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JP7207284B2 - Gas separation and recovery equipment and gas separation and recovery method - Google Patents

Gas separation and recovery equipment and gas separation and recovery method Download PDF

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JP7207284B2
JP7207284B2 JP2019226648A JP2019226648A JP7207284B2 JP 7207284 B2 JP7207284 B2 JP 7207284B2 JP 2019226648 A JP2019226648 A JP 2019226648A JP 2019226648 A JP2019226648 A JP 2019226648A JP 7207284 B2 JP7207284 B2 JP 7207284B2
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JP2021094513A (en
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伸行 紫垣
康弘 茂木
たかし 原岡
正大 田部
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Description

本発明は、ガス分離回収設備およびガス分離回収方法に関する。 The present invention relates to a gas separation and recovery facility and a gas separation and recovery method.

従来、原料ガスに含まれる所定のガス成分を分離する方法として、圧力スイング吸着（Pressure Swing Adsorption、ＰＳＡ）法が用いられてきた（例えば、特許文献１、非特許文献１および２参照）。ＰＳＡ法は、吸着剤に対するガス成分の吸着量がガス成分の種類およびその分圧によって異なることを利用した分離方法である。 Conventionally, a pressure swing adsorption (PSA) method has been used as a method for separating a predetermined gas component contained in a raw material gas (see, for example, Patent Document 1, Non-Patent Documents 1 and 2). The PSA method is a separation method that utilizes the fact that the amount of gas components adsorbed on an adsorbent varies depending on the type of gas component and its partial pressure.

ＰＳＡ法は、通常、吸着剤にガス成分を吸着させる工程（吸着工程）、他の吸着塔で脱着された脱着ガスの一部を洗浄ガスとして供給して不純物ガスを追い出す工程（洗浄工程）、および吸着したガス成分を吸着剤から脱着させてガスを回収する工程（脱着工程）を有する。 The PSA method usually includes a step of adsorbing gas components to an adsorbent (adsorption step), a step of supplying a part of the desorbed gas desorbed in another adsorption tower as a cleaning gas to drive out impurity gases (cleaning step), and a step of desorbing the adsorbed gas component from the adsorbent to recover the gas (desorption step).

このＰＳＡ法は、種々の分野に適用されているが、原料ガスに含まれる一成分を吸着させることにより、高濃度のガスを製造する方法として利用されることが多い。ＰＳＡ法は、「加圧－常圧」の圧力差を用いる加圧方式と、「常圧（または微加圧）－減圧」の圧力差を用いる吸引方式があり、後者についてはＶＳＡ（Vacuum Swing Adsorption）法と呼ばれることもある。 This PSA method is applied in various fields, and is often used as a method for producing high-concentration gas by adsorbing one component contained in the source gas. The PSA method includes a pressurization method that uses a pressure difference of "pressurization - normal pressure" and a suction method that uses a pressure difference of "normal pressure (or slight pressure) - decompression". Adsorption) method.

近年、製鉄プロセス等から排出される二酸化炭素（以下、「ＣＯ2」とも言う。）からメタノールなどの有用な化学品を製造するＣＯ2有効利用プロセスが検討されている。この反応は、例えば水素（以下、「Ｈ2」とも言う。）を利用する反応として、以下の反応式（１）にて表される。
ＣＯ2 ＋ ３Ｈ2 → ＣＨ3ＯＨ ＋Ｈ2Ｏ （１） In recent years, a CO 2 effective utilization process for producing useful chemicals such as methanol from carbon dioxide (hereinafter also referred to as “CO 2 ”) discharged from iron manufacturing processes and the like has been studied. This reaction is represented by the following reaction formula (1) as a reaction utilizing hydrogen (hereinafter also referred to as “H 2 ”), for example.
CO2 +3H2-> CH3OH + H2O (1)

上記反応に用いられるＣＯ2およびＨ2は、何れも製鉄所の副生ガス（以下、副生ガス）に含まれるため、副生ガスからＣＯ2およびＨ2を分離することによって、上記反応式（１）の原料ガスとして用いることができる。 Both CO 2 and H 2 used in the above reaction are contained in the by-product gas (hereinafter referred to as by-product gas) of steelworks, so by separating CO 2 and H 2 from the by-product gas, the above reaction formula It can be used as the raw material gas of (1).

副生ガスからのＣＯ2分離およびＨ2分離は、何れも上述のＰＳＡ法により行うことができる。例えばＣＯ2－ＰＳＡプロセスとしては、吸着剤としてゼオライトを用いる方法（例えば、非特許文献３参照）がある。また、Ｈ2－ＰＳＡプロセスとしては、吸着剤として活性炭およびゼオライトを用いる方法（例えば、特許文献２参照）がある。 Both CO 2 separation and H 2 separation from the by-product gas can be performed by the PSA method described above. For example, as a CO 2 -PSA process, there is a method using zeolite as an adsorbent (see, for example, Non-Patent Document 3). Also, as an H 2 -PSA process, there is a method using activated carbon and zeolite as adsorbents (see, for example, Patent Document 2).

一般的に、ＰＳＡ装置は、１種類の特定ガス成分の分離のみを目的として設計されるため、副生ガスなどの多成分（３種類以上のガス成分）混合ガスからＣＯ2およびＨ2をそれぞれ分離するためには、ＣＯ2－ＰＳＡ装置およびＨ2－ＰＳＡ装置を両方設ける必要があり、設備コストが増加する。多成分混合ガスが、例えばＣＯ2、Ｎ2、Ｈ2の３成分のみであれば、Ｎ2－ＰＳＡプロセスによりＮ2のみを分離する方法も考えられるが、Ｎ2はＣＯ2、Ｈ2に対して中間的な吸着力を有するため、Ｎ2のみを選択的に吸着分離してＣＯ2およびＨ2を得ることは難しい。 In general, a PSA apparatus is designed for the purpose of separating only one specific gas component, so CO2 and H2 are respectively separated from a multi-component (3 or more gas components) mixed gas such as by-product gas. For separation, both a CO 2 -PSA device and an H 2 -PSA device must be installed, which increases equipment costs. For example, if the multi-component mixed gas contains only the three components of CO 2 , N 2 and H 2 , a method of separating only N 2 by the N 2 -PSA process is also possible. Since it has an intermediate adsorptive power, it is difficult to selectively adsorb and separate only N 2 to obtain CO 2 and H 2 .

一方、例えば特許文献３に開示されるように、吸着剤からのガス脱着時間が吸着したガス成分の種類によって異なる特性を利用して、ガス脱着時間差によりガス分離を行う方法もある。図１は、ガス脱着時間差によりガス分離を行うガス分離回収設備の一例を示している。 On the other hand, as disclosed in Patent Document 3, for example, there is also a method of performing gas separation based on the gas desorption time difference by utilizing the characteristic that the gas desorption time from the adsorbent varies depending on the type of the adsorbed gas component. FIG. 1 shows an example of a gas separation and recovery facility that performs gas separation using a gas desorption time difference.

