TW201716326A - Separation recovery method and separation recovery system for carbon dioxide capable of efficiently recovering carbon dioxide even if the carbon dioxide concentration in the gaseous raw material varies when carbon dioxide is being liquefaction-recovered from a gaseous raw material including carbon dioxide and impurities - Google Patents

Separation recovery method and separation recovery system for carbon dioxide capable of efficiently recovering carbon dioxide even if the carbon dioxide concentration in the gaseous raw material varies when carbon dioxide is being liquefaction-recovered from a gaseous raw material including carbon dioxide and impurities Download PDF

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TW201716326A
TW201716326A TW105122360A TW105122360A TW201716326A TW 201716326 A TW201716326 A TW 201716326A TW 105122360 A TW105122360 A TW 105122360A TW 105122360 A TW105122360 A TW 105122360A TW 201716326 A TW201716326 A TW 201716326A
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carbon dioxide
gas
raw material
psa
separation
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TWI698396B (en
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Toshihiko Sumida
Masanori Miyake
Takuya Iwaki
Kenichi Komine
Katsuya Komine
Yasushi Toguchi
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Sumitomo Seika Chemicals
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

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Abstract

The present invention provides a method and a device which is capable of efficiently recovering carbon dioxide, when carbon dioxide is being liquefaction-recovered from a gaseous raw material including carbon dioxide and impurities, even if the carbon dioxide concentration in the gaseous raw material varies. Provided is a carbon dioxide separation recovery device X1 used to separate and recover carbon dioxide from a gaseous raw material containing carbon dioxide and impurities, under the condition that the carbon dioxide concentration in the gaseous raw material varies, comprising: a liquefaction recovery apparatus 5 wherein carbon dioxide is liquefaction-recovered from the gaseous raw material under low temperature high pressure while exhausting the waste gas; and a PSA gas separation apparatus 6 wherein a PSA method is employed to concentratedly separate the carbon dioxide included in the waste gas, and the gas separation is performed in such a manner that the treatment of the gas separation is changed according to the state change of at least either the gaseous raw material or the waste gas.

Description

二氧化碳的分離回收方法及分離回收系統 Carbon dioxide separation and recovery method and separation and recovery system

本發明係有關於從含有二氧化碳及不純物的原料氣體液化回收二氧化碳的方法及裝置。 The present invention relates to a method and apparatus for liquefying and recovering carbon dioxide from a raw material gas containing carbon dioxide and impurities.

例如在啤酒製造工廠中，將酒精發酵時產生的發酵氣體中所包含的二氧化碳液化回收，利用於啤酒充填等的用途。啤酒發酵氣體中包含的不純物氣體大半來自空氣。更具體來說，不純物氣體來自於啤酒發酵時將原料放進發酵槽來添加酵母這段時間同時吹進去的空氣。吹進空氣是因為發酵過程初期要幫助酵母以空氣中的氧為餌而增值。此時，氧的大半被消耗，因此剩餘的幾乎都是氮(N2)。 For example, in a beer manufacturing plant, carbon dioxide contained in a fermentation gas generated during alcohol fermentation is liquefied and recovered, and is used for applications such as beer filling. Most of the impurities contained in the beer fermentation gas come from the air. More specifically, the impurity gas is derived from the air that is blown in while the raw material is put into the fermentation tank to add the yeast during the beer fermentation. The air is blown in because the yeast helps the yeast to add value by taking oxygen from the air as a bait at the beginning of the fermentation process. At this time, most of the oxygen is consumed, so almost all of the remaining nitrogen (N 2 ).

