JP4107781B2 - Method for producing 13CO enriched CO gas - Google Patents
Method for producing 13CO enriched CO gas Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は13ＣＯ及び12ＣＯを含むＣＯガスから、吸着剤を利用して濃縮された13ＣＯを含む13ＣＯ富化ＣＯガスの製造方法に関する。
【０００２】
【従来の技術】
13Ｃは胃、十二指腸潰瘍の診断用マーカとしての使用が開始されており、安価な13Ｃの分離技術に対するニーズは非常に大きい。現在12Ｃからの13Ｃの分離方法としては、これらの同位体を含むＣＯ又はＣＨ4 を原料として、極低温条件下での精密蒸留法による分離が行われている。これらの方法の中ではＣＯの方が分離性は高いとされているが、12ＣＯと13ＣＯの沸点の差は１℃以下のため非常に大きな分離段数が要求され、また、極低温での液化であることから侵入熱の排除のためにかなりの寒冷発生が必要となる。ＣＨ4 での分離についてはＬＮＧの寒冷が利用できる長所はあるがＣＯよりも更に沸点の差が小さいため更に大きな分離段数が必要となる。
【０００３】
【発明が解決しようとする課題】
本発明はこのような従来技術の実状に鑑み、簡単な操作で効率よく同位体の分離ができ、低コストで13ＣＯが濃縮された13ＣＯ富化ＣＯガスを得ることができる13ＣＯ富化ＣＯガスの製造方法を提供することを目的とする。
【０００４】
【課題を解決するための手段】
本発明者等は、各種吸着剤を用いてＣＯの吸着挙動を検討する過程で、ゼオライト系吸着剤を充填した吸着塔にＣＯ含有ガスを供給すると、13ＣＯが選択的に吸着されて吸着塔出口から12ＣＯ富化ＣＯガスが流過し、一定の時間後に吸着塔を減圧に導くことにより13ＣＯ富化ＣＯガスが離脱して回収できることを見出し、本発明を完成した。
【０００５】
すなわち、本発明は次の（１）〜（５）の構成を有するものである。
（１）ＣＯ吸着剤を充填した吸着塔に13ＣＯ及び12ＣＯを含むＣＯガスを導入し、相対的に易吸着性の13ＣＯを吸着させ、相対的に難吸着性の12ＣＯを流過させて相対的に13ＣＯ濃度の低下したＣＯガスを回収し、所定時間後にＣＯガスの導入を止め、吸着塔内を減圧にすることによって吸着されている相対的に13ＣＯ濃度の高められたＣＯガスを脱離させて回収する 13 ＣＯ富化ＣＯガスの製造方法であって、前記ＣＯ吸着剤がゼオライト系吸着剤であり、同ゼオライト系吸着剤がフォウジャサイト、ペンタシルゼオライト又はモルデナイトであることを特徴とする 13 ＣＯ富化ＣＯガスの製造方法。
（２）前記ゼオライト系吸着剤がＳｉＯ2 ／Ａｌ2 Ｏ3 のモル比が２〜４０００の範囲のものであることを特徴とする前記（１）の13ＣＯ富化ＣＯガスの製造方法。
（３）前記ゼオライト系吸着剤がアルカリ金属、アルカリ土類金属及び遷移金属からなる群より選ばれる１種以上のイオンを含むものであることを特徴とする前記（１）又は（２）の13ＣＯ富化ＣＯガスの製造方法。
（４）前記ゼオライト系吸着剤がＮａ、Ｌｉ、Ｃａ、Ｆｅ、Ｃｏ及びＣｕからなる群より選ばれる１種以上のイオンを含むものであることを特徴とする前記（３）の13ＣＯ富化ＣＯガスの製造方法。
（５）前記吸着時の前記 13 ＣＯ及び 12 ＣＯを含むＣＯガスを含有する供給ガス中のＣＯの分圧が０．０１０２〜０．０３ＭＰａであることを特徴とする請求項（１）〜（４）のいずれか１つの13ＣＯ富化ＣＯガスの製造方法。
【０００６】
【発明の実施の形態】
以下、図面を参照して本発明を詳細に説明する。図１は本発明の方法を実施するための装置構成の１例を示す説明図である。
図１において、吸着時にはバルブ３、６を開き、バルブ９、１０、１４を閉じた状態でＣＯ：１０ｖｏｌ％、Ｈｅ：９０ｖｏｌ％からなる混合ガス１を質量流量計２を通して一定流量でバルブ３から吸着塔４に供給する。吸着塔４にはゼオライト系吸着剤５が充填されており、ここで13ＣＯが選択的に吸着されて吸着塔４出口からはバルブ６、流量計７を通して12ＣＯ富化ガスが流過する。
【０００７】