図１に示したガス分離回収設備１００においては、各吸着塔１０１、１０２は、原料ガスを吸着塔１０１、１０２内に導入するガス導入配管１０１ａと、吸着塔１０１、１０２内からガスを排出するガス排出配管１０１ｂ、１０２ｂとを有する。また、各吸着塔１０１、１０２のガス排出配管にガス排気手段ＶＰが接続されており、ガス排気手段ＶＰの出側に、バルブ操作によって切り替え可能な２系統のガス回収配管１０３ａ、１０３ｂが設けられている。吸着塔１０１、１０２には、ゼオライトや活性炭など、ＣＯ2を吸着しやすい吸着剤が充填される。 In gas separation and recovery equipment 100 shown in FIG. It has gas discharge pipes 101b and 102b. A gas exhaust means VP is connected to the gas discharge pipes of the adsorption towers 101 and 102, and two gas recovery pipes 103a and 103b switchable by valve operation are provided on the outlet side of the gas exhaust means VP. ing. The adsorption towers 101 and 102 are filled with an adsorbent that easily adsorbs CO 2 such as zeolite and activated carbon.

図１に示したガス分離回収設備１００においては、図２に示すように、まず吸着工程において、吸着剤に吸着しない（すなわち、吸着力が極めて小さい）Ｈ2を吸着オフガスとして分離して回収する。次に、脱着工程において、ＣＯ2とＮ2とをガス脱着時間差によって分離する。具体的には、まず脱着工程（１）において、吸着力が比較的弱いＮ2を分離し、次いで脱着工程（２）において、吸着力が比較的強いＣＯ2を分離する。こうして、原料ガスからＨ2およびＣＯ2をＰＳＡの１工程の中で分離して回収することができる。 In the gas separation and recovery equipment 100 shown in FIG. 1, as shown in FIG. 2, first, in the adsorption step, H 2 that is not adsorbed by the adsorbent (that is, the adsorption force is extremely small) is separated and recovered as adsorption off-gas. . Next, in the desorption step, CO 2 and N 2 are separated by the gas desorption time difference. Specifically, first, in the desorption step (1), N 2 with relatively weak adsorption force is separated, and then in desorption step (2), CO 2 with relatively strong adsorption force is separated. Thus, H 2 and CO 2 can be separated and recovered from the feed gas in one PSA step.

なお、図２において、白いバルブは開状態のバルブ、黒いバルブは閉状態のバルブ、破線は閉状態のバルブによりガスが流通していないガス配管をそれぞれ示している。また、図２におけるＨ2およびＣＯ2は、正確にはＨ2やＣＯ2以外の不純物ガスを含むガス（すなわち、Ｈ2リッチガスおよびＣＯ2リッチガス）であるが、以下、説明の簡略化のため、単にＨ2ガスおよびＣＯ2ガスと称する。 In FIG. 2, white valves indicate open valves, black valves indicate closed valves, and broken lines indicate gas pipes through which gas is not circulated due to the closed valves. Also, H 2 and CO 2 in FIG. 2 are precisely gases containing impurity gases other than H 2 and CO 2 (that is, H 2 rich gas and CO 2 rich gas), but for the sake of simplification of explanation, , simply referred to as H 2 gas and CO 2 gas.

特開平０６－１４４８１８号公報JP-A-06-144818 特開２０１８－１１４４６４号公報JP 2018-114464 A 特開２００２－３５５５１９号公報JP 2002-355519 A

N. Heymans et al.，「Experimental and theoretical study of the adsorption of pure molecules and binary systems containing methane, carbon monoxide, carbon dioxide and nitrogen. Application to the syngas generation」, Chemical Engineering Science 66（2011）pp. 3850-3858N. Heymans et al., "Experimental and theoretical study of the adsorption of pure molecules and binary systems containing methane, carbon monoxide, carbon dioxide and nitrogen. Application to the syngas generation", Chemical Engineering Science 66 (2011) pp. 3850- 3858 A. Arefi Pour et al.，「Adsorption separation of CO2/CH4 on the synthesized NaA zeolite shaped with montmorillonite clay in natural gas purification process」，Journal of Natural Gas Science and Engineering 36（2016）pp. 630-643A. Arefi Pour et al., "Adsorption separation of CO2/CH4 on the synthesized NaA zeolite shaped with montmorillonite clay in natural gas purification process", Journal of Natural Gas Science and Engineering 36 (2016) pp. 630-643 斉間等、茂木康弘、原岡たかし：ＰＳＡ法による高炉ガスからの炭酸ガス分離技術の開発，ＪＦＥ技報，Ｎｏ．３２（２０１３），ｐ４４－４９Saima et al., Motegi Yasuhiro, Haraoka Takashi: Development of Technology for Separating Carbon Dioxide from Blast Furnace Gas by PSA Method, JFE Technical Report, No. 32 (2013), p44-49

原料ガスが、例えばＣＯ2、Ｎ2、Ｈ2の３成分で構成された混合ガスである場合、図２に示したＰＳＡプロセスにおいて、Ｈ2濃度の高い吸着オフガスを得るためには、ＣＯ2およびＮ2の両方を吸着剤に吸着させて分離する必要がある。例えば、吸着剤として１３Ｘゼオライトを用いる場合、同じガス分圧に対する１３ＸゼオライトへのＮ2の吸着量は、ＣＯ2の吸着量よりも少ない。そのため、図３（ａ）に示すように、原料ガスの供給量が多い場合には、吸着剤に吸着されない不純物ガスＮ2が吸着オフガスに流出して排出される。 If the raw material gas is, for example, a mixed gas composed of the three components of CO 2 , N 2 and H 2 , in the PSA process shown in FIG . and N 2 must be separated by adsorption on an adsorbent. For example, when using 13X zeolite as an adsorbent, the amount of N2 adsorbed on 13X zeolite is less than the amount of CO2 adsorbed for the same gas partial pressure. Therefore, as shown in FIG. 3A, when the supply amount of the source gas is large, the impurity gas N2 that is not adsorbed by the adsorbent flows out into the adsorption off-gas and is discharged.

吸着オフガスに流出するＮ2量が多くなると、吸着オフガスのＨ2濃度が低下してしまう。そのため、吸着オフガスのＨ2濃度を高めるためには、図３（ｂ）に示すように、原料ガスの供給量を少なくして、吸着オフガスに流出するＮ2量を抑制する必要がある。 When the amount of N 2 flowing out to the adsorption off-gas increases, the H 2 concentration of the adsorption off-gas decreases. Therefore, in order to increase the H 2 concentration of the adsorption off-gas, it is necessary to reduce the amount of raw material gas supplied to suppress the amount of N 2 flowing out to the adsorption off-gas, as shown in FIG. 3(b).

しかしながら、本発明者らが、図３（ｂ）に示すように、原料ガスの供給量を少なくしたところ、今度は、図２に示す脱着工程においてガス脱着時間差によりＣＯ2を分離回収する際に、回収ガスにおけるＣＯ2の回収率が低下することが判明した。 However, when the inventors of the present invention reduced the supply amount of the source gas as shown in FIG . , the recovery of CO 2 in the recovered gas was found to decrease.