當酵母增殖開始發酵時，二氧化碳及乙醇產生。當二氧化碳增加，會將存在於發酵槽中的來自空氣的成分擠出。因此，剩餘的來自空氣的成分被慢慢擠出，而置換成二氧化碳，同時被擠出的發酵氣體中的來自空氣的成分降低。當發酵持續進行，最後發酵槽內被置換成高純度的二氧化碳，所產生的啤酒發酵氣體也會以高純度地供給。另一方面，初期的啤酒發酵氣體，含有不純物的來自空氣的成分(主要為氮)的比例較高，而處於二氧化碳濃度相對低的狀態。而如果啤酒發酵氣體中的二氧化碳濃度太低，以精餾塔等的液化回收裝置液化 回收二氧化碳時，廢氣(不被液化的氣體成分)的量增加，液化二氧化碳的回收率下降。 When yeast proliferation begins to ferment, carbon dioxide and ethanol are produced. As carbon dioxide increases, the air-derived components present in the fermenter are extruded. Therefore, the remaining components derived from the air are slowly extruded and replaced with carbon dioxide, while the components derived from the air in the extruded fermentation gas are lowered. When the fermentation is continued, the fermentation tank is finally replaced with high-purity carbon dioxide, and the produced beer fermentation gas is also supplied in high purity. On the other hand, in the initial beer fermentation gas, the proportion of air-derived components (mainly nitrogen) containing impurities is high, and the carbon dioxide concentration is relatively low. If the concentration of carbon dioxide in the beer fermentation gas is too low, liquefaction is carried out by a liquefaction recovery unit such as a rectification column. When carbon dioxide is recovered, the amount of exhaust gas (a gas component that is not liquefied) increases, and the recovery rate of liquefied carbon dioxide decreases.

做為解決二氧化碳的回收率下降的方法，有一種將二氧化碳濃度低的氣體以吸收法或吸附法等直接濃縮的方法。又，發酵氣體的二氧化碳濃度會隨著發酵的進行而上升，到達不需要濃縮的純度。因此，過去在液化回收啤酒發酵氣體中的二氧化碳的情況下，一般會在某種程度的啤酒發酵氣體中的二氧化碳濃度上升之後，才開始將啤酒發酵氣體供給到液化回收裝置。 As a method for solving the decrease in the recovery rate of carbon dioxide, there is a method of directly concentrating a gas having a low carbon dioxide concentration by an absorption method or an adsorption method. Further, the carbon dioxide concentration of the fermentation gas rises as the fermentation progresses, and reaches a purity that does not require concentration. Therefore, in the past, in the case of liquefying and recovering carbon dioxide in the beer fermentation gas, the beer fermentation gas is generally supplied to the liquefaction recovery device after the carbon dioxide concentration in the beer fermentation gas is increased to some extent.

然而，使用這種方法，直到二氧化碳的濃度上升之前的啤酒發酵氣體無法有效利用而產生浪費。又，啤酒發酵期間，在發酵過程的初期以外也有因為槽搬運等目的而執行氣體供給操作。氣體供給操作時，空氣會經過發酵槽而流入二氧化碳的液化回收裝置，因此上述液化回收裝置，也就是精餾塔內部的二氧化碳濃度會暫時地下降。這樣一來，在啤酒發酵期間，啤酒發酵氣體中的二氧化碳濃度會反覆變動(上升及下降)，當啤酒發酵氣體中的二氧化碳濃度低時，會廢棄這些啤酒發酵氣體，使得浪費增加。關於經過液化回收裝置(精餾塔等)的廢氣，做為濃縮二氧化碳的方法，有一種壓力變動吸附法(例如參照專利文獻1)。然而，像啤酒發酵氣體一樣，原料氣體中的二氧化碳濃度變動的情況下，並沒有一種有效率地回收廢氣中的二氧化碳的方法被提出。 However, with this method, the beer fermentation gas before the increase in the concentration of carbon dioxide cannot be effectively utilized and waste is generated. Further, during the beer fermentation, the gas supply operation is performed for the purpose of tank transportation or the like in addition to the initial stage of the fermentation process. In the gas supply operation, air flows into the liquefaction recovery device of the carbon dioxide through the fermentation tank, and thus the concentration of carbon dioxide in the liquefaction recovery device, that is, inside the rectification column, temporarily drops. In this way, during beer fermentation, the concentration of carbon dioxide in the beer fermentation gas will change (rise and fall) repeatedly. When the concentration of carbon dioxide in the beer fermentation gas is low, the beer fermentation gas will be discarded, resulting in increased waste. The exhaust gas which has passed through the liquefaction recovery apparatus (refinery column, etc.) is a pressure fluctuation adsorption method as a method of concentrating carbon dioxide (see, for example, Patent Document 1). However, in the case where the concentration of carbon dioxide in the material gas fluctuates like the beer fermentation gas, there is no method for efficiently recovering carbon dioxide in the exhaust gas.