13ＣＯの吸着が進むと吸着能が低下するので、所定時間経過後にバルブ３を閉じて混合ガス１の供給を停止する。混合ガス１の供給を停止する時期は吸着剤の種類や吸着条件等に応じて適宜定めればよく、例えば出口の13ＣＯ濃度が上昇し始めた時点、あるいはその条件下で出口の13ＣＯ濃度が上昇し始めるまでの時間を予め実験により求めておき、出口の13ＣＯ濃度が上昇する直前などに設定すればよい。
【０００８】
その後、バルブ３、６、１０、１５を閉じ、バルブ９、１９を開いた状態で真空ポンプ８と結んだバルブ９から減圧条件下、吸着した13ＣＯ富化ガスを取り出し、更に所定の真空圧力に達したところでバルブ１０を開いて吸着塔４の後流側から減圧弁１２を通してＨｅガス１１を向流（混合ガス１の供給方向とは反対の方向）に流して13ＣＯ富化ガスの回収と吸着剤５の完全な再生を行う。
【０００９】
なお、図１の構成では、適宜バルブ１４、１５を開くことによって吸着塔４出口及び真空ポンプ８出口のガスをサンプリングし、４重極子型質量分析計１３により質量数４、２８、２９のイオン数をカウントすることにより12ＣＯ、13ＣＯ、Ｈｅの濃度を測定できるようになっている。
ガス中の濃度測定時にはサンプリングポンプ１６を作動させ、そのガス分岐し、バルブ１８を開きターボ分子ポンプ１７を作動させて４重極子型質量分析計１３へ分岐ガスを導入して測定する。吸着塔出口ガス濃度Ｃ1 の測定時にはバルブ１４を開き、脱着ガス濃度Ｃ2 の測定時にはバルブ１５を開いてそれぞれのガスを分析計に導入する。
【００１０】
吸着剤５としてはゼオライト系吸着剤や活性炭、シリカゲル、アルミナなどが使用できるが、特にゼオライト系吸着剤が好ましく、中でもフォウジャサイト、ペンタシルゼオライト又はモルデナイトが特に好適である。
また、ゼオライト系吸着剤のＳｉＯ2 ／Ａｌ2 Ｏ3 の比率はモル比で２〜４０００の範囲が好ましい。モル比が４０００より大きくなると吸着量が少なくなり、２より小さいとゼオライトの定義に入らなくなる。
ゼオライト系吸着剤は通常、ＳｉＯ2 ／Ａｌ2 Ｏ3 の骨格中にＮａなどの陽イオンを含む形で得られるが、前記陽イオンとしてはアルカリ金属、アルカリ土類金属及び遷移金属からなる群より選ばれる１種以上のイオンを含むもが好ましく、中でもＮａ、Ｌｉ、Ｃａ、Ｆｅ、Ｃｏ又はＣｕが特に好ましい。
【００１１】
本発明の方法において、供給ガス中のＣＯ濃度が１０ vol ％である供給ガスの吸着時の圧力は０．１０２〜０．３ＭＰａ、すなわち同供給ガス中のＣＯの分圧に換算して０．０１０２〜０．０３ＭＰａの範囲とするのが好ましい。吸着時の圧力がこの範囲より低くなると吸着困難となり、また、高くなると動力費が高くなってしまう。なお、脱離時の圧力は０．０００５〜０．１ＭＰａとするのが好ましく、脱離時の圧力がこの範囲を外れると再生が難しくなる。
【００１２】
通常のＣＯガス中に含まれる13ＣＯは１．１％程度であるが、本発明の方法により13ＣＯが１．１５〜１．３％程度の13ＣＯ富化ＣＯガスを得ることができる。
なお、適宜吸着塔の数を増やし、吸着工程と13ＣＯ富化ＣＯガスの脱離工程を順次切り替えて行うようにすれば、13ＣＯ富化ＣＯガス（及び12ＣＯ富化ＣＯガス）を連続的に製造することができる。また、得られた13ＣＯ富化ＣＯガスを再度吸着塔に導入して複数段の処理を行うことにより13ＣＯの濃度を高めることも可能である。
【００１３】
【実施例】
以下、実施例により本発明の方法をさらに具体的に説明する。
（実施例）
図１の構成の装置を使用し、吸着剤としては後述する方法で作製したゼオライト系吸着剤を使用して圧力スイング吸着法（ＰＳＡ）により12ＣＯと13ＣＯの分離試験を行った。吸着−減圧−向流パージ−昇圧からなるシーケンスのバルブの開閉状況を表１に、分離操作条件を表２に示す。
【００１４】
【表１】
【表２】
（吸着剤の合成）
１．フォウジャサイト型ゼオライト吸着剤の合成
水ガラスとアルミン酸ナトリウムを表３に示すケイ素とアルミニウムの比率となるように仕込み、水酸化ナトリウムをｐＨ１１となるように添加する。このとき水は分子比で１５以上添加する。温度を９０℃として３時間十分撹拌し、その後７０℃で一夜静置し、結晶を得る。デカンテーションで得られた固形分を３回水で洗浄し、表３に示すＳｉＯ2 ／Ａｌ2 Ｏ3 比のフォウジャサイトを得た。
【００１７】
２．ペンタシル型ゼオライト吸着剤の合成