本発明は、上記技術課題を解決するためになされたものであり、その目的とするところは、多成分混合ガスから複数の特定のガス成分を効率的に分離して回収することができるガス分離回収設備およびガス分離回収方法を提案することにある。 The present invention has been made to solve the above technical problems, and an object of the present invention is to provide a gas separator capable of efficiently separating and recovering a plurality of specific gas components from a multi-component mixed gas. The object of the present invention is to propose a recovery facility and a gas separation recovery method.

上記課題を解決する本発明は、以下の通りである。
［１］圧力スイング吸着法によって３種類以上のガス成分を有する原料ガスから２種類以上のガス成分を分離して回収するためのガス分離回収設備であって、
２つ以上の吸着塔が直列に配置された吸着塔列であって、各吸着塔は、前記２種類以上のガス成分のうちの少なくとも１種類のガス成分を吸着する吸着剤が充填され、吸着塔内にガスを導入するガス導入配管と、吸着塔内からガスを排出するガス排出配管とを有し、隣接する２つの吸着塔の上流側の吸着塔のガス排出配管と下流側の吸着塔のガス導入配管とが接続されている、吸着塔列と、
各吸着塔のガス排出配管に接続され、各吸着塔に充填された吸着剤に吸着したガス成分を脱着して脱着ガスとして吸着塔から排出する排気手段と、
前記排気手段の出側に接続され、バルブ操作により切り替え可能な２系統のガス回収配管と、
を具えることを特徴とするガス分離回収装置。 The present invention for solving the above problems is as follows.
[1] A gas separation and recovery facility for separating and recovering two or more gas components from a raw material gas having three or more gas components by a pressure swing adsorption method,
An adsorption tower train in which two or more adsorption towers are arranged in series, each adsorption tower being filled with an adsorbent that adsorbs at least one gas component out of the two or more gas components. It has a gas introduction pipe that introduces gas into the tower and a gas discharge pipe that discharges gas from the adsorption tower, and the gas discharge pipe of the upstream adsorption tower and the downstream adsorption tower of two adjacent adsorption towers. an adsorption tower row connected to the gas introduction pipe of
an exhaust means connected to the gas discharge pipe of each adsorption tower for desorbing the gas component adsorbed by the adsorbent packed in each adsorption tower and discharging it from the adsorption tower as desorbed gas;
two gas recovery pipes connected to the outlet side of the exhaust means and switchable by valve operation;
A gas separation and recovery device comprising:

［２］前記吸着剤が、前記３種類以上のガス成分に対してそれぞれ異なる吸着等温線を有する、前記［１］に記載のガス分離回収設備。 [2] The gas separation and recovery equipment according to [1], wherein the adsorbent has different adsorption isotherms for the three or more gas components.

［３］前記［１］または［２］に記載のガス分離回収設備を用いて、圧力スイング吸着法によって３種類以上のガス成分を有する原料ガスから２種類以上のガス成分のガスを分離して回収するガス分離回収方法であって、
各吸着塔列における吸着塔に充填された吸着剤にガス成分を吸着させる吸着工程では、前記吸着塔列の最上流の吸着塔から最下流の吸着塔に向かって前記原料ガスを流通させ、前記最下流の吸着塔のガス排出配管から排出された、前記３種類以上のガス成分のうち前記吸着塔列における吸着塔に充填された吸着剤に吸着されなかったガス成分のガスを吸着オフガスとして分離して回収し、
前記吸着工程において前記吸着剤に吸着させたガス成分を脱着させる脱着工程では、前記吸着塔列における吸着塔のうちの１つ以上の吸着塔において、脱着工程を複数の時間帯に区分けして、時間帯毎に前記３種類以上のガス成分のうちの異なるガス成分のガスを分離して回収することを特徴とするガス分離回収方法。 [3] Using the gas separation and recovery equipment described in [1] or [2] above, a gas having two or more gas components is separated from a raw material gas having three or more gas components by a pressure swing adsorption method. A gas separation and recovery method for recovering,
In the adsorption step of adsorbing the gas component to the adsorbent packed in the adsorption tower in each adsorption tower row, the source gas is circulated from the most upstream adsorption tower to the most downstream adsorption tower in the adsorption tower row, The gas of the gas component that is not adsorbed by the adsorbent filled in the adsorption towers in the adsorption tower row among the three or more types of gas components discharged from the gas discharge pipe of the adsorption tower at the most downstream is separated as adsorption off-gas. to collect and
In the desorption step of desorbing the gas components adsorbed by the adsorbent in the adsorption step, in one or more adsorption towers among the adsorption towers in the adsorption tower row, the desorption step is divided into a plurality of time zones, 1. A gas separation and recovery method, comprising separating and recovering gases of different gas components out of the three or more types of gas components for each time slot.

本発明によれば、多成分混合ガスから複数の特定のガス成分を効率的に分離して回収することができる。 ADVANTAGE OF THE INVENTION According to this invention, several specific gas components can be efficiently isolate|separated and collect|recovered from multi-component mixed gas.

ガス脱着時間差によりガス分離を行うことができるガス分離回収装置の一例を示す図である。FIG. 2 is a diagram showing an example of a gas separation and recovery apparatus capable of gas separation based on a gas desorption time difference. 図１に示した装置を用いて、ＰＳＡの１工程において２種類のガス成分を分離する方法を説明する図である。It is a figure explaining the method of isolate|separating two types of gas components in 1 process of PSA using the apparatus shown in FIG. 原料ガスの供給量と吸着オフガスの水素濃度との関係を説明する図であり、（ａ）は原料ガスの供給量が多い場合、（ｂ）は原料ガスの供給量が少ない場合に関する図である。FIG. 4 is a diagram for explaining the relationship between the supply amount of the raw material gas and the hydrogen concentration of the adsorption off-gas, where (a) is a diagram for when the supply amount of the raw material gas is large, and (b) is a diagram for when the supply amount of the raw material gas is small. . 従来法における、原料ガスの供給量と、吸着オフガスのＨ2濃度およびＨ2回収率、回収ガスのＣＯ2濃度およびＣＯ2回収率との関係を示す図である。FIG. 4 is a graph showing the relationship between the supply amount of raw material gas, the H 2 concentration and H 2 recovery rate of adsorption off-gas, and the CO 2 concentration and CO 2 recovery rate of recovered gas, in a conventional method. 本発明によるガス分離回収設備の一例を示す図である。It is a figure which shows an example of the gas-separation-and-recovery installation by this invention. 本発明によるガス分離回収方法を説明する図である。BRIEF DESCRIPTION OF THE DRAWINGS It is a figure explaining the gas separation recovery method by this invention. 従来法および本発明による、吸着オフガスのＨ2濃度およびＨ2回収率、回収ガスのＣＯ2濃度およびＣＯ2回収率、をそれぞれ比較した図である。FIG. 3 compares the H 2 concentration and H 2 recovery of the adsorption off-gas and the CO 2 concentration and CO 2 recovery of the recovered gas according to the conventional method and the present invention, respectively.

