JPWO2019171882A1 - A method for removing oxygen from crude carbon monoxide gas and a method for purifying carbon monoxide gas - Google Patents

A method for removing oxygen from crude carbon monoxide gas and a method for purifying carbon monoxide gas Download PDF

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JPWO2019171882A1
JPWO2019171882A1 JP2020504879A JP2020504879A JPWO2019171882A1 JP WO2019171882 A1 JPWO2019171882 A1 JP WO2019171882A1 JP 2020504879 A JP2020504879 A JP 2020504879A JP 2020504879 A JP2020504879 A JP 2020504879A JP WO2019171882 A1 JPWO2019171882 A1 JP WO2019171882A1
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孝爾 横野
孝爾 横野
晃裕 桑名
晃裕 桑名
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Abstract

金属の混入を可能な限り回避しつつ粗一酸化炭素ガス中の酸素を除去する方法が提供される。当該酸素除去方法は、不純物として酸素を含む粗一酸化炭素ガスを、触媒槽（１）にて、金属を担持させていない活性炭（１ａ）と接触させることにより、当該ガス中の酸素を除去する。さらに、酸素除去後の生成ガスをアルカリ水溶液（２ａ）に接触させて、二酸化炭素を吸収除去することにより、精製一酸化炭素ガスを得る。A method for removing oxygen in crude carbon monoxide gas while avoiding metal contamination as much as possible is provided. The oxygen removing method removes oxygen in the gas by bringing a crude carbon monoxide gas containing oxygen as an impurity into contact with activated carbon (1a) on which no metal is supported in the catalyst tank (1). .. Further, the produced gas after oxygen removal is brought into contact with the alkaline aqueous solution (2a) to absorb and remove carbon dioxide to obtain purified carbon monoxide gas.

Description

本発明は、粗一酸化炭素ガスから酸素を除去する方法に関する。本発明は、さらにそのような酸素除去方法を利用した一酸化炭素ガスの精製方法にも関する。 The present invention relates to a method for removing oxygen from crude carbon monoxide gas. The present invention further relates to a method for purifying carbon monoxide gas using such an oxygen removing method.

一酸化炭素は化学合成や金属精錬などの幅広い産業で使用されており、特に最近では、シリコン半導体製造工程のクリーニング・エッチング用のガスとして９９．９９５モル％程度の高純度の一酸化炭素が使用されている。一酸化炭素の一般的な製造方法としては、鉱酸で修飾したゼオライト系触媒を用いて蟻酸の脱水反応（ＨＣＯＯＨ→Ｈ2Ｏ＋ＣＯ）を進行させ、一酸化炭素を得る方法が知られている（例えば特許文献１，２を参照）。前記反応で得られた粗一酸化炭素ガスは、水、水素、酸素、窒素、メタン、二酸化炭素、および未反応の蟻酸ミスト等を不純物として含んでいる。これらの不純物を除去することで高純度一酸化炭素（以下、「精製一酸化炭素ガス」と記すこともある）を得ている。Carbon monoxide is used in a wide range of industries such as chemical synthesis and metal refining, and recently, carbon monoxide with a high purity of about 99.995 mol% is used as a gas for cleaning and etching in the silicon semiconductor manufacturing process. Has been done. As a general method for producing carbon monoxide, a method is known in which a dehydration reaction of formic acid (HCOOH → H 2 O + CO) is carried out using a zeolite-based catalyst modified with a mineral acid to obtain carbon monoxide (HCOOH → H 2 O + CO). For example, see Patent Documents 1 and 2). The crude carbon monoxide gas obtained by the above reaction contains water, hydrogen, oxygen, nitrogen, methane, carbon dioxide, unreacted formic acid mist and the like as impurities. By removing these impurities, high-purity carbon monoxide (hereinafter, also referred to as "purified carbon monoxide gas") is obtained.