水ガラスと硫酸アルミニウムを表３に示すケイ素とアルミニウムの比率となるように仕込み、水酸化ナトリウムをｐＨ１０．２〜１０．４となるように添加する。なお、テンプレートとして４級アミンを使用した。次にオートクレーブにて結晶化（結晶化温度１５０〜１７０℃、結晶化時間２０時間以上）を行い、結晶化終了後約７０℃まで空冷し、生成物を吸引ろ過する。最後に乾燥器中で乾燥させ（７０〜１１０℃）、空気中で５３０℃で焼成し、Ｎａ−ＺＳＭ−５タイプのペンタシル型ゼオライトを得た。
【００１８】
３．モルデナイトの合成
水ガラスと硫酸アルミニウムを表３に示すケイ素とアルミニウムの比率となるように仕込み、水酸化ナトリウムをｐＨ１０．２〜１０．４となるように添加する。次にオートクレーブにて結晶化（結晶化温度１２０〜１４０℃、結晶化時間２０時間以上）を行い、結晶化終了後約７０℃まで空冷し、生成物を吸引ろ過する。最後に乾燥器中で乾燥させ（７０〜１１０℃）、空気中で５３０℃で焼成し、Ｎａ−モルデナイトを得た。
【００１９】
４．ゼオライトのイオン交換
前記の方法で作製したゼオライトを使用し、次の操作によりイオン交換を行いＮａをＣｕ、Ｌｉ又はＣａでイオン交換したゼオライトを作製した。
１）スラリ化：ゼオライトを精製水中に添加し、撹拌してスラリとした。
２）脱気：１００℃で３時間煮沸・撹拌（水分の蒸発に応じて適宜精製水を加える）して脱気した。
３）冷却：加熱を止め、精製水を加え液温４０℃以下まで自然冷却した。
４）イオン交換：目的とする金属でイオン交換するため、３）で得たスラリに塩化リチウム、硝酸カルシウム又はシュウ酸銅を選択投入し、２時間撹拌してイオン交換した。
５）吸引ろ過：イオン交換後のスラリを吸引ろ過して固形分を分離。
６）洗浄：分離した固形分を精製水中に投じて撹拌後、吸引ろ過し未交換金属を洗い流した。
７）乾燥：洗浄後の固形分を１１０℃で１５時間乾燥した。
８）焼成：６５０℃にてテンプレートがなくなるまで焼成し、表３のイオン交換ゼオライトとした。
【００２０】
前記のようにして作製したゼオライト系吸着剤を使用し、表２に示した分離操作条件により、12ＣＯと13ＣＯの分離試験を行った結果を表３に示す。なお、表３中のＣａ−Ａ（試料１９）及びＮａ−Ａ（試料２０）はそれぞれ市販のＡ型ゼオライト（Ｃａ−Ａは５Ａ、Ｎａ−Ａは４Ａ）を７００℃で熱処理したものである。
【００２１】
【表３】
表３から次のことがわかる。
１）表３に示したゼオライト系吸着剤は、供給ガスの13ＣＯ／12ＣＯ同位体比（％）が１．１％（天然存在比）であるのに対し、吸着工程出口ガス中の同位体比（％）がＮａ−Ａを除いていずれも１．１％を下回ることから、13ＣＯが選択的に吸着剤に吸着されていることがわかる。
【００２３】
２）出口13ＣＯ／12ＣＯ同位体比が小さいほど13ＣＯを選択的に吸着することとなるので、最も13ＣＯ選択性の高いのは試料４〜１５のＮａ、Ｌｉ、Ｃａ等のアルカリ金属、アルカリ土類金属を交換カチオンとして有するフォウジャサイト（ faujasite）であり、これに続いて試料１６〜１８のモルデナイト（ mordenite）、試料１〜３のペンタシル（ pentasil ）の順となる。
３）試料６、７、９のフォウジャサイト、試料１６、１８のモルデナイト、試料２、３のペンタシルの比較では、いずれもＳｉＯ2 ／Ａｌ2 Ｏ3 比が小さいほど高い13ＣＯ選択性を示した。
【００２４】
４）13ＣＯ吸着量も12ＣＯ／13ＣＯ分離においては重要な要素となる。本試験では出口12ＣＯ流過率が２０％における出口ガス量が大きいほど13ＣＯ吸着量が大きく、吸着剤としてはファウジャサイト、モルデナイト、ペンタシルの順である（試料９、１６、２の比較）。また各吸着剤でＳｉＯ2 ／Ａｌ2 Ｏ3 比が小さいほど13ＣＯ吸着量が大きい。交換カチオンとしてはアルカリ金属、アルカリ土類金属、遷移金属の場合13ＣＯ吸着量が大きい。
５）試料９、１１、１２、１３の比較から吸着温度の降下に伴い13ＣＯ選択性の増大、13ＣＯ吸着量の増加が認められる。
６）試料９、１４、１５の比較から吸着圧力の増大に伴い13ＣＯ吸着量の増加が認められる。
【００２５】
【発明の効果】
本発明の方法に従い、12ＣＯと13ＣＯを含有するガスをゼオライト系吸着剤を使用して圧力スイング吸着法（ＰＳＡ）で処理することにより、13ＣＯを選択的に吸着させることができるので、効率よく13ＣＯを分離・濃縮し、13ＣＯ富化ＣＯガスを製造することができる。
【図面の簡単な説明】