專利文獻1：日本特開平3-165809號公報 Patent Document 1: Japanese Patent Laid-Open No. Hei 3-165809

本發明是根據上述問題而思考出來，主要的目的 是提供一種方法及裝置，當要從含有二氧化碳及不純物的原料氣體液化回收二氧化碳時，即使原料氣體中的二氧化碳的濃度變動，也能夠以高回收率有效率地進行回收。 The present invention is based on the above problems, the main purpose Provided is a method and an apparatus. When carbon dioxide is liquefied from a raw material gas containing carbon dioxide and impurities, even if the concentration of carbon dioxide in the raw material gas fluctuates, it can be efficiently recovered at a high recovery rate.

根據本發明的第1觀點所提供的二氧化碳的分離回收方法，用以對含有二氧化碳及不純物的原料氣體，在該原料氣體的二氧化碳濃度變動的狀況下分離回收二氧化碳，包括：液化步驟，在低溫高壓下從該原料氣體液化回收二氧化碳，並排出廢氣；以及PSA氣體分離步驟，藉由PSA法將該廢氣中含有的二氧化碳濃縮分離，其中因應該原料氣體的二氧化碳的濃度，變動該PSA氣體分離步驟中的氣體分離的處理量。 According to a first aspect of the present invention, a method for separating and recovering carbon dioxide is provided for separating and recovering carbon dioxide in a raw material gas containing carbon dioxide and impurities in a state in which a carbon dioxide concentration of the material gas is changed, including: a liquefaction step, at a low temperature and a high pressure The carbon dioxide is liquefied and recovered from the raw material gas, and the exhaust gas is discharged; and the PSA gas separation step is performed by separating and separating the carbon dioxide contained in the exhaust gas by a PSA method, wherein the PSA gas separation step is changed according to the concentration of carbon dioxide of the raw material gas. The amount of gas separation processed.

一個實施型態中，檢測出該原料氣體的二氧化碳濃度，當該原料氣體的二氧化碳濃度在既定值以上的情況下，減少該PSA氣體分離步驟中的氣體分離的處理量，或者是停止氣體分離的處理，當該原料氣體的二氧化碳濃度低於既定值的情況下，增加該PSA氣體分離步驟中的氣體分離的處理量，或者是實行氣體分離的處理。 In one embodiment, the carbon dioxide concentration of the material gas is detected, and when the carbon dioxide concentration of the material gas is greater than or equal to a predetermined value, the amount of gas separation in the PSA gas separation step is reduced, or the gas separation is stopped. The treatment increases the treatment amount of the gas separation in the PSA gas separation step or the treatment of the gas separation when the carbon dioxide concentration of the material gas is lower than a predetermined value.

另一實施型態中，檢測出該廢氣的壓力，當該廢氣的壓力在既定值以下的情況下，減少該PSA氣體分離步驟中的氣體分離的處理量，或者是停止氣體分離的處理，當該廢氣的壓力超過既定值的情況下，增加該PSA氣體分離步驟中的氣體分離的處理量，或者是實行氣體分離的處理。 In another embodiment, the pressure of the exhaust gas is detected, and when the pressure of the exhaust gas is below a predetermined value, the processing amount of the gas separation in the PSA gas separation step is reduced, or the process of stopping the gas separation is performed. When the pressure of the exhaust gas exceeds a predetermined value, the amount of treatment for gas separation in the PSA gas separation step is increased, or the treatment for gas separation is performed.

又另一實施型態中，檢測出該原料氣體的流量，當該原料氣體的流量在既定值以下的情況下，減少該PSA氣體分 離步驟中的氣體分離的處理量，或者是停止氣體分離的處理，當該原料氣體的流量超過既定值的情況下，增加該PSA氣體分離步驟中的氣體分離的處理量，或者是實行氣體分離的處理。 In still another embodiment, the flow rate of the material gas is detected, and when the flow rate of the material gas is below a predetermined value, the PSA gas fraction is decreased. The treatment amount for separating the gas in the step, or the treatment for stopping the gas separation, increasing the treatment amount of the gas separation in the PSA gas separation step, or performing the gas separation when the flow rate of the material gas exceeds a predetermined value Processing.

較佳的是，更包括：追加的PSA氣體分離步驟，在該液化步驟之前，藉由PSA法將該原料氣體中含有的二氧化碳濃縮分離。 Preferably, the method further comprises: an additional PSA gas separation step of concentrating and separating the carbon dioxide contained in the material gas by a PSA method before the liquefaction step.