粗一酸化炭素ガスから高純度一酸化炭素を得るための精製方法としては、吸着、蒸留などの手段により不純物を除去する方法が知られている。しかしながら、不純物に酸素が含まれている場合、酸素の分子サイズが一酸化炭素の分子サイズに近く、分子篩吸着剤によって酸素と一酸化炭素とを吸着分離することは困難である。また、酸素と一酸化炭素の沸点は近いため、酸素と一酸化炭素とを蒸留分離することも困難であった。そこで、銅触媒や銅−亜鉛触媒に酸素が含まれている粗一酸化炭素ガスを接触させ、酸素を一酸化炭素と反応させて二酸化炭素に変換してから除去する方法が提案されている（例えば特許文献３を参照）。 As a purification method for obtaining high-purity carbon monoxide from crude carbon monoxide gas, a method of removing impurities by means such as adsorption and distillation is known. However, when oxygen is contained in the impurities, the molecular size of oxygen is close to the molecular size of carbon monoxide, and it is difficult to adsorb and separate oxygen and carbon monoxide with a molecular sieve adsorbent. Moreover, since the boiling points of oxygen and carbon monoxide are close to each other, it is difficult to distill and separate oxygen and carbon monoxide. Therefore, a method has been proposed in which a crude carbon monoxide gas containing oxygen is brought into contact with a copper catalyst or a copper-zinc catalyst, and oxygen is reacted with carbon monoxide to convert it into carbon dioxide before removal ( For example, see Patent Document 3).

しかしながら、前記金属触媒を用い、酸素を一酸化炭素と反応させて二酸化炭素に変換する方法では、金属触媒の一部が製品一酸化炭素ガス中に混入しうる。混入した金属は、製品一酸化炭素ガス中では金属カルボニル構造をとり、前記金属カルボニルは、極微量に存在するだけで半導体製造工程においては甚大な悪影響を及ぼすことが知られている。したがって、製品一酸化炭素ガスの製造において、金属成分の混入回避が強く望まれている。 However, in the method of reacting oxygen with carbon monoxide to convert it into carbon dioxide using the metal catalyst, a part of the metal catalyst can be mixed in the product carbon monoxide gas. It is known that the mixed metal has a metal carbonyl structure in the product carbon monoxide gas, and that the metal carbonyl is present in a very small amount and has a great adverse effect in the semiconductor manufacturing process. Therefore, in the production of product carbon monoxide gas, avoidance of mixing of metal components is strongly desired.

特開平１０−００７４１３号公報Japanese Unexamined Patent Publication No. 10-007413 特開平７−３３４２１号公報Japanese Unexamined Patent Publication No. 7-333421 特開昭６０−１６１３１７号公報Japanese Unexamined Patent Publication No. 60-161317

本発明は、このような事情の下でなされたものであって、酸素を含む粗一酸化炭素ガスから、問題となる金属の混入を可能な限り回避しつつ、粗一酸化炭素ガスから酸素を除去する方法を提供することを主たる課題とする。 The present invention has been made under such circumstances, and oxygen is removed from the crude carbon monoxide gas containing oxygen while avoiding the mixing of problematic metals as much as possible. The main task is to provide a method for removal.

上記課題について本発明者らが鋭意検討した結果、酸素を含む粗一酸化炭素ガスを活性炭と接触させることにより、活性炭が酸素と一酸化炭素との反応の触媒として作用し、二酸化炭素が生成することを見出し、本発明を完成させるに至った。 As a result of diligent studies by the present inventors on the above problems, when crude carbon monoxide gas containing oxygen is brought into contact with activated carbon, the activated carbon acts as a catalyst for the reaction between oxygen and carbon monoxide, and carbon dioxide is generated. This has led to the completion of the present invention.

本発明の第１の側面によれば、酸素を含む粗一酸化炭素ガスを、金属を担持させていない活性炭と接触させることを特徴とする、粗一酸化炭素ガスから酸素を除去する方法が提供される。 According to the first aspect of the present invention, there is provided a method for removing oxygen from crude carbon monoxide gas, which comprises contacting a crude carbon monoxide gas containing oxygen with activated carbon on which no metal is supported. Will be done.

好ましくは、前記粗一酸化炭素ガスと前記活性炭との接触は、前記活性炭を充填した触媒槽に前記粗一酸化炭素ガスを導入することにより行う。 Preferably, the contact between the crude carbon monoxide gas and the activated carbon is performed by introducing the crude carbon monoxide gas into a catalyst tank filled with the activated carbon.