【図１】本発明の方法を実施するための装置構成の１例を示す説明図。[0001]
BACKGROUND OF THE INVENTION
The present invention is a CO gas containing 13 CO and 12 CO, a method for producing a 13 CO-enriched CO gas containing 13 CO enriched using an adsorbent.
[0002]
[Prior art]
13 C has been used as a diagnostic marker for stomach and duodenal ulcers, and there is a great need for an inexpensive 13 C separation technique. At present, as a method for separating 13 C from 12 C, separation by precision distillation under cryogenic conditions is performed using CO or CH 4 containing these isotopes as a raw material. Among these methods, CO is considered to be more separable, but the difference in boiling point between 12 CO and 13 CO is 1 ° C. or less, so a very large number of separation stages is required. Since it is a liquefaction, considerable cold generation is required to eliminate intrusion heat. The separation with CH 4 has the advantage that the coldness of LNG can be used, but since the difference in boiling point is smaller than that of CO, a larger number of separation stages is required.
[0003]
[Problems to be solved by the invention]
In view of the circumstances of the prior art, can be separated efficiently isotopes by a simple operation, 13 CO enrichment 13 CO at low cost can be obtained 13 CO-enriched CO gas enriched It aims at providing the manufacturing method of CO gas.
[0004]
[Means for Solving the Problems]
In the process of examining the adsorption behavior of CO using various adsorbents, the present inventors supplied 13 CO selectively to an adsorption tower packed with a zeolite-based adsorbent, so that 13 CO was selectively adsorbed. It was found that 12 CO-enriched CO gas flows from the outlet, and 13 CO-enriched CO gas can be separated and recovered by introducing the adsorption tower to a reduced pressure after a certain period of time, thereby completing the present invention.