較佳的是，讓該PSA氣體分離步驟中濃縮二氧化碳而得的二氧化碳濃縮氣體，與上述原料氣體合流。 Preferably, the carbon dioxide concentrated gas obtained by concentrating the carbon dioxide in the PSA gas separation step is combined with the raw material gas.

根據本發明的第2觀點所提供的二氧化碳的分離回收系統，用以對含有二氧化碳及不純物的原料氣體，在該原料氣體的二氧化碳濃度變動的狀況下分離回收二氧化碳，包括：液化裝置，在低溫高壓下從該原料氣體液化回收二氧化碳，並排出廢氣；PSA分離裝置，能夠藉由PSA法將該廢氣中含有的二氧化碳濃縮分離，根據該原料氣體及該廢氣中的至少一者的狀態變化，來變化氣體分離的處理狀態。 According to a second aspect of the present invention, a carbon dioxide separation and recovery system is provided for separating and recovering carbon dioxide in a raw material gas containing carbon dioxide and impurities, in a state in which a carbon dioxide concentration of the material gas is changed, including: a liquefaction apparatus, at a low temperature and a high pressure The carbon dioxide is liquefied and recovered from the raw material gas, and the exhaust gas is discharged. The PSA separation device can condense and separate the carbon dioxide contained in the exhaust gas by the PSA method, and change according to the state change of at least one of the material gas and the exhaust gas. The processing state of gas separation.

較佳的是，更包括以下三者中的至少一者：濃度檢測裝置，檢測出該原料氣體的二氧化碳濃度；壓力檢測裝置，檢測出該廢氣的壓力；以及流量檢測裝置，檢測出該原料氣體的流量。 Preferably, at least one of the following three is included: a concentration detecting device that detects a carbon dioxide concentration of the material gas; a pressure detecting device that detects a pressure of the exhaust gas; and a flow rate detecting device that detects the material gas Traffic.

較佳的是，更包括：返回線，用以讓上述PSA氣體分離裝置所濃縮分離的二氧化碳濃縮氣體，與上述原料氣體合流。 Preferably, the method further comprises: a return line for converging and separating the carbon dioxide concentrated gas separated and separated by the PSA gas separation device and the raw material gas.

本發明的其他的特徵及優點可透過參照圖式而進行的以下的詳細說明來進一步了解。 Other features and advantages of the present invention will be understood from the following detailed description.

X1、X2‧‧‧二氧化碳分離回收系統 X1, X2‧‧‧ Carbon dioxide separation and recovery system

1‧‧‧升壓風機 1‧‧‧Booster fan

2‧‧‧脫臭器 2‧‧‧ Deodorizer

3‧‧‧壓縮機 3‧‧‧Compressor

4‧‧‧冷卻器 4‧‧‧ cooler

5‧‧‧液化回收裝置 5‧‧‧Liquid recovery unit

51‧‧‧精餾塔 51‧‧‧Rectifier

52‧‧‧凝縮器 52‧‧‧Condenser

6‧‧‧PSA氣體分離裝置 6‧‧‧PSA gas separation device

7‧‧‧PSA氣體分離裝置 7‧‧‧PSA gas separation unit

8‧‧‧壓縮機 8‧‧‧Compressor

9、10‧‧‧開閉閥 9, 10‧‧‧Opening valve

11~17‧‧‧配管 11~17‧‧‧Pipe

18‧‧‧配管(返回線) 18‧‧‧Pipe (return line)

21‧‧‧二氧化碳感測器(濃度檢測裝置) 21‧‧‧ Carbon dioxide sensor (concentration detection device)

22‧‧‧流量計(流量檢測裝置) 22‧‧‧Flowmeter (flow detection device)

23‧‧‧壓力計(壓力檢測裝置) 23‧‧‧ Pressure gauge (pressure detection device)

24‧‧‧壓力控制閥 24‧‧‧ Pressure Control Valve

25‧‧‧流量控制閥 25‧‧‧Flow control valve

第1圖係表示實行本發明的二氧化碳的分離回收方法所能夠使用的二氧化碳分離回收系統的概略架構。 Fig. 1 is a schematic view showing a schematic configuration of a carbon dioxide separation and recovery system which can be used in the method for separating and recovering carbon dioxide according to the present invention.