好ましくは、前記粗一酸化炭素ガスにおける酸素濃度が０．１〜１０００モルｐｐｍである。 Preferably, the oxygen concentration in the crude carbon monoxide gas is 0.1 to 1000 mol ppm.

好ましくは、前記粗一酸化炭素ガスと前記活性炭との接触温度が２０〜８０℃の範囲である。 Preferably, the contact temperature between the crude carbon monoxide gas and the activated carbon is in the range of 20 to 80 ° C.

好ましくは、前記粗一酸化炭素ガスと前記活性炭との接触温度が３０〜５０℃の範囲である。 Preferably, the contact temperature between the crude carbon monoxide gas and the activated carbon is in the range of 30 to 50 ° C.

本発明の第２の側面によれば、本発明の第１の側面に係る酸素除去方法により粗一酸化炭素ガスから酸素を除去する工程と、前記酸素除去工程により得られる生成ガスをアルカリ水溶液で洗浄することにより二酸化炭素を除去する工程と、を含む、一酸化炭素の精製方法が提供される。 According to the second aspect of the present invention, the step of removing oxygen from the crude carbon monoxide gas by the oxygen removing method according to the first aspect of the present invention and the produced gas obtained by the oxygen removing step are mixed with an alkaline aqueous solution. A method for purifying carbon monoxide is provided, which comprises a step of removing carbon dioxide by washing.

好ましくは、前記酸素除去工程と前記二酸化炭素除去工程とが、一酸化炭素が目的とする純度になるまで繰り返される。 Preferably, the oxygen removal step and the carbon dioxide removal step are repeated until carbon monoxide has the desired purity.

本発明の一実施形態に従い、酸素除去工程と二酸化炭素除去工程とを含む一酸化炭素精製方法を実施するための装置を示す概略構成図である。It is a schematic block diagram which shows the apparatus for carrying out the carbon monoxide purification method including an oxygen removal step and a carbon dioxide removal step according to one Embodiment of this invention.

以下、添付図面を参照しながら、本発明の一実施形態を具体的に説明するが、当該実施形態は本発明の保護範囲を限定するものではない。 Hereinafter, an embodiment of the present invention will be specifically described with reference to the accompanying drawings, but the embodiment does not limit the scope of protection of the present invention.

本実施形態に係る方法は、例えば図１に示すような一酸化炭素精製装置を用いて実施される。具体的には、一酸化炭素精製装置は、主として、活性炭１ａが充填された触媒槽１と、アルカリ水溶液２ａを収容したガス洗浄容器２と、を含んでいる。触媒槽１には、原料ガスしての粗一酸化炭素ガスがライン３を介して供給され、ライン３には、粗一酸化炭素ガスを所定の圧力まで加圧するためのコンプレッサ４が設けられている。触媒槽１では、粗一酸化炭素ガスに不純物として含まれる酸素の一部が一酸化炭素との反応により二酸化炭素に変換されて除去される。触媒槽１から排出される生成ガスはライン５を介してガス洗浄容器２に送られ、さらに導入管６を介してアルカリ水溶液２ａ中に導入される。この結果、酸性ガスである二酸化炭素はアルカリ水溶液２ａに吸収されて除去され、精製された一酸化炭素ガスがライン７を介して取り出される。ライン７は、排出ライン７ａと循環ライン７ｂとに接続されており、これらのライン７ａ，７ｂにはそれぞれ開閉弁８，９が設けられている。ライン７から排出される精製一酸化炭素ガスが目的とする純度に到達している場合には、開閉弁８が開状態とされ（開閉弁９は閉状態）、排出ライン７ａを介して精製一酸化炭素ガスが取り出される。一方、ライン７から排出される精製一酸化炭素ガスが目的とする純度に到達していない場合には、開閉弁９が開状態とされ（開閉弁８は閉状態）、循環ライン７ｂを介して不十分な精製一酸化炭素ガスとして再び触媒槽１に送られ、追加の酸素除去が行われる。なお、加圧が必要でない場合は、コンプレッサ４をブロワで置換してもよい。 The method according to this embodiment is carried out using, for example, a carbon monoxide purification apparatus as shown in FIG. Specifically, the carbon monoxide purification apparatus mainly includes a catalyst tank 1 filled with activated carbon 1a and a gas cleaning container 2 containing an alkaline aqueous solution 2a. A crude carbon monoxide gas as a raw material gas is supplied to the catalyst tank 1 via a line 3, and a compressor 4 for pressurizing the crude carbon monoxide gas to a predetermined pressure is provided in the line 3. There is. In the catalyst tank 1, a part of oxygen contained as an impurity in the crude carbon monoxide gas is converted into carbon dioxide by a reaction with carbon monoxide and removed. The generated gas discharged from the catalyst tank 1 is sent to the gas cleaning container 2 via the line 5, and further introduced into the alkaline aqueous solution 2a via the introduction pipe 6. As a result, carbon dioxide, which is an acid gas, is absorbed and removed by the alkaline aqueous solution 2a, and the purified carbon monoxide gas is taken out via the line 7. The line 7 is connected to a discharge line 7a and a circulation line 7b, and on-off valves 8 and 9 are provided in these lines 7a and 7b, respectively. When the purified carbon monoxide gas discharged from the line 7 has reached the desired purity, the on-off valve 8 is opened (the on-off valve 9 is closed), and the purified carbon monoxide gas is purified via the discharge line 7a. Carbon oxide gas is taken out. On the other hand, when the purified carbon monoxide gas discharged from the line 7 does not reach the desired purity, the on-off valve 9 is opened (the on-off valve 8 is in the closed state), and the on-off valve 8 is opened via the circulation line 7b. It is sent back to the catalyst tank 1 as insufficiently purified carbon monoxide gas for additional oxygen removal. If pressurization is not required, the compressor 4 may be replaced with a blower.

