereof.

[0027] The Mg compound may be an oxide, a salt, or a mixture thereof. In one embodiment, the Mg compound may be selected from the group consisting of magnesium oxide, magnesium nitrate, magnesium nitrite, magnesium sulfate, and combinations thereof.

[0028] The Si compound, in one embodiment, may be selected from the group consisting of silica, diatomaceous earth, liquid glass, and combinations thereof. In one embodiment, the Al compound can be selected from the group consisting of boehmite, alumina sol, and combinations thereof. The Al compound can also function as a binder for the Ni and Mg compounds. In another embodiment, the Al compound can be mixed separately with the precipitate because the Al compound can function as a binder for the precipitate. The Na compound may be sodium carbonate in one embodiment.

[0029] In one embodiment, the metal compounds can be mixed by precipitation using a solution containing dissolved Ni and Mg compounds. The Ni and Mg compounds can be soluble salts, such as nitrates, nitrites, and hydrogen sulfates, in another embodiment. The Ni compound can be nickel nitrate in another embodiment. The Mg compound can be magnesium nitrate in another embodiment. The Si and / or Al compounds can be added and dissolved in the solution in another embodiment. In another embodiment, the Si compound can be dissolved in the solution. In one embodiment, the solvent is water. In one embodiment, the solution is heated to 40° C. or higher for 1 hour or more to form a precipitate. In one embodiment, the precipitate is isolated by filtration. In one embodiment, the precipitate is a powder or particles. In another embodiment, the precipitate is optionally mixed with the Si and / or Al components.

[0030] The metal compound mixture is calcined. In another embodiment, calcination is carried out after the step of shaping the metal compound mixture. The calcination temperature can be 100 to 900°C in one embodiment, 120 to 680°C in another embodiment, 180 to 500°C in another embodiment, and 200 to 400°C in another embodiment. The calcination time is 30 minutes or more in one embodiment, and 1 hour or more in another embodiment. The calcination time is 5 hours or less in one embodiment, and 3 hours or less in another embodiment.

[0031] In one embodiment, the mixture of metal compounds can be formed into a desired shape. The forming method is not limited, but in one embodiment, the mixture of metal compounds is formed by extrusion or molding. The shaped metal compound mixture can be calcined, in one embodiment. In one embodiment, the precipitate, optionally mixed with the Si component and / or the Al component, is calcined.

[0032] In one embodiment, the CO2 / O2 removal agent is reduced by exposure to hydrogen gas, which in one embodiment is a gas flow at 300-550°C for 5-30 hours. After reduction, in one embodiment, an oxide layer is formed on the surface of the CO2 / O2 removal agent for stabilization, such as by exposure to a gas containing O2. In the precipitation method, in one embodiment, the solutions can be prepared separately as an acid solution and an alkaline solution. In one embodiment, the acid solution is prepared by dissolving a Ni compound and a Mg compound in the solution. In one embodiment, the alkaline solution is prepared by dissolving an additional metal compound, such as a Na compound, in the solution. In one embodiment, the Si compound can be dissolved in the acid solution. In one embodiment, the acid solution is gradually added to the alkaline solution until the mixed solution has a pH of about 7. The precipitate is removed from the mixed solution and calcined.

[0033] In another embodiment, a method for producing a CO2 and O2 removing agent includes the steps of mixing a nickel compound and a magnesium compound, shaping the mixture of the nickel compound and the magnesium compound, and calcining the shaped mixture.

[0034] In another embodiment, a method for producing a CO2 and O2 removing agent includes mixing a nickel compound and a magnesium compound, calcining the mixture of the nickel compound and the magnesium compound, and shaping the calcined mixture.

[0035] In another embodiment, the CO2 / O2 removal agent can also be made by a dry method. In another embodiment, the Ni compound and the Mg compound are mixed and calcined. CO2 / O2 scavenger can be used anywhere CO2 or O2 in the air is undesirable. For example, CO2 / O2 scavenger is applied to gas purification systems in semiconductor manufacturing plants. [Example]

[0036] The CO2 / O2 removal agent was prepared as follows. An acid solution was prepared by dissolving 7.5 kg of nickel nitrate, 1.6 kg of magnesium nitrate, and 0.3 kg of diatomaceous earth in 14.7 kg of deionized water. Separately, an alkaline solution was prepared by dissolving 3.9 kg of sodium carbonate in 17.4 kg of purified water. The acid solution was added to the alkaline solution until the mixture was neutral. The resulting precipitate was filtered, washed, and extracted. The precipitate was dried and calcined at 350 °C for 2 hours. The precipitate powder and boehmite were mixed in a weight ratio of 9:1 (precipitate powder:boehmite). The mixture was extruded using a vertical extruder to produce a CO2 / O2 removal agent precursor. The CO2 / O2 removal agent precursor had a diameter of 21.6 mm, a length of 22.7 mm, and a trilobe cross section (Figure 2).

[0037] CO2 / O2 remover 300cm 3 The CO2 / O2 removal agent was packed into a quartz tube (inner diameter 40 mm, length 950 mm) with an inlet and an outlet. The CO2 / O2 removal agent was reduced by exposing it to pure hydrogen gas. After cooling to room temperature, the hydrogen gas was switched to nitrogen gas. After the hydrogen gas was gone, oxygen-containing nitrogen gas was flowed into the tube, forming an oxide film on the surface of the CO2 / O2 removal agent, stabilizing it. The specific surface area (SA BET ) was measured using a MOUNTECH Macsorb Model 1210 and was approximately 150 m 2 The composition of the prepared CO2 / O2 removal agent was analyzed using an X-ray fluorescence spectrometer (XRF, Rigaku Super Mini 200).