第2圖係係表示實行本發明的二氧化碳的分離回收方法所能夠使用的二氧化碳分離回收系統的其他例子的概略架構。 Fig. 2 is a schematic view showing another example of a carbon dioxide separation and recovery system which can be used in the method for separating and recovering carbon dioxide according to the present invention.

以下，參照圖式具體地說明本發明較佳的實施型態。 Hereinafter, preferred embodiments of the present invention will be specifically described with reference to the drawings.

第1圖係表示實行本發明的二氧化碳的分離回收方法所能夠使用的二氧化碳分離回收系統的概略架構。二氧化碳分離回收系統X1包括：升壓風機1、脫臭器2、壓縮機3、冷卻器4、液化回收裝置5、壓力變動吸附式氣體分離裝置(PSA氣體分離裝置)6以及將這些要素連接的配管。二氧化碳分離回收系統X1的架構會做成能夠一邊連續地供給含有二氧化碳的原料氣體，一邊液化回收該原料氣體中的二氧化碳。 Fig. 1 is a schematic view showing a schematic configuration of a carbon dioxide separation and recovery system which can be used in the method for separating and recovering carbon dioxide according to the present invention. The carbon dioxide separation and recovery system X1 includes a booster fan 1, a deodorizer 2, a compressor 3, a cooler 4, a liquefaction recovery device 5, a pressure fluctuation adsorption gas separation device (PSA gas separation device) 6, and a connection of these elements. Piping. The carbon dioxide separation and recovery system X1 has a structure in which carbon dioxide in the raw material gas can be liquefied while continuously supplying a raw material gas containing carbon dioxide.

被供給到二氧化碳分離回收系統X1的原料氣體例如可舉出啤酒發酵氣體。啤酒發酵氣體是在啤酒發酵時從發酵槽送出的氣體，主要包含存在於發酵槽的內部空間的成分(主要是來自空氣的成分，氮)以及啤酒發酵所產生的成分(主要是二氧化碳)。 The raw material gas supplied to the carbon dioxide separation and recovery system X1 is, for example, a beer fermentation gas. The beer fermentation gas is a gas that is sent from the fermentation tank during beer fermentation, and mainly contains components (mainly air-derived components, nitrogen) present in the inner space of the fermentation tank and components (mainly carbon dioxide) produced by beer fermentation.

啤酒發酵氣體(原料氣體)中的二氧化碳濃度在例如發酵開始後的初期階段較低，隨著發酵進行而上升，最終到達99.9%以上。又，發酵槽有時會有因為槽搬運等目的而執 行氣體供給操作的情況，這個氣體供給操作會使不純物(主要是來自空氣的成分)增加，啤酒發酵氣體(原料氣體)中的二氧化碳濃度降低到例如80~90%。像這樣，做為原料氣體的啤酒發酵氣體中的二氧化碳濃度隨著時間經過而反覆地在既定的範圍(例如80~99.9%)內上升下降變動。 The concentration of carbon dioxide in the beer fermentation gas (raw material gas) is, for example, lower in the initial stage after the start of fermentation, and rises as the fermentation progresses, and finally reaches 99.9% or more. In addition, the fermentation tank may be carried out for the purpose of handling the tank. In the case of a gas supply operation, this gas supply operation increases impurities (mainly components derived from air), and the concentration of carbon dioxide in the beer fermentation gas (raw material gas) is lowered to, for example, 80 to 90%. As described above, the concentration of carbon dioxide in the beer fermentation gas as the material gas rises and falls within a predetermined range (for example, 80 to 99.9%) over time.

啤酒製造工廠中，會準備複數的發酵槽(例如10~20槽左右)做為發酵設備，從這些發酵槽送出的啤酒發酵氣體(原料氣體)會透過未圖示的集合管供給到二氧化碳分離回收系統X1。啤酒發酵氣體(原料氣體)對二氧化碳分離回收系統X1的的供給量會因應啤酒製造設備的規模或啤酒製造量而異，但例如在40~180Nm3/h左右。 In the beer manufacturing plant, a plurality of fermentation tanks (for example, about 10 to 20 tanks) are prepared as fermentation equipment, and beer fermentation gas (raw material gas) sent from these fermentation tanks is supplied to a carbon dioxide separation and recovery through a collecting pipe (not shown). System X1. The supply amount of the beer fermentation gas (raw material gas) to the carbon dioxide separation and recovery system X1 varies depending on the scale of the beer production equipment or the amount of beer produced, but is, for example, about 40 to 180 Nm 3 /h.