原料ガスしての粗一酸化炭素ガスは、主成分である一酸化炭素と、不純物としての酸素等とを含む。粗一酸化炭素ガスは、例えば鉱酸で修飾したゼオライト系触媒を用いた蟻酸の脱水反応（ＨＣＯＯＨ→Ｈ2Ｏ＋ＣＯ）後に、生成したＨ2Ｏと未反応のＨＣＯＯＨを凝縮器で一酸化炭素ガスから分離することによって得られる。粗一酸化炭素ガスにおける主成分たる一酸化炭素の純度は、例えば９９．９モル％以上、１００モル％未満である。精製一酸化炭素ガスの純度を高くする観点からは、粗一酸化炭素ガスにおける一酸化炭素の純度は、好ましくは９９．９９モル％以上、１００モル％未満である。また、該粗一酸化炭素ガス中の酸素の濃度は、好ましくは０．１〜１０００モルｐｐｍである。酸素濃度が１０００モルｐｐｍを超える場合は酸素を除去しきれずに精製一酸化炭素ガス中に残存する恐れがある。酸素の除去効率の観点から、粗一酸化炭素ガス中の酸素濃度は、０．１〜１００モルｐｐｍであるのが更に好ましい。粗一酸化炭素ガスは、酸素以外の不純物として、例えば水素、窒素、二酸化炭素、メタンを含んでいてもよい。これら不純物の各々の濃度は、例えば０．１〜１０モルｐｐｍ程度である。The crude carbon monoxide gas as a raw material gas contains carbon monoxide as a main component and oxygen as an impurity. The crude carbon monoxide gas is, for example, carbon monoxide gas produced by dehydrating formic acid using a zeolite-based catalyst modified with mineral acid (HCOOH → H 2 O + CO), and then using a condenser to combine the produced H 2 O with unreacted H COOH. Obtained by separating from. The purity of carbon monoxide, which is the main component of the crude carbon monoxide gas, is, for example, 99.9 mol% or more and less than 100 mol%. From the viewpoint of increasing the purity of the purified carbon monoxide gas, the purity of carbon monoxide in the crude carbon monoxide gas is preferably 99.99 mol% or more and less than 100 mol%. The concentration of oxygen in the crude carbon monoxide gas is preferably 0.1 to 1000 molppm. If the oxygen concentration exceeds 1000 mol ppm, the oxygen may not be completely removed and may remain in the purified carbon monoxide gas. From the viewpoint of oxygen removal efficiency, the oxygen concentration in the crude carbon monoxide gas is more preferably 0.1 to 100 mol ppm. The crude carbon monoxide gas may contain, for example, hydrogen, nitrogen, carbon dioxide, and methane as impurities other than oxygen. The concentration of each of these impurities is, for example, about 0.1 to 10 mol ppm.