以下、図面を参照して、本発明の実施形態について説明する。本発明によるガス分離回収設備は、圧力スイング吸着法によって３種類以上のガス成分を有する原料ガスから２種類以上のガス成分を分離して回収するためのガス分離回収設備であり、２つ以上の吸着塔が直列に配置された吸着塔列であって、各吸着塔は、２種類以上のガス成分のうちの少なくとも１種類のガス成分を吸着する吸着剤が充填され、吸着塔内にガスを導入するガス導入配管と、吸着塔内からガスを排出するガス排出配管とを有し、隣接する２つの吸着塔の上流側の吸着塔のガス排出配管と下流側の吸着塔のガス導入配管とが接続されている、吸着塔列と、各吸着塔のガス排出配管に接続され、各吸着塔に充填された吸着剤に吸着したガス成分を脱着して脱着ガスとして吸着塔から排出する排気手段と、排気手段の出側に接続され、バルブ操作により切り替え可能な２系統のガス回収配管とを具えることを特徴とする。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. A gas separation and recovery facility according to the present invention is a gas separation and recovery facility for separating and recovering two or more gas components from a raw material gas having three or more gas components by a pressure swing adsorption method. An adsorption tower row in which adsorption towers are arranged in series, each adsorption tower being filled with an adsorbent that adsorbs at least one gas component out of two or more gas components, and the adsorption tower is filled with a gas. It has a gas introduction pipe for introducing gas and a gas discharge pipe for discharging gas from the adsorption tower, and the gas discharge pipe for the upstream adsorption tower and the gas introduction pipe for the downstream adsorption tower of two adjacent adsorption towers. and an exhaust means connected to the gas discharge pipe of each adsorption tower, desorbing the gas component adsorbed by the adsorbent packed in each adsorption tower and discharging it from the adsorption tower as desorbed gas. and two gas recovery pipes connected to the outlet side of the exhaust means and switchable by valve operation.

上述のように、図１に示したガス分離回収設備１００において、吸着塔１０１（１０２）に供給する原料ガスの供給量を少なくすれば、吸着オフガスのＨ2濃度を高めることができるが、今度は回収ガスにおけるＣＯ2の回収率が低下することが判明した。以下、この知見を得るに至ったラボスケールのＰＳＡ実験について説明する。 As described above, in the gas separation and recovery equipment 100 shown in FIG. 1, if the supply amount of the raw material gas supplied to the adsorption tower 101 (102) is reduced, the H 2 concentration of the adsorption off-gas can be increased. was found to reduce the recovery of CO2 in the recovered gas. The lab-scale PSA experiments that led to this finding are described below.

上記ラボスケールのＰＳＡ実験は、図１に示したような２つの吸着塔を用いて行った。具体的には、原料ガスとして、３７％ＣＯ2、４１％Ｎ2、２２％Ｈ2の混合ガスを使用し、内径４２ｍｍ×高さ２００ｍｍのＳＵＳで構成された吸着塔に１３Ｘゼオライト吸着剤を１塔当り１９０ｇ充填した。吸着塔の運転条件は、サイクルタイムを８０～１５０ｓｅｃ／ｃｙｃｌｅ、原料ガスの供給量を６．７～１２．７ＮＬ／ｋｇ吸着剤／ｃｙｃｌｅとした。また、吸着塔内の圧力は、吸着圧５０ｋＰａＧ、脱着圧－９５ｋＰａＧとした。 The above lab-scale PSA experiments were performed using two adsorption towers as shown in FIG. Specifically, a mixed gas of 37% CO 2 , 41% N 2 , and 22% H 2 was used as the raw material gas, and 13X zeolite adsorbent was added to an adsorption tower made of SUS with an inner diameter of 42 mm and a height of 200 mm. 190 g was packed per column. The operating conditions of the adsorption tower were a cycle time of 80 to 150 sec/cycle and a feed gas supply rate of 6.7 to 12.7 NL/kg adsorbent/cycle. The pressure in the adsorption tower was set to an adsorption pressure of 50 kPaG and a desorption pressure of -95 kPaG.

図４は、上記ラボスケールＰＳＡ実験において、ＣＯ2、Ｎ2およびＨ2の分離実験を行った際の原料ガスの供給量と吸着オフガスのＨ2濃度および回収ガスのＣＯ2回収率との関係を示している。図４に示すように、原料ガス供給量が少なくなると、吸着オフガスのＨ2濃度は上昇した。しかしながら、回収ガスの特にＣＯ2回収率（回収ＣＯ2濃度９０％）については、原料ガスの供給量が少なくなるほど低下した。 Fig. 4 shows the relationship between the supply amount of raw material gas, the H2 concentration of the adsorption off - gas, and the CO2 recovery rate of the recovered gas when the separation experiment of CO2 , N2 and H2 was conducted in the lab - scale PSA experiment. is shown. As shown in FIG. 4, the H 2 concentration of the adsorption off-gas increased as the raw material gas supply rate decreased. However, especially the CO 2 recovery rate (recovered CO 2 concentration 90%) of the recovered gas decreased as the supply amount of the raw material gas decreased.

本発明者らは、上記ＣＯ2回収の低下の原因について鋭意調査した。その結果、図３（ｂ）に示したような原料ガス供給量が少ない運転条件では、吸着工程の完了時に吸着塔内に残存する不純物ガスＮ2の量が多くなるため、図２に示した脱着工程（１）における不純物ガスの除去（脱着）時間が増加し、それに伴い、図２に示した不純物ガスとともに、回収ガスＣＯ2の一部が脱着して不純物ガスＮ2のガス回収配管１０３ａに流出してしまうことが原因であることが判明した。 The present inventors diligently investigated the cause of the decline in CO 2 recovery. As a result, under the operating conditions where the raw material gas supply amount is small as shown in FIG . The impurity gas removal (desorption) time in the desorption step (1) increases, and along with this, part of the recovery gas CO 2 is desorbed together with the impurity gas shown in FIG . It was found that the cause was that the

そこで本発明者らは、上述のような回収ガスのＣＯ2回収率の低下を抑制しつつ、高濃度のＨ2を回収する方途について鋭意検討した。その結果、ガス分離回収装置を２つ以上の吸着塔が直列に配置された吸着塔列として構成するとともに、各吸着塔における吸着剤に吸着したガス成分を脱着させる排気手段を各吸着塔のガス排出配管に接続し、かつガス排気手段の出側に、バルブ操作により切り替え可能な２系統のガス回収配管を設けることに想到した。 Therefore, the present inventors have earnestly studied methods for recovering high-concentration H 2 while suppressing the above-described decrease in the CO 2 recovery rate of the recovered gas. As a result, the gas separation and recovery apparatus is configured as an adsorption tower train in which two or more adsorption towers are arranged in series, and the exhaust means for desorbing the gas components adsorbed by the adsorbent in each adsorption tower is used as the gas of each adsorption tower. The inventors have come up with the idea of providing two systems of gas recovery pipes which are connected to the discharge pipe and which can be switched by operating a valve on the outlet side of the gas discharge means.