[0038] Example 2 A CO2 / O2 removing agent was prepared in the same manner as in Example 1, except that 2.43 kg of magnesium nitrate hexahydrate and 0.14 kg of silica were used. BET ) is about 150m 2 / g.

[0039] Comparative Example 1 The CO2 / O2 removing agent was prepared in the same manner as in Example 1, except for the composition. The composition of the CO2 / O2 removing agent is shown in Table 1. The specific surface area (SA BET ) is about 150m2 / g.

[0040] measurement

[0041] CO2 removal amount In a quartz tube (inner diameter 20 mm, height 500 mm), 40 cm of the CO2 / O2 removal agent obtained above was placed. 3 The quartz tube had an inlet at the top and an outlet at the bottom. Reduction was performed to remove the oxide layer. After reduction, 30 ppm CO2 gas (CO2 / N2) was pumped from the inlet through the CO2 / O2 remover to the outlet for approximately 3,500 hours. -1 The flow of CO2 gas was stopped when the CO2 concentration at the outlet increased from 0 to 0.5 ppm.

[0042] The CO2 concentration of the gas from the outlet was measured using a gas chromatograph analyzer equipped with a flame ionization detector (FID) and a methanizer (Shimadzu GC-8A / MTN-1).

[0043] O2 removal amount 200 ppm O2 gas (air / N2) was passed from the inlet through the CO2 / O2 remover to the outlet for approximately 3,500 hours. -1 The O2 gas was flowed at an SV of 0.05 ppm. When the O2 concentration of the gas from the outlet increased from 0 to 7.0 ppm, the flow of the O2 gas was stopped. The O2 concentration of the gas from the outlet was measured using a recording oxygen analyzer (Advanced Micro Instruments, Model 1000-RS). "CO2 absorption amount" and "O2 absorption amount" were calculated using the following formula. CO2 removal amount (m 3 / kg) = CO2 gas flow rate (m 3 / h) x CO2 gas flow time (h) x CO2 concentration 30 ppm / removal agent weight (kg) O2 removal amount (m 3 / kg) = O2 gas flow rate (m 3 / h) x O2 gas flow time (h) x O2 concentration 200 ppm / removal agent weight (kg)

[0044] The results are shown in Table 1 below. In Examples 1 and 2, the amount of CO2 removed was 1.6 x 10 -3 m 3 / kg or more and O2 removal rate is 20x10 -3 m 3 / kg or more, which was sufficient. In Comparative Example 1, the O2 removal amount was 14x10 -3 m 3 / kg, which was insufficient.

[0045] [Table 1]

Claims

[Request 1] The nickel oxide (NiO) is 65 to 85% by weight, and the magnesium oxide (MgO) is 5 to 20% by weight, and the weight ratio of the nickel oxide to the magnesium oxide (NiO / MgO) is 4 to 11, and the weight percentage is CO ２ and O ２ CO2 for removing CO2 and O2 contained in the inert gas based on the weight of the remover ２ and O ２ Remover. Request 2 Aluminum oxide (Al ２ O ３ ), silicon oxide (SiO ２ 10. The CO of claim 1, further comprising one or more other metal oxides selected from the group consisting of: alkali metal oxides, and mixtures thereof. ２ and O ２ Remover. Request 3 The CO ２ and O ２ 1 to 30% by weight of aluminum oxide (Al ２ O ３ 2. The CO of claim 1, further comprising ２ and O ２ Remover. Request 4 The CO ２ and O ２ 1 to 20 wt. % silicon oxide (SiO ２ 2. The CO of claim 1, further comprising ２ and O ２ Remover. Request 5 The CO ２ and O ２ 10. The CO scavenger of claim 1, further comprising 0 to 2 wt. % of an alkali metal oxide, based on the weight of the scavenger. ２ and O ２ Remover. [Request 6] 10. The CO of claim 1, which is free of alkali metal oxides. ２ and O ２ Remover. Request 7 Specific surface area (S ＢＥＴ ) is 10 to 1000m ２ / g of CO ２ and O ２ Remover. Request 8 mixing a nickel compound with a magnesium compound and calcining the mixture to produce CO ２ and O ２ forming a CO scavenger, ２ and O ２ The scavenger comprises 65-85 wt % nickel oxide (NiO) and 5-20 wt % magnesium oxide (MgO), the weight ratio of the nickel oxide and the magnesium oxide (NiO / MgO) being 4-11, and the weight % is CO ２ and O ２ CO based on the weight of the scavenger ２ and O ２ How to make the remover. [Request 9] 9. The CO2 solution of claim 8, further comprising adding an aluminum compound to the mixture of the nickel compound and the magnesium compound before or after the calcination step. ２ and O ２ How to make the remover. Request 10 9. The CO2 of claim 8, further comprising shaping the mixture of the nickel compound and the magnesium compound. ２ and O ２ How to make the remover. [Request 11] CO ２ and O ２ placing a CO scavenger in a container, ２ and O ２ The scavenger contains 65-85 wt % nickel oxide (NiO) and 5-20 wt % magnesium oxide (MgO), and the weight ratio of the nickel oxide and the magnesium oxide (NiO / MgO) is 4-11, and the weight % is CO ２ and O ２ based on the weight of the remover; and An inert gas is passed through the container, and the CO contained in the inert gas is ２ and O ２ removing the from an inert gas containing CO ２ and O ２ How to remove.

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