触媒槽１に充填される活性炭１ａは、ヤシ殻、木材等の植物系、石炭、石油等の鉱物系のいずれを用いてもよい。活性炭の形状としては、粉末状、破砕状、円柱状、球状、ハニカム状のいずれを使用してもよい。 As the activated carbon 1a filled in the catalyst tank 1, any of a plant-based material such as coconut shell and wood, and a mineral-based material such as coal and petroleum may be used. As the shape of the activated carbon, any of powder, crushed, columnar, spherical, and honeycomb may be used.

触媒層１に充填される活性炭１ａは、金属を担持しておらず、活性炭１ａ単体として触媒機能を発揮する。触媒槽１では、粗一酸化炭素ガスに含まれる酸素が一酸化炭素と反応し、二酸化炭素に変換される。ここで、触媒槽１での粗一酸化炭素ガスの処理量は、空間速度にして例えば０．０１〜７０／ｍｉｎであり、酸化反応効率の観点から、好ましくは５〜５０／ｍｉｎである。 The activated carbon 1a filled in the catalyst layer 1 does not support a metal and exhibits a catalytic function as the activated carbon 1a alone. In the catalyst tank 1, oxygen contained in the crude carbon monoxide gas reacts with carbon monoxide and is converted into carbon dioxide. Here, the amount of crude carbon monoxide gas treated in the catalyst tank 1 is, for example, 0.01 to 70 / min in terms of space velocity, and is preferably 5 to 50 / min from the viewpoint of oxidation reaction efficiency.

活性炭１ａを充填した触媒槽１の温度（即ち、粗一酸化炭素ガスと活性炭との接触温度）は、好ましくは２０〜８０℃の範囲であり、より好ましくは３０〜５０℃である。 The temperature of the catalyst tank 1 filled with the activated carbon 1a (that is, the contact temperature between the crude carbon monoxide gas and the activated carbon) is preferably in the range of 20 to 80 ° C, more preferably 30 to 50 ° C.

活性炭１ａを充填した触媒槽１に導入する粗一酸化炭素ガスの圧力は、例えば０．１〜１０ＭＰａである。反応効率の観点から、好ましくは９〜１０ＭＰａである。 The pressure of the crude carbon monoxide gas introduced into the catalyst tank 1 filled with the activated carbon 1a is, for example, 0.1 to 10 MPa. From the viewpoint of reaction efficiency, it is preferably 9 to 10 MPa.

活性炭１ａを充填した触媒槽１は、高圧ガスの通気時に槽の気密性を保持できればよく、その形状は円筒型、角型、球形の何れでもよい。 The catalyst tank 1 filled with the activated carbon 1a may have a cylindrical shape, a square shape, or a spherical shape as long as the airtightness of the tank can be maintained when the high pressure gas is aerated.

触媒槽１では上述のように、粗一酸化炭素ガスに含まれる酸素が一酸化炭素と反応し、二酸化炭素に変換される。当該変換により生じた二酸化炭素は、蒸留あるいはＰＳＡ装置などによる分離手法や、分子篩やアルカリ水溶液に通すことにより除去される。経済的な観点から、図１に示したように、アルカリ水溶液による洗浄（吸収）が好ましく、アルカリ水溶液２ａとしては苛性ソーダ水溶液が好ましい。 In the catalyst tank 1, as described above, oxygen contained in the crude carbon monoxide gas reacts with carbon monoxide and is converted into carbon dioxide. Carbon dioxide generated by the conversion is removed by a separation method such as distillation or a PSA apparatus, or by passing through a molecular sieve or an alkaline aqueous solution. From an economical point of view, as shown in FIG. 1, washing (absorption) with an alkaline aqueous solution is preferable, and the caustic soda aqueous solution is preferable as the alkaline aqueous solution 2a.

アルカリ洗浄後得られる処理ガスを水洗してから水分をモレキュラーシーブで乾燥させることで、高純度一酸化炭素（製品一酸化炭素ガス）が得られる。 High-purity carbon monoxide (product carbon monoxide gas) can be obtained by washing the treatment gas obtained after alkaline washing with water and then drying the water with a molecular sieve.