図５は、本発明によるガス分離回収設備の一例を示している。図５に示したガス分離回収設備１は、２つ以上の吸着塔を直列に配置された吸着塔列１０、２０を備え、図５の例では、各吸着塔列１０、２０において、２塔の吸着塔１１（２１）および１２（２２）が直列に配置されている。 FIG. 5 shows an example of gas separation and recovery equipment according to the present invention. The gas separation and recovery facility 1 shown in FIG. 5 includes adsorption tower trains 10 and 20 in which two or more adsorption towers are arranged in series. In the example of FIG. adsorption towers 11 (21) and 12 (22) are arranged in series.

ガス分離回収設備１における各吸着塔１１、１２、２１、２２は、２種類以上のガス成分のうちの少なくとも１種類のガス成分を吸着する吸着剤が充填され、吸着塔内にガスを導入するガス導入配管１１ａ、１２ａ、２１ａ、２２ａと、吸着塔内からガスを排出するガス排出配管１１ｂ、１２ｂ、２１ｂ、２２ｂとを有する。そして、隣接する２つの吸着塔の上流側の吸着塔１１（２１）のガス排出配管１１ａ（２１ａ）と下流側の吸着塔１２（２２）のガス導入配管１２ｂ（２２ｂ）とが接続されており、上流側吸着塔１１（２１）から排出されたガスが下流側吸着塔１２（２２）に導入されるように構成されている。 Each of the adsorption towers 11, 12, 21, 22 in the gas separation and recovery equipment 1 is filled with an adsorbent that adsorbs at least one gas component out of two or more gas components, and the gas is introduced into the adsorption tower. It has gas introduction pipes 11a, 12a, 21a, 22a and gas discharge pipes 11b, 12b, 21b, 22b for discharging gas from the adsorption tower. Then, the gas discharge pipe 11a (21a) of the adsorption tower 11 (21) on the upstream side of the two adjacent adsorption towers and the gas introduction pipe 12b (22b) of the adsorption tower 12 (22) on the downstream side are connected. , the gas discharged from the upstream side adsorption tower 11 (21) is introduced into the downstream side adsorption tower 12 (22).

また、排気手段ＶＰが各吸着塔１１、１２、２１、２２のガス排出配管１１ｂ、１２ｂ、２１ｂ、２２ｂに接続されており、各吸着塔１１、１２、２１、２２に充填された吸着剤に吸着したガス成分を脱着して脱着ガスとして吸着塔１１、１２、２１、２２から排出する。そして、排気手段ＶＰの出側には、バルブ操作により切り替え可能な２系統のガス回収配管３０ａ、３０ｂが設けられている。 In addition, the exhaust means VP is connected to the gas discharge pipes 11b, 12b, 21b, and 22b of the adsorption towers 11, 12, 21, and 22, and the adsorbent filled in the adsorption towers 11, 12, 21, and 22 The adsorbed gas components are desorbed and discharged from the adsorption towers 11, 12, 21 and 22 as desorbed gas. Two systems of gas recovery pipes 30a and 30b switchable by valve operation are provided on the outlet side of the exhaust means VP.

上記ガス分離回収設備１においては、吸着工程では、上流側吸着塔１１（２１）から下流側吸着塔１２（２２）に向かって原料ガスを流通させて、主に吸着剤に吸着しやすいガス成分１およびガス成分２を吸着させた後に、吸着オフガスとしてガス成分３を分離して回収する。そして、吸着工程で吸着剤に吸着させたガス成分を脱着させてガスを回収する脱着工程では、これら吸着塔列１０、２０の吸着塔１１（２１）、１２（２２）のうち、１つ以上の吸着塔において、脱着工程を複数の時間帯に区分けして、時間帯毎に異なるガス成分のガスを回収することによって、吸着剤に吸着したガス成分をガス成分毎に分離して回収する。 In the gas separation and recovery equipment 1, in the adsorption step, the raw material gas is circulated from the upstream side adsorption tower 11 (21) toward the downstream side adsorption tower 12 (22), and mainly gas components that are easily adsorbed by the adsorbent After adsorption of 1 and gas component 2, gas component 3 is separated and recovered as adsorption off-gas. Then, in the desorption step of desorbing the gas component adsorbed by the adsorbent in the adsorption step and recovering the gas, one or more of the adsorption towers 11 (21) and 12 (22) of the adsorption tower rows 10 and 20 In the adsorption tower of (1), the desorption process is divided into a plurality of time zones, and different gas components are recovered for each time zone, thereby separating and recovering the gas components adsorbed by the adsorbent for each gas component.

例えば、ガス成分１がＣＯ2、ガス成分２がＮ2、ガス成分３がＨ2である場合、ゼオライトや活性炭への吸着力は一般的にはＣＯ2＞Ｎ2＞Ｈ2であるため、吸着工程においてガス成分１～３を有する原料ガスをゼオライトや活性炭が充填された吸着塔１１、１２、２１、２２へ流通させると、ガス成分のガス分圧が同程度であれば、吸着剤に吸着しづらいＨ2が最も早く吸着オフガスとして排出され、次にＮ2が吸着オフガスに流出して排出され、最後にＣＯ2が吸着オフガスに流出して排出される。従って、吸着工程の吸着オフガスの組成は時間により変動する。 For example, when the gas component 1 is CO 2 , the gas component 2 is N 2 , and the gas component 3 is H 2 , the adsorption power to zeolite and activated carbon is generally CO 2 >N 2 >H 2 , so In the adsorption step, when the raw material gas having gas components 1 to 3 is passed through the adsorption towers 11, 12, 21, 22 filled with zeolite or activated carbon, if the gas partial pressures of the gas components are about the same, the adsorbent H 2 , which is difficult to adsorb, is discharged as adsorption off-gas first, then N 2 flows out into adsorption off-gas and is discharged, and finally CO 2 flows out into adsorption off-gas and is discharged. Therefore, the composition of the adsorption offgas of the adsorption step varies with time.

例えば、吸着オフガスのＨ2濃度に着目すると、初期の吸着オフガスはＨ2濃度が高く、次第に吸着オフガスへのＮ2の流出が開始してＨ2濃度が低下し、最後にＣＯ2が吸着オフガスに流出し出して、原料ガスが吸着せずにそのまま流出（破過）するようになり、吸着オフガスのＨ2濃度は原料ガスのＨ2濃度と等しくなる。したがって、Ｈ2（ガス成分３）を高濃度で分離して回収するためには、ＣＯ2（ガス成分１）およびＮ2（ガス成分２）が吸着オフガスに流出するのを開始する前に原料ガスの供給を停止して吸着工程を終了し、脱着工程へ移行することが肝要となる。 For example, focusing on the H 2 concentration of the adsorption off - gas, the initial adsorption off - gas has a high H 2 concentration. As a result, the H 2 concentration of the adsorbed off-gas becomes equal to the H 2 concentration of the raw material gas. Therefore, in order to separate and recover H 2 (gas component 3) at high concentrations, the feedstock must be depleted before CO 2 (gas component 1) and N 2 (gas component 2) begin to flow into the adsorption offgas. It is essential to stop the supply of gas, terminate the adsorption step, and shift to the desorption step.