升壓風機1將透過配管11導入的原料氣體以既定壓力送出。脫臭器2除去例如原料氣體中所含有的碳氫化物等的不純物成分。壓縮機3將經過脫臭器2的原料氣體以既定的高壓狀態送出。冷卻器4例如是殼管式(shell and tube type)熱交換器，原料氣體被流動於傳熱管內的鹽水(冷媒)冷卻。通過冷卻器4的原料氣體會透過配管12送到液化回收裝置5。 The booster fan 1 feeds the material gas introduced through the pipe 11 at a predetermined pressure. The deodorizer 2 removes, for example, an impurity component such as a hydrocarbon contained in the material gas. The compressor 3 sends the material gas that has passed through the deodorizer 2 at a predetermined high pressure state. The cooler 4 is, for example, a shell and tube type heat exchanger, and the material gas is cooled by brine (refrigerant) flowing in the heat transfer tube. The material gas that has passed through the cooler 4 is sent to the liquefaction recovery device 5 through the pipe 12.

配管12設置有二氧化碳感測器21。二氧化碳感測器21會持續檢測出流過配管12內的原料氣體的二氧化碳濃度。配管12更設置有用來檢測流過該配管12的原料氣體的流量的流量計22。 The pipe 12 is provided with a carbon dioxide sensor 21. The carbon dioxide sensor 21 continuously detects the concentration of carbon dioxide flowing through the material gas in the pipe 12. The pipe 12 is further provided with a flow meter 22 for detecting the flow rate of the material gas flowing through the pipe 12.

另外，雖省略詳細的圖式說明，但關於供給到液化回收裝置5的原料氣體，可以在供給前適當地進行事先除去水分或氣泡等的作業。 In addition, the detailed description of the drawings is omitted. However, the raw material gas supplied to the liquefaction recovery device 5 can be appropriately subjected to an operation of removing moisture or bubbles in advance before supply.

液化回收裝置5是用來從原料氣體液化回收二氧化碳，被例如精餾塔51及凝縮器52。凝縮器52藉由將原料氣體維持在低溫高壓狀態而主要使二氧化碳液化。凝縮器52中，進行利用鹽水(冷媒)的冷卻，內部壓力被調節在2.1MPaG(G表示表壓，以下亦同)的程度以下。 The liquefaction recovery device 5 is for recovering carbon dioxide from the raw material gas, and is, for example, a rectification column 51 and a condenser 52. The condenser 52 mainly liquefies carbon dioxide by maintaining the material gas in a low temperature and high pressure state. In the condenser 52, cooling with brine (refrigerant) is performed, and the internal pressure is adjusted to the extent of 2.1 MPaG (G is the gauge pressure, the same applies hereinafter).

通過冷卻器4的原料氣體透過配管12導入精餾塔51。精餾塔51內的氣體會透過連接在其上部的配管13而導入凝縮器52。在凝縮器52中，二氧化碳在低溫高壓下液化，該液化二氧化碳通過連接在出口側下部的配管14回到精餾塔51。滯留於精餾塔51內的液化二氧化碳會從該精餾塔51的底部當作是產品取出。 The raw material gas that has passed through the cooler 4 is introduced into the fractionator 51 through the pipe 12. The gas in the fractionator 51 is introduced into the condenser 52 through the pipe 13 connected to the upper portion. In the condenser 52, carbon dioxide is liquefied at a low temperature and high pressure, and the liquefied carbon dioxide is returned to the rectification column 51 through a pipe 14 connected to the lower portion of the outlet side. The liquefied carbon dioxide retained in the rectification column 51 is taken out as a product from the bottom of the rectification column 51.

凝縮器52的出口側上部連接了用來使通過該凝縮器52的氣體(廢氣)流通的配管15。配管15設置有壓力計23。藉由這個壓力計23，能夠檢測出配管15內的廢氣的壓力。又，配管15分歧連接了用來排出廢氣的配管16。配管16設置有壓力控制閥24。壓力控制閥24在配管15、16內的廢氣的壓力超過既定值(例如2.1MPaG以上的設定值)時開放，將廢氣排放到外部。 A pipe 15 for circulating a gas (exhaust gas) passing through the condenser 52 is connected to an upper portion of the outlet side of the condenser 52. The piping 15 is provided with a pressure gauge 23. With this pressure gauge 23, the pressure of the exhaust gas in the pipe 15 can be detected. Further, the piping 15 is connected to the piping 16 for exhausting the exhaust gas. The piping 16 is provided with a pressure control valve 24. The pressure control valve 24 is opened when the pressure of the exhaust gas in the pipes 15 and 16 exceeds a predetermined value (for example, a set value of 2.1 MPaG or more), and the exhaust gas is discharged to the outside.