本実施形態に係る方法は、触媒として単体の活性炭１ａを用いることで金属の混入を避けつつ、不純物として含まれる酸素の除去が可能であるから、半導体製造工程などの工業的用途に用いられる高純度一酸化炭素を製造するのに適している。 In the method according to the present embodiment, by using a single activated carbon 1a as a catalyst, it is possible to remove oxygen contained as an impurity while avoiding the mixing of metals. Therefore, it is highly used in industrial applications such as semiconductor manufacturing processes. Suitable for producing pure carbon monoxide.

以下に実施例を挙げて本発明をさらに詳しく説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.

〔実施例１〕
内径１１ｃｍ、長さ１２０ｃｍのＳＵＳ製の管に活性炭(粒状白鷺Ｇ２Ｘ、大阪ガスケミカル(株)製)を５．２ｋｇ充填し、触媒槽を調製した。９．８ＭＰaに圧縮した粗一酸化炭素ガス（原料ガス）を、前記触媒槽の温度を２０〜２５℃に保ちながら、空間速度にして３６．６／ｍｉｎで前記触媒槽に連続で導入した。導入した粗一酸化炭素ガス中の酸素濃度は１．４０モルｐｐｍであり、二酸化炭素は検出されなかった。酸素と二酸化炭素の濃度については、ガスクロマトグラフ(パルス放電型光イオン化検出器:ＰＤＤ)で分析した。前記触媒槽への粗一酸化炭素ガスの導入開始から２０分後、触媒槽出口から排出される一酸化炭素ガスの分析を行い、酸素と二酸化炭素の濃度を確認した。その結果、酸素濃度が１．３５モルｐｐｍ、二酸化炭素濃度が０．１０モルｐｐｍであった。[Example 1]
A SUS tube having an inner diameter of 11 cm and a length of 120 cm was filled with 5.2 kg of activated carbon (granular Shirasagi G2X, manufactured by Osaka Gas Chemical Co., Ltd.) to prepare a catalyst tank. Crude carbon monoxide gas (raw material gas) compressed to 9.8 MPa was continuously introduced into the catalyst tank at a space velocity of 36.6 / min while maintaining the temperature of the catalyst tank at 20 to 25 ° C. The oxygen concentration in the introduced crude carbon monoxide gas was 1.40 mol ppm, and carbon dioxide was not detected. The concentrations of oxygen and carbon dioxide were analyzed by gas chromatography (pulse discharge type photoionization detector: PDD). Twenty minutes after the start of introduction of the crude carbon monoxide gas into the catalyst tank, the carbon monoxide gas discharged from the outlet of the catalyst tank was analyzed to confirm the concentrations of oxygen and carbon dioxide. As a result, the oxygen concentration was 1.35 molppm and the carbon dioxide concentration was 0.10 molppm.

〔実施例２〕
触媒槽の温度を３５〜４０℃に変更した以外は実施例１と同様にして実験を行った。触媒槽から排出される一酸化炭素ガスの分析を行ったところ、酸素濃度が１．００モルｐｐｍ、二酸化炭素濃度が０．８０モルｐｐｍであった。[Example 2]
The experiment was carried out in the same manner as in Example 1 except that the temperature of the catalyst tank was changed to 35-40 ° C. When the carbon monoxide gas discharged from the catalyst tank was analyzed, the oxygen concentration was 1.00 molppm and the carbon dioxide concentration was 0.80 molppm.