次に、吸着処理完了後に、各吸着塔１１、１２、２１、２２を開閉バルブで縁切りした後に、個別に脱着処理を行う。上述のように、図５に示したガス分離回収設備１においては、バルブ操作により切り替え可能な２系統のガス回収配管３０ａ、３０ｂが設けられており、脱着処理では、脱着ガスの組成変動を利用して脱着ガスを時間により分岐させることによって、不純物ガスＮ2（ガス成分２）と回収ガスＣＯ2（ガス成分１）とを分離して回収する。 Next, after the adsorption process is completed, the adsorption towers 11, 12, 21, and 22 are disconnected by opening/closing valves, and the desorption process is performed individually. As described above, the gas separation and recovery equipment 1 shown in FIG. 5 is provided with two systems of gas recovery pipes 30a and 30b that can be switched by valve operation. The impurity gas N 2 (gas component 2) and the recovery gas CO 2 (gas component 1) are separated and recovered by branching the desorption gas according to time.

図５に示した吸着塔列１０、２０のように、吸着塔１１、１２、２１、２２を上流側の吸着塔１１、２１と下流側の吸着塔１２、２２とに分割することによって、上流側吸着塔１１、２１の下部に残存する不純物ガスＮ2の量を少なくすることができる。そのため、上流側吸着塔１１、２１の脱着処理を行う際に、真空ポンプＶＰの出側における不純物ガスＮ2の分離時間を短縮することができるため、不純物ガスＮ2のガス回収配管３０ａに流出するＣＯ2の量を削減して、回収ガスのＣＯ2回収率を向上させることができる。 Like the adsorption tower trains 10 and 20 shown in FIG. The amount of impurity gas N 2 remaining in the lower portions of the side adsorption towers 11 and 21 can be reduced. Therefore, when the desorption treatment of the upstream adsorption towers 11 and 21 is performed, the separation time of the impurity gas N 2 on the outlet side of the vacuum pump VP can be shortened. The amount of CO2 generated can be reduced and the CO2 recovery rate of the recovered gas can be improved.

なお、図５に示した吸着塔列１０、２０においては、各吸着塔列１０（２０）を上流側吸着塔１１（２１）と下流側吸着塔１２（２２）の２塔で構成しているが、原料ガスに含まれるガス成分の数や分離するガス成分の数に応じて３塔以上としてもよい。 In the adsorption tower rows 10 and 20 shown in FIG. 5, each adsorption tower row 10 (20) is composed of two towers, an upstream adsorption tower 11 (21) and a downstream adsorption tower 12 (22). However, the number of towers may be three or more depending on the number of gas components contained in the raw material gas and the number of gas components to be separated.

また、図５に示した吸着塔列１０、２０においては、真空ポンプＶＰは１基のみとしているが、上流側吸着塔１１、２１の脱着処理用の真空ポンプと、下流側吸着塔１２、２２の脱着処理用の真空ポンプとを別個で設けて、上流側吸着塔１１、２１および下流側吸着塔１２、２２の脱着処理を同時に実行するような設備構成としてもよい。 In the adsorption tower trains 10 and 20 shown in FIG. 5, only one vacuum pump VP is provided. A vacuum pump for the desorption treatment may be separately provided, and the equipment configuration may be such that the desorption treatments of the upstream adsorption towers 11 and 21 and the downstream adsorption towers 12 and 22 are performed simultaneously.

さらに、本発明において、吸着塔列１０、２０における各吸着塔１１、１２、２１、２２に充填される吸着剤が、３種類以上のガス成分に対してそれぞれ異なる吸着等温線を有することが好ましい。すなわち、吸着塔列１０、２０において直列配置される各吸着塔１１、１２、２１、２２には、それぞれの吸着塔において、主に吸着させるガス成分の平衡吸着量が多い吸着剤を充填することが好ましい。これにより、各吸着塔から排出されるオフガスの組成に応じて目的ガス（主に吸着させるガス成分）を効率的に分離できるようになるため、設備スケールを小さくすることができる。 Furthermore, in the present invention, it is preferable that the adsorbents filled in the respective adsorption towers 11, 12, 21, 22 in the adsorption tower rows 10, 20 have different adsorption isotherms for three or more gas components. . That is, each of the adsorption towers 11, 12, 21, and 22 arranged in series in the adsorption tower rows 10 and 20 is filled with an adsorbent that has a large equilibrium adsorption amount of the gas component to be mainly adsorbed in each adsorption tower. is preferred. As a result, the target gas (mainly the gas component to be adsorbed) can be efficiently separated according to the composition of the off-gas discharged from each adsorption tower, so the facility scale can be reduced.

次に、本発明によるガス分離方法について説明する。本発明によるガス分離回収方法は、上述した本発明によるガス分離回収設備１を用いたガス分離回収方法であり、圧力スイング吸着法（ＰＳＡ法）によって多成分（３種類以上のガス成分）を有する原料ガスから２種類以上のガス成分のガスを分離して回収する方法である。 Next, the gas separation method according to the present invention will be described. The gas separation and recovery method according to the present invention is a gas separation and recovery method using the gas separation and recovery equipment 1 according to the present invention described above, and has multiple components (three or more gas components) by the pressure swing adsorption method (PSA method). This is a method of separating and recovering two or more types of gas components from a raw material gas.

図６は、本発明によるガス分離回収方法を説明する図を示している。実際のＰＳＡ操作では、図５に示したガス分離回収設備１のように、複数の吸着塔列１０、１１を設けて原料ガス流通ラインを切り替えながら運転を行うが、図６には、説明のために、１つの吸着塔列１０の工程図およびガス配管のみを示している。 FIG. 6 shows a diagram for explaining the gas separation and recovery method according to the present invention. In actual PSA operation, as in the gas separation and recovery equipment 1 shown in FIG. Therefore, only the process chart and gas piping of one adsorption tower row 10 are shown.

また、図６では、吸着工程および脱着工程のガス流通方法のみが示されており、放圧工程および充圧工程については省略されている。また、図６において、白いバルブは開状態のバルブ、黒いバルブは閉状態のバルブ、破線は閉状態のバルブによりガスが流通していないガス配管をそれぞれ示している。 Further, FIG. 6 shows only the gas distribution method of the adsorption process and the desorption process, and omits the pressure release process and the pressure charging process. In FIG. 6, white valves indicate open valves, black valves indicate closed valves, and broken lines indicate gas pipes through which gas is not circulated due to the closed valves.