配管15設置有流量調整閥25，配管15的下流側連接了PSA氣體分離裝置6。從凝縮器52排出的廢氣在滿足既定條件的情況下，會透過配管15及流量調整閥25送出至PSA氣體分離裝置6。 The pipe 15 is provided with a flow rate adjusting valve 25, and the downstream side of the pipe 15 is connected to the PSA gas separating device 6. The exhaust gas discharged from the condenser 52 is sent to the PSA gas separation device 6 through the pipe 15 and the flow rate adjusting valve 25 when the predetermined conditions are satisfied.

PSA氣體分離裝置6具備複數的吸附塔(圖式省略)，填充了用來選擇性地吸附二氧化碳的吸附劑。PSA氣體 分離裝置6進行壓力變動吸附式氣體分離步驟(PSA氣體分離步驟)。填充於上述吸附塔的吸附劑例如能夠採用具有以椰子殼或竹子等的植物物質、石炭物質、石油物質等物做為原料的分子篩功能的CMS(Carbon Molecular Sieve)或合成ZMS(Zeolite Molecular Sieve)。 The PSA gas separation device 6 is provided with a plurality of adsorption towers (not shown), and is filled with an adsorbent for selectively adsorbing carbon dioxide. PSA gas The separation device 6 performs a pressure fluctuation adsorption type gas separation step (PSA gas separation step). The adsorbent to be filled in the adsorption tower can be, for example, a CMS (Carbon Molecular Sieve) or a synthetic ZMS (Zeolite Molecular Sieve) having a molecular sieve function using a plant material such as a coconut shell or bamboo, a charcoal substance, or a petroleum substance as a raw material. .

PSA氣體分離步驟中，單一的吸附塔會重複循環1個包含有例如吸附步驟、洗淨步驟及脫附步驟的週期。吸附步驟是將上述廢氣導入塔內處於既定的高壓狀態的吸附塔，使該廢氣中的二氧化碳吸附到吸附劑上，再從該吸附塔導出非附著氣體的步驟。洗淨步驟是利用處於脫附步驟中的其他的吸附塔所導出的脫附氣體的一部分，洗淨已完成吸附步驟的吸附塔的步驟。脫附步驟是將吸附塔內減壓使二氧化碳從吸附劑脫附，將塔內的二氧化碳濃縮氣體(主要是脫附氣體)導出至塔外的步驟。另外，關於吸附塔的個數，當以上述3個步驟為1個週期重複循環的情況下，較佳的是3塔。然而，也可以是具備2塔或4塔以上的吸附塔。又，PSA氣體分離步驟中，至少將包含吸附步驟及脫附步驟的複數步驟做為1個週期來重複循環即可。 In the PSA gas separation step, a single adsorption column repeats a cycle including, for example, an adsorption step, a washing step, and a desorption step. The adsorption step is a step of introducing the above-mentioned exhaust gas into an adsorption tower having a predetermined high pressure state in the column, adsorbing carbon dioxide in the exhaust gas onto the adsorbent, and then introducing a non-adhered gas from the adsorption tower. The washing step is a step of washing the adsorption tower having completed the adsorption step by using a part of the desorbed gas derived from the other adsorption towers in the desorption step. The desorption step is a step of decompressing the inside of the adsorption column to desorb carbon dioxide from the adsorbent, and discharging the carbon dioxide concentrated gas (mainly desorbed gas) in the column to the outside of the column. Further, in the case where the number of adsorption columns is repeated in one cycle in the above three steps, it is preferably three columns. However, it is also possible to have an adsorption tower having two or four columns or more. Further, in the PSA gas separation step, at least the plurality of steps including the adsorption step and the desorption step may be repeated as one cycle.