〔実施例３〕
内径１ｃｍ、長さ３０ｃｍのＳＵＳ製の管に活性炭(粒状白鷺Ｇ２Ｘ、大阪ガスケミカル(株)製)を１０．６ｇ充填し、触媒槽を調製した。０．１ＭＰaに圧縮した一酸化炭素ガス（原料ガス）を、前記触媒槽の温度を４０〜４５℃に保ちながら、空間速度にして８．７／ｍｉｎで前記触媒槽に連続で導入した。導入した粗一酸化炭素ガス中の酸素濃度は２５.０モルｐｐｍであり、二酸化炭素は検出されなかった。触媒槽出口から排出される一酸化炭素ガスの分析を行ったところ、１時間経過後には酸素濃度が２３．２モルｐｐｍ、二酸化炭素濃度が４．２モルｐｐｍであった。２時間経過後には酸素濃度が２３．６モルｐｐｍ、二酸化炭素濃度が４．７モルｐｐｍであった。２ヶ月経過後には、酸素濃度が２３．４モルｐｐｍ、二酸化炭素濃度が４．５モルｐｐｍであった。[Example 3]
A catalyst tank was prepared by filling 10.6 g of activated carbon (granular Shirasagi G2X, manufactured by Osaka Gas Chemical Co., Ltd.) in a SUS tube having an inner diameter of 1 cm and a length of 30 cm. Carbon monoxide gas (raw material gas) compressed to 0.1 MPa was continuously introduced into the catalyst tank at an air velocity of 8.7 / min while maintaining the temperature of the catalyst tank at 40 to 45 ° C. The oxygen concentration in the introduced crude carbon monoxide gas was 25.0 mol ppm, and carbon dioxide was not detected. When the carbon monoxide gas discharged from the outlet of the catalyst tank was analyzed, the oxygen concentration was 23.2 molppm and the carbon dioxide concentration was 4.2 molppm after 1 hour. After 2 hours, the oxygen concentration was 23.6 molppm and the carbon dioxide concentration was 4.7 molppm. After 2 months, the oxygen concentration was 23.4 mol ppm and the carbon dioxide concentration was 4.5 mol ppm.

〔参考例１〕
実施例３における活性炭に代えてＡｌ2Ｏ3（住友化学(株)製）を用いて、実施例３と同様の実験を行った。触媒槽出口から排出される一酸化炭素ガスの分析を行ったところ、１時間経過後には酸素濃度が２４．５モルｐｐｍ、二酸化炭素濃度が０モルｐｐｍであった。２時間後には酸素濃度が２５モルｐｐｍ、二酸化炭素濃度が０モルｐｐｍであった。[Reference Example 1]
The same experiment as in Example 3 was carried out using Al 2 O 3 (manufactured by Sumitomo Chemical Co., Ltd.) instead of the activated carbon in Example 3. When the carbon monoxide gas discharged from the outlet of the catalyst tank was analyzed, the oxygen concentration was 24.5 molppm and the carbon dioxide concentration was 0 molppm after 1 hour. After 2 hours, the oxygen concentration was 25 mol ppm and the carbon dioxide concentration was 0 mol ppm.

〔評価〕
実施例１では、触媒槽で処理する前の粗一酸化炭素ガス中の酸素濃度は１．４０モルｐｐｍであったものが、触媒槽から排出された生成ガスにおいては酸素濃度が１．３５モルｐｐｍに減少して、０.１０モルｐｐｍの二酸化炭素が生成されていた。このことより、触媒槽における活性炭が触媒として作用し、酸素と一酸化炭素を反応させて二酸化炭素を生成させているものと理解される。なお、酸素の反応割合が小さいのは、もともと酸素濃度が極めて低いからであり、粗一酸化炭素ガスにおける酸素濃度が低くなればなるほど、その反応割合低下傾向は強くなる。また、反応割合が低い場合でも、図１に基づいて説明したように、同じ酸素除去工程を繰り返すことで、目標とする一酸化炭素ガスの純度に到達することはできる。[Evaluation]
In Example 1, the oxygen concentration in the crude carbon monoxide gas before treatment in the catalyst tank was 1.40 mol ppm, but in the produced gas discharged from the catalyst tank, the oxygen concentration was 1.35 mol. Decreased to ppm, 0.10 mol ppm of carbon dioxide was produced. From this, it is understood that the activated carbon in the catalyst tank acts as a catalyst and reacts oxygen with carbon monoxide to generate carbon dioxide. The reaction ratio of oxygen is small because the oxygen concentration is originally extremely low, and the lower the oxygen concentration in the crude carbon monoxide gas, the stronger the tendency of the reaction ratio to decrease. Further, even when the reaction ratio is low, the target purity of carbon monoxide gas can be reached by repeating the same oxygen removal step as described with reference to FIG.