[0005]
That is, this invention has the structure of following (1)-( 5 ).
(1) to the adsorption column filled with the CO adsorbent by introducing CO gas containing 13 CO and 12 CO, adsorbed relatively readily adsorbable of 13 CO, flowing through the 12 CO relatively flame adsorptive The CO gas having a relatively reduced 13 CO concentration was recovered, and after a predetermined time, the introduction of the CO gas was stopped and the inside of the adsorption tower was depressurized to increase the relatively 13 CO concentration being adsorbed. the CO gas to a method for producing a 13 C O enriched CO gas you recovered desorbed, the CO adsorbent Ri zeolite adsorbent der, the zeolite adsorbent is Fou faujasite, pentasil zeolite 13 C O method for producing enriched CO gas you wherein the or mordenite.
(2) The method of producing 13 CO-enriched CO gas in the said zeolite adsorbent is a molar ratio of SiO 2 / Al 2 O 3 is characterized in that in the range of 2 to 4000 (1).
( 3 ) The 13 CO rich material according to ( 1 ) or (2 ) above, wherein the zeolitic adsorbent contains one or more ions selected from the group consisting of alkali metals, alkaline earth metals and transition metals. CO gas production method.
(4) the zeolite adsorbent is Na, Li, Ca, Fe, 13 CO -enriched CO gas in the (3), characterized in that those comprising one or more ions selected from the group consisting of Co and Cu Manufacturing method.
(5) the preceding claims, the partial pressure of CO in the feed gas containing CO gas containing 13 CO and 12 CO during adsorption, characterized in that a 0.0102 ~ 0.03 MPa (1) ~ ( 4 ) The manufacturing method of any one 13 CO-enriched CO gas.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 is an explanatory diagram showing an example of a device configuration for carrying out the method of the present invention.
In FIG. 1, the valves 3 and 6 are opened at the time of adsorption, and the mixed gas 1 composed of CO: 10 vol% and He: 90 vol% is passed through the mass flow meter 2 at a constant flow rate from the valve 3 with the valves 9, 10 and 14 closed. Supply to the adsorption tower 4. The adsorption tower 4 is filled with a zeolitic adsorbent 5, where 13 CO is selectively adsorbed, and 12 CO-enriched gas flows from the outlet of the adsorption tower 4 through a valve 6 and a flow meter 7.
[0007]
As the adsorption of 13 CO proceeds, the adsorbing capacity decreases, so that the valve 3 is closed after a predetermined time has elapsed and the supply of the mixed gas 1 is stopped. Time to stop the supply of the mixed gas 1 may be appropriately determined depending on such kind and adsorption conditions of the adsorbent, for example, point 13 CO concentration at the outlet began to rise or 13 CO concentration at the outlet under these conditions, The time until the start of the rise may be obtained in advance by experiments, and may be set immediately before the 13 CO concentration at the outlet rises.
[0008]
Thereafter, the adsorbed 13 CO-enriched gas is taken out from the valve 9 connected to the vacuum pump 8 with the valves 3, 6, 10, 15 closed and the valves 9, 19 opened, and further, a predetermined vacuum pressure is obtained. The valve 10 is opened and the He gas 11 is caused to flow counter-currently (in the direction opposite to the supply direction of the mixed gas 1) from the downstream side of the adsorption tower 4 through the pressure reducing valve 12 to recover 13 CO-enriched gas. And complete regeneration of the adsorbent 5.
[0009]
In the configuration of FIG. 1, the gas at the outlet of the adsorption tower 4 and the outlet of the vacuum pump 8 is sampled by opening the valves 14 and 15 as appropriate, and ions having mass numbers of 4, 28, and 29 are detected by the quadrupole mass spectrometer 13. The concentration of 12 CO, 13 CO, and He can be measured by counting the number.
At the time of measuring the concentration in the gas, the sampling pump 16 is operated, the gas is branched, the valve 18 is opened, the turbo molecular pump 17 is operated, and the branched gas is introduced into the quadrupole mass spectrometer 13 for measurement. When the adsorption tower outlet gas concentration C 1 is measured, the valve 14 is opened, and when the desorption gas concentration C 2 is measured, the valve 15 is opened to introduce each gas into the analyzer.