まず、吸着工程において、吸着塔列１０の最上流の吸着塔である吸着塔１１の上部から原料ガスを導入し、最下流の吸着塔１２に向かって原料ガスを流通させる。そして、原料ガスに含まれるガス成分のうち吸着塔列１０における吸着塔１１、１２に充填された吸着剤に吸着されなかったガス成分のガスを吸着オフガスとして分離して回収する。原料ガスは、例えばＣＯ2、Ｎ2、Ｈ2の３種類のガス成分で構成することができる。 First, in the adsorption step, the raw material gas is introduced from the upper part of the adsorption tower 11, which is the most upstream adsorption tower in the adsorption tower row 10, and is circulated toward the most downstream adsorption tower 12. Then, among the gas components contained in the raw material gas, those gas components that are not adsorbed by the adsorbents filled in the adsorption towers 11 and 12 in the adsorption tower row 10 are separated and recovered as adsorption off-gas. The raw material gas can be composed of, for example, three kinds of gas components, CO 2 , N 2 and H 2 .

吸着圧は、当該吸着塔列１０の出側の背圧弁（図示せず）により調整されている。吸着塔１１、１２の内部には、ゼオライトまたは活性炭などの吸着剤が充填されている。このような吸着塔列１０に原料ガスを供給して、ＣＯ2およびＮ2を吸着剤に吸着させ、吸着されなかったガス成分を吸着オフガスとして分離して回収する。この吸着オフガスは、主にＨ2を含む。 The adsorption pressure is adjusted by a back pressure valve (not shown) on the exit side of the adsorption tower row 10 . The adsorption towers 11 and 12 are filled with an adsorbent such as zeolite or activated carbon. The raw material gas is supplied to the adsorption tower train 10, CO 2 and N 2 are adsorbed by the adsorbent, and the non-adsorbed gas components are separated and recovered as adsorption off-gas. This adsorption off - gas contains mainly H2.

次に、脱着工程の初期工程である脱着工程（１）において、図６に示すようにガス配管を切り替え、主にＮ2を吸着した下流側吸着塔１２から不純物ガスであるＮ2を脱着して除去する。 Next, in the desorption step ( 1 ), which is the initial step of the desorption step, the gas piping is switched as shown in FIG . to remove.

続いて、脱着工程の中期工程である脱着工程（２）において、主にＣＯ2を吸着した上流側吸着塔１１内部を真空ポンプＶＰにより減圧することによって、脱着し易い不純物ガスＮ2をまず除去して回収する。 Subsequently, in the desorption step (2), which is the intermediate step of the desorption step, the interior of the upstream adsorption tower 11 that mainly adsorbed CO 2 is decompressed by the vacuum pump VP, thereby first removing the easily desorbed impurity gas N 2 . and collect.

そして、脱着工程の後期工程である脱着工程（３）において、真空ポンプＶＰの出側のガス配管をガス回収配管３０ｂに切り替えて、脱着し難いＣＯ2を後から分離して回収する。こうして、原料ガスから、ＣＯ2、Ｎ2およびＨ2を１回のＰＳＡ操作で分離して回収することができる。 Then, in the desorption step (3), which is the later step of the desorption step, the gas pipe on the outlet side of the vacuum pump VP is switched to the gas recovery pipe 30b to separate and recover CO 2 that is difficult to desorb later. Thus, CO 2 , N 2 and H 2 can be separated and recovered from the feed gas in one PSA operation.

図６においては、上流側吸着塔１１からのガス脱着と下流側吸着塔１２からのガス脱着を同一の真空ポンプＶＰを用いて行っているが、それぞれに別の真空ポンプを設ける構造としてもよい。また、吸着工程における吸着圧を高めるために吸着塔１１、２１の入側にガスコンプレッサーを設ける場合や、ガス脱着工程に放圧処理を含む場合においても、図６に示した場合と同様の設備および運転方法にてＣＯ2、Ｎ2およびＨ2を１回のＰＳＡ操作で分離して回収することが可能である。 In FIG. 6, gas desorption from the upstream side adsorption tower 11 and gas desorption from the downstream side adsorption tower 12 are performed using the same vacuum pump VP, but a structure in which separate vacuum pumps are provided for each may be employed. . In addition, even when a gas compressor is provided on the entrance side of the adsorption towers 11 and 21 in order to increase the adsorption pressure in the adsorption step, or when the gas desorption step includes pressure release treatment, the same equipment as shown in FIG. and the method of operation allows CO 2 , N 2 and H 2 to be separated and recovered in a single PSA operation.

また、図６では、下流側吸着塔１２の脱着処理を行った後に上流側吸着塔１１の脱着処理を行っているが、上流側吸着塔１１の脱着処理を行った後に下流側吸着塔１２の脱着処理を行ってもよい。しかし、上流側吸着塔１１の脱着処理を行った後に下流側吸着塔１２の脱着処理を行うと、配管内を回収ガス（ＣＯ2）と不純物ガス（Ｎ2）とが交互に流通することになり、分離回収したガスの濃度が低下する。そのため、下流側吸着塔１２の脱着処理を行った後に上流側吸着塔１１の脱着処理を行うことが好ましい。 Further, in FIG. 6, the desorption treatment of the upstream adsorption tower 11 is performed after the desorption treatment of the downstream adsorption tower 12 is performed. A desorption process may be performed. However, when the desorption treatment of the downstream adsorption tower 12 is performed after the desorption treatment of the upstream adsorption tower 11, the recovery gas (CO 2 ) and the impurity gas (N 2 ) alternately flow through the pipe. As a result, the concentration of the separated and recovered gas decreases. Therefore, it is preferable to perform the desorption treatment of the upstream adsorption tower 11 after performing the desorption treatment of the downstream adsorption tower 12 .

以下、本発明の実施例について説明するが、本発明は実施例に限定されない。 Examples of the present invention will be described below, but the present invention is not limited to these examples.

（発明例）
図５に示した本発明によるガス分離回収設備１を用いて、ラボスケールのＰＳＡ実験を行った。具体的には、原料ガスとして、３７％ＣＯ2、４１％Ｎ2、２２％Ｈ2の混合ガスを使用し、内径４２ｍｍ×高さ２００ｍｍのＳＵＳ吸着塔に１３Ｘゼオライト吸着剤を上段側吸着塔に５７ｇ、下段側吸着塔に１９０ｇそれぞれ充填した。また、ＰＳＡ運転条件は、サイクルタイムを１００ｓｅｃ／ｃｙｃｌｅ、原料ガスの供給量を８．５ＮＬ／ｋｇ吸着剤／ｃｙｃｌｅとし、吸着塔内の圧力は、吸着圧５０ｋＰａＧ、脱着圧－９５ｋＰａＧとした。 (Invention example)
A lab-scale PSA experiment was conducted using the gas separation and recovery equipment 1 according to the present invention shown in FIG. Specifically, a mixed gas of 37% CO 2 , 41% N 2 , and 22% H 2 was used as the raw material gas, and 13X zeolite adsorbent was added to the SUS adsorption tower having an inner diameter of 42 mm and a height of 200 mm. 57 g was packed in the bottom side adsorption tower, and 190 g was packed in the lower adsorption tower. The PSA operating conditions were a cycle time of 100 sec/cycle, a source gas supply rate of 8.5 NL/kg adsorbent/cycle, and pressures in the adsorption tower of adsorption pressure of 50 kPaG and desorption pressure of -95 kPaG.