実施例２からは、反応温度を高めることで１回の工程で除去できる酸素の割合を高めることができることが理解できる。 From Example 2, it can be understood that the proportion of oxygen that can be removed in one step can be increased by increasing the reaction temperature.

実施例３によれば、触媒槽における反応圧力を大気圧まで低下させても、反応温度を４０〜４５℃まで若干高めることで酸素を除去が可能であることが理解できる。また、活性炭の触媒活性は、反応を２ヶ月続けても低下しないことも分かり、酸素除去工程を目的とする一酸化炭素の純度が達成されるまで繰り返しても、何も問題ないことが了解される。さらに、参考例１を実施例３と対比すれば、活性炭と同じ反応条件ではＡｌ2Ｏ3を用いても触媒作用を示すことはなく、活性炭単体による触媒作用が確認できる。According to Example 3, it can be understood that even if the reaction pressure in the catalyst tank is lowered to atmospheric pressure, oxygen can be removed by slightly raising the reaction temperature to 40 to 45 ° C. It was also found that the catalytic activity of activated carbon did not decrease even if the reaction was continued for 2 months, and it was understood that there would be no problem even if the reaction was repeated until the purity of carbon monoxide for the purpose of the oxygen removal step was achieved. To. Further, when Reference Example 1 is compared with Example 3, the catalytic action by the activated carbon alone can be confirmed without showing the catalytic action even if Al 2 O 3 is used under the same reaction conditions as the activated carbon.

１：触媒槽
１ａ：活性炭
２：ガス洗浄容器
２ａ：アルカリ水溶液
４：コンプレッサ
７ｂ：循環ライン1: Catalyst tank 1a: Activated carbon 2: Gas cleaning container 2a: Alkaline aqueous solution 4: Compressor 7b: Circulation line

Claims (7)

酸素を含む粗一酸化炭素ガスを、金属を担持させていない活性炭と接触させることを特徴とする、粗一酸化炭素ガスから酸素を除去する方法。 A method for removing oxygen from crude carbon monoxide gas, which comprises contacting a crude carbon monoxide gas containing oxygen with activated carbon on which no metal is supported. 前記粗一酸化炭素ガスと前記活性炭との接触は、前記活性炭を充填した触媒槽に前記粗一酸化炭素ガスを導入することにより行う、請求項１に記載の方法。 The method according to claim 1, wherein the contact between the crude carbon monoxide gas and the activated carbon is performed by introducing the crude carbon monoxide gas into a catalyst tank filled with the activated carbon. 前記粗一酸化炭素ガスにおける酸素濃度が０．１〜１０００モルｐｐｍである、請求項１に記載の方法。 The method according to claim 1, wherein the oxygen concentration in the crude carbon monoxide gas is 0.1 to 1000 mol ppm. 前記粗一酸化炭素ガスと前記活性炭との接触温度が２０〜８０℃の範囲である、請求項１に記載の方法。 The method according to claim 1, wherein the contact temperature between the crude carbon monoxide gas and the activated carbon is in the range of 20 to 80 ° C. 前記粗一酸化炭素ガスと前記活性炭との接触温度が３０〜５０℃の範囲である、請求項１に記載の方法。 The method according to claim 1, wherein the contact temperature between the crude carbon monoxide gas and the activated carbon is in the range of 30 to 50 ° C. 請求項１ないし５のいずれかに記載の酸素除去方法により粗一酸化炭素ガスから酸素を除去する工程と、前記酸素除去工程により得られる生成ガスをアルカリ水溶液で洗浄することにより二酸化炭素を除去する工程と、を含む、一酸化炭素の精製方法。 Carbon dioxide is removed by washing the produced gas obtained by the step of removing oxygen from the crude carbon monoxide gas by the oxygen removing method according to any one of claims 1 to 5 and the oxygen removing step with an alkaline aqueous solution. A method for purifying carbon monoxide, including steps. 前記酸素除去工程と前記二酸化炭素除去工程とが、一酸化炭素が目的とする純度になるまで繰り返される、請求項６に記載の方法。 The method according to claim 6, wherein the oxygen removing step and the carbon dioxide removing step are repeated until carbon monoxide reaches the desired purity.
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