[0010]
As the adsorbent 5, a zeolite adsorbent, activated carbon, silica gel, alumina or the like can be used, and a zeolite adsorbent is particularly preferable, among which faujasite, pentasil zeolite or mordenite is particularly preferable.
In addition, the molar ratio of SiO 2 / Al 2 O 3 in the zeolite adsorbent is preferably in the range of 2 to 4000. When the molar ratio is larger than 4000, the amount of adsorption decreases, and when it is smaller than 2, the zeolite is not defined.
Zeolite-based adsorbent is usually obtained in a form containing a cation such as Na in the SiO 2 / Al 2 O 3 skeleton, and the cation is selected from the group consisting of alkali metals, alkaline earth metals and transition metals. One containing at least one selected ion is preferable, and Na, Li, Ca, Fe, Co, or Cu is particularly preferable.
[0011]
In the method of the present invention, the pressure at the time of adsorption of the supply gas having a CO concentration of 10 vol % in the supply gas is 0.102 to 0.3 MPa , that is , 0. 0 in terms of the partial pressure of CO in the supply gas. preferably that it is in the range of 0102~0.03MPa. If the pressure at the time of adsorption is lower than this range, it will be difficult to adsorb, and if it is higher, the power cost will be higher. The pressure at the time of desorption is preferably 0.0005 to 0.1 MPa. If the pressure at the time of desorption is out of this range, regeneration becomes difficult.
[0012]
Although 13 CO contained in the normal CO gas is about 1.1%, 13 CO by the method of the present invention can be obtained 13 CO-enriched CO gas of about 1.15 to 1.3%.
If the number of adsorption towers is appropriately increased and the adsorption process and the 13 CO-enriched CO gas desorption process are sequentially switched, 13 CO-enriched CO gas (and 12 CO-enriched CO gas) is continuously used. Can be manufactured automatically. It is also possible to increase the concentration of 13 CO by introducing the obtained 13 CO-enriched CO gas again into the adsorption tower and performing a plurality of stages of treatment.
[0013]
【Example】
Hereinafter, the method of the present invention will be described more specifically with reference to examples.
(Example)
A separation test of 12 CO and 13 CO was conducted by a pressure swing adsorption method (PSA) using a zeolite-type adsorbent prepared by the method described later as the adsorbent using the apparatus having the configuration shown in FIG. Table 1 shows the valve opening / closing status of the sequence consisting of adsorption-decompression-countercurrent purge-pressurization, and Table 2 shows the separation operation conditions.
[0014]
[Table 1]
[Table 2]
(Synthesis of adsorbent)
1. Synthetic water glass of faujasite type zeolite adsorbent and sodium aluminate are charged so as to have a ratio of silicon and aluminum shown in Table 3, and sodium hydroxide is added so as to have a pH of 11. At this time, water is added in a molecular ratio of 15 or more. The temperature is set to 90 ° C., and the mixture is sufficiently stirred for 3 hours, and then allowed to stand at 70 ° C. overnight to obtain crystals. The solid content obtained by decantation was washed with water three times to obtain faujasite having a SiO 2 / Al 2 O 3 ratio shown in Table 3.
[0017]
2. A synthetic water glass and aluminum sulfate of a pentasil-type zeolite adsorbent are charged so as to have a ratio of silicon and aluminum shown in Table 3, and sodium hydroxide is added so as to have a pH of 10.2 to 10.4. A quaternary amine was used as a template. Next, crystallization is performed in an autoclave (crystallization temperature: 150 to 170 ° C., crystallization time: 20 hours or more). Finally, it was dried in a drier (70 to 110 ° C.) and calcined in air at 530 ° C. to obtain a Na-ZSM-5 type pentasil-type zeolite.
[0018]
3. A synthetic water glass of mordenite and aluminum sulfate are charged so as to have a ratio of silicon and aluminum shown in Table 3, and sodium hydroxide is added so as to have a pH of 10.2 to 10.4. Next, crystallization is performed in an autoclave (crystallization temperature: 120 to 140 ° C., crystallization time: 20 hours or more). Finally, it was dried in a drier (70 to 110 ° C.) and calcined in air at 530 ° C. to obtain Na-mordenite.