図７は、従来法および本発明によるラボＰＳＡ実験結果を比較した図である。図７では、回収ＣＯ2濃度９０％および回収Ｈ2濃度６０％がほぼ等しい条件で、ＣＯ2回収率およびＨ2回収率を比較した。図７から、発明例については、吸着オフガスのＨ2濃度を従来例と同程度に維持しつつ、回収ガスのＣＯ2回収率が大幅に上昇していることが分かる。 FIG. 7 compares laboratory PSA experimental results according to the conventional method and the present invention. In FIG. 7, the CO 2 recovery rate and the H 2 recovery rate were compared under the condition that the recovered CO 2 concentration of 90% and the recovered H 2 concentration of 60% were almost equal. From FIG. 7, it can be seen that in the example of the invention, the CO 2 recovery rate of the recovered gas is greatly increased while maintaining the H 2 concentration of the adsorption off-gas at the same level as in the conventional example.

本発明によれば、多成分混合ガスから複数の特定のガス成分を効率的に分離して回収することができるため、製鉄業において有用である。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to efficiently separate and recover a plurality of specific gas components from a multi-component mixed gas, which is useful in the steel industry.

１，１００ ガス分離回収設備
１０，２０，１０１，１０２ 吸着塔列
１１，１２，２１，２２ 吸着塔
１１ａ，１２ａ，１０１ａ，１０２ａ ガス導入配管
１１ｂ，１２ｂ，１０１ｂ，１０２ｂ ガス排出配管
３０ａ，３０ｂ，１０３ａ，１０３ｂ ガス回収配管
ＶＰ 真空ポンプ 1,100 gas separation and recovery equipment 10, 20, 101, 102 adsorption tower rows 11, 12, 21, 22 adsorption towers 11a, 12a, 101a, 102a gas introduction pipes 11b, 12b, 101b, 102b gas discharge pipes 30a, 30b, 103a, 103b gas recovery pipe VP vacuum pump

Claims (3)

圧力スイング吸着法によって３種類以上のガス成分を有する原料ガスから２種類以上のガス成分を分離して回収するためのガス分離回収設備であって、
２つ以上の吸着塔が直列に配置された吸着塔列であって、各吸着塔は、前記２種類以上のガス成分のうちの少なくとも１種類のガス成分を吸着する吸着剤が充填され、吸着塔内にガスを導入するガス導入配管と、吸着塔内からガスを排出するガス排出配管とを有し、前記ガス排出配管の本数が１本であり、隣接する２つの吸着塔の上流側の吸着塔のガス排出配管と下流側の吸着塔のガス導入配管とが接続され、吸着工程において前記原料ガスが最上流の吸着塔から最下流の吸着塔に向かって流通するように構成されている、吸着塔列と、
各吸着塔のガス排出配管に接続され、各吸着塔に充填された吸着剤に吸着したガス成分を脱着して脱着ガスとして吸着塔から排出する排気手段と、
前記排気手段の出側に接続され、バルブ操作により切り替え可能な２系統のガス回収配管と、
を具えることを特徴とするガス分離回収設備。 Gas separation and recovery equipment for separating and recovering two or more types of gas components from a raw material gas having three or more types of gas components by a pressure swing adsorption method,
An adsorption tower train in which two or more adsorption towers are arranged in series, each adsorption tower being filled with an adsorbent that adsorbs at least one gas component out of the two or more gas components. It has a gas introduction pipe for introducing gas into the tower and a gas discharge pipe for discharging gas from the adsorption tower. The gas discharge pipe of the adsorption tower and the gas introduction pipe of the downstream adsorption tower are connected, and the raw material gas is configured to flow from the most upstream adsorption tower to the most downstream adsorption tower in the adsorption step. , an adsorption tower row, and
an exhaust means connected to the gas discharge pipe of each adsorption tower for desorbing the gas component adsorbed by the adsorbent packed in each adsorption tower and discharging it from the adsorption tower as desorbed gas;
two gas recovery pipes connected to the outlet side of the exhaust means and switchable by valve operation;
A gas separation and recovery facility comprising: 前記吸着剤が、前記３種類以上のガス成分に対してそれぞれ異なる吸着等温線を有する、請求項１に記載のガス分離回収設備。 2. The gas separation and recovery equipment according to claim 1, wherein said adsorbent has different adsorption isotherms for said three or more gas components. 請求項１または２に記載のガス分離回収設備を用いて、圧力スイング吸着法によって３種類以上のガス成分を有する原料ガスから２種類以上のガス成分のガスを分離して回収するガス分離回収方法であって、
各吸着塔列における吸着塔に充填された吸着剤にガス成分を吸着させる前記吸着工程では、前記吸着塔列の最上流の吸着塔から最下流の吸着塔に向かって前記原料ガスを流通させ、前記最下流の吸着塔のガス排出配管から排出された、前記３種類以上のガス成分のうち前記吸着塔列における吸着塔に充填された吸着剤に吸着されなかったガス成分のガスを吸着オフガスとして分離して回収し、
前記吸着工程において前記吸着剤に吸着させたガス成分を脱着させる脱着工程では、前記吸着塔列における吸着塔のうちの１つ以上の吸着塔において、脱着工程を複数の時間帯に区分けして、時間帯毎に前記バルブ操作により前記２系統のガス回収配管を切り替えて、前記３種類以上のガス成分のうちの異なるガス成分のガスを分離して回収することを特徴とするガス分離回収方法。 A gas separation and recovery method for separating and recovering two or more types of gas components from a raw material gas having three or more types of gas components by pressure swing adsorption using the gas separation and recovery equipment according to claim 1 or 2. and
In the adsorption step of adsorbing a gas component to an adsorbent packed in an adsorption tower in each adsorption tower row, the raw material gas is circulated from the most upstream adsorption tower to the most downstream adsorption tower in the adsorption tower row, Among the three or more types of gas components discharged from the gas discharge pipe of the most downstream adsorption tower, the gas of the gas component that is not adsorbed by the adsorbent packed in the adsorption tower in the adsorption tower row is used as the adsorption off gas. Separate and collect
In the desorption step of desorbing the gas components adsorbed by the adsorbent in the adsorption step, in one or more adsorption towers among the adsorption towers in the adsorption tower row, the desorption step is divided into a plurality of time zones, A gas separation and recovery method, characterized in that the two systems of gas recovery pipes are switched by the valve operation for each time period to separate and recover gases of different gas components among the three or more types of gas components.
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