[0019]
4). Ion exchange of zeolite Using the zeolite produced by the above method, ion exchange was performed by the following operation to produce zeolite in which Na was ion exchanged with Cu, Li or Ca.
1) Slurry: Zeolite was added to purified water and stirred to make a slurry.
2) Degassing: Degassing by boiling and stirring at 100 ° C. for 3 hours (adding purified water as appropriate according to evaporation of water).
3) Cooling: Heating was stopped, purified water was added, and the mixture was naturally cooled to a liquid temperature of 40 ° C. or lower.
4) Ion exchange: In order to perform ion exchange with the target metal, lithium chloride, calcium nitrate or copper oxalate was selectively added to the slurry obtained in 3), and ion exchange was performed by stirring for 2 hours.
5) Suction filtration: The slurry after ion exchange is suction filtered to separate the solids.
6) Washing: The separated solid was poured into purified water and stirred, and then suction filtered to wash away unexchanged metal.
7) Drying: The solid content after washing was dried at 110 ° C. for 15 hours.
8) Firing: Firing was performed at 650 ° C. until the template disappeared, and the ion-exchanged zeolite shown in Table 3 was obtained.
[0020]
Table 3 shows the results of a separation test for 12 CO and 13 CO using the zeolite-based adsorbent prepared as described above under the separation operation conditions shown in Table 2. In Table 3, Ca-A (sample 19) and Na-A (sample 20) are obtained by heat-treating commercially available A-type zeolite (Ca-A is 5A, Na-A is 4A) at 700 ° C. .
[0021]
[Table 3]
Table 3 shows the following.
1) The zeolitic adsorbents shown in Table 3 show that the 13 CO / 12 CO isotope ratio (%) of the feed gas is 1.1% (natural abundance ratio), whereas the isotope in the adsorption process outlet gas Since the body ratio (%) is less than 1.1% except for Na-A, it is understood that 13 CO is selectively adsorbed by the adsorbent.
[0023]
2) The smaller the outlet 13 CO / 12 CO isotope ratio, the more selectively 13 CO is adsorbed, so the 13 CO selectivity is the highest in alkali metals such as Na, Li, and Ca of Samples 4-15. Faujasite having an alkaline earth metal as an exchange cation, followed by mordenite of samples 16 to 18 and pentasil of samples 1 to 3.
3) In the comparison of faujasite of samples 6, 7 and 9, mordenite of samples 16 and 18, and pentasil of samples 2 and 3, all show higher 13 CO selectivity as the SiO 2 / Al 2 O 3 ratio is smaller. It was.
[0024]
4) The amount of 13 CO adsorption is also an important factor in 12 CO / 13 CO separation. In this test, the larger the outlet gas amount when the outlet 12 CO flow rate is 20%, the larger the 13 CO adsorption amount, and the adsorbents are in the order of faujasite, mordenite, and pentasil (comparison of samples 9, 16, and 2). ). Further, the smaller the SiO 2 / Al 2 O 3 ratio in each adsorbent, the greater the 13 CO adsorption amount. In the case of alkali metals, alkaline earth metals, and transition metals as exchange cations, 13 CO adsorption is large.
5) From the comparison of samples 9, 11, 12, and 13 , an increase in 13 CO selectivity and an increase in 13 CO adsorption amount are observed as the adsorption temperature decreases.
6) From the comparison of samples 9, 14, and 15, an increase in 13 CO adsorption amount is observed with an increase in adsorption pressure.
[0025]
【The invention's effect】
According to the method of the present invention, 13 CO can be selectively adsorbed by treating a gas containing 12 CO and 13 CO by a pressure swing adsorption method (PSA) using a zeolitic adsorbent. 13 CO can be efficiently separated and concentrated to produce 13 CO-enriched CO gas.
[Brief description of the drawings]
FIG. 1 is an explanatory diagram showing an example of an apparatus configuration for carrying out a method of the present invention.
Claims (5)
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| JP3462678B2 (en) * | 1996-10-29 | 2003-11-05 | 三菱重工業株式会社 | Separation method of N14 ammonia and N15 ammonia using copper ion exchanged zeolite |
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