PSA氣體分離裝置6連接了配管17、18。配管17是用來將從吸附塔導出的非吸附氣體排出到外部。配管18是用來將從吸附塔導出的二氧化碳濃縮氣體與原料氣體合流後回收。配管18的下流側端連接到原料氣體流通的配管11的上流側。 The PSA gas separation device 6 is connected to the pipes 17, 18. The piping 17 is for discharging the non-adsorbed gas derived from the adsorption tower to the outside. The piping 18 is used to recover the carbon dioxide concentrated gas derived from the adsorption tower and the raw material gas. The downstream side end of the pipe 18 is connected to the upstream side of the pipe 11 through which the material gas flows.

使用具有上述構造的二氧化碳分離回收系統X1，從啤酒發酵氣體(原料氣體)中液化回收二氧化碳。本實施型 態中，原料氣體中的二氧化碳濃度會如上所述隨著時間經過而反覆上升及下降，變動於既定範圍(例如約80~99.9%)內。原料氣體中含有的二氧化碳被液化回收裝置5液化回收時，該被液化回收的液化二氧化碳的純度幾乎是100%。因此，關於不液化而殘存於精餾塔51等的氣體(廢氣)，其二氧化碳的濃度比原料氣體低。 The carbon dioxide separation and recovery system X1 having the above configuration is used to liquefy and recover carbon dioxide from the beer fermentation gas (raw material gas). This embodiment In the state, the concentration of carbon dioxide in the material gas rises and falls over time as described above, and varies within a predetermined range (for example, about 80 to 99.9%). When the carbon dioxide contained in the material gas is liquefied and recovered by the liquefaction recovery device 5, the purity of the liquefied carbon dioxide recovered by the liquefaction is almost 100%. Therefore, the gas (exhaust gas) remaining in the rectification column 51 or the like without being liquefied has a lower concentration of carbon dioxide than the material gas.

例如，以原料氣體的供給量是165Nm3/h，廢氣量是20Nm3/h的狀態下操作的液化回收裝置5(凝縮器52)的溫度是-20℃時，在凝縮壓力為1.87MPaG的條件基礎下，當原料氣體中的二氧化碳濃度為約99.9%的情況下，廢氣中的二氧化碳濃度為約99%。又，在上述原料氣體供給態樣及冷卻加壓條件下，原料氣體的二氧化碳濃度為約99%的情況下，廢氣氣體的二氧化碳濃度為約92.7%；原料氣體的二氧化碳濃度為約98%的情況下，廢氣氣體的二氧化碳濃度為約85.7%；原料氣體的二氧化碳濃度為約97%的情況下，廢氣氣體的二氧化碳濃度為約78.7%。當廢氣的二氧化碳濃度是92.7%時，為了維持塔壓力1.87MPaG，因為二氧化碳的分壓下降，必須將液化回收裝置5(濃縮器52)的溫度下降到-22.8℃。又，當廢氣的二氧化碳濃度降低到78.7%時，溫度就必須降低到-28.3℃，運轉變得困難。 For example, when the temperature of the liquefaction recovery device 5 (condenser 52) operated in a state where the supply amount of the raw material gas is 165 Nm 3 /h and the exhaust gas amount is 20 Nm 3 /h is -20 ° C, the condensation pressure is 1.87 MPaG. On the basis of conditions, when the concentration of carbon dioxide in the material gas is about 99.9%, the concentration of carbon dioxide in the exhaust gas is about 99%. Further, in the case of the raw material gas supply state and the cooling and pressurization conditions, when the carbon dioxide concentration of the material gas is about 99%, the carbon dioxide concentration of the exhaust gas is about 92.7%; and the carbon dioxide concentration of the raw material gas is about 98%. The carbon dioxide concentration of the exhaust gas is about 85.7%; and the carbon dioxide concentration of the raw material gas is about 97%, the carbon dioxide concentration of the exhaust gas is about 78.7%. When the carbon dioxide concentration of the exhaust gas is 92.7%, in order to maintain the column pressure of 1.87 MPaG, since the partial pressure of carbon dioxide is lowered, the temperature of the liquefaction recovery device 5 (concentrator 52) must be lowered to -22.8 °C. Further, when the carbon dioxide concentration of the exhaust gas is lowered to 78.7%, the temperature must be lowered to -28.3 ° C, and the operation becomes difficult.

如上述，當廢氣中的二氧化碳濃度降低時，因為二氧化碳的分壓下降，所以液化變得困難。增加廢氣量的話，二氧化碳濃度會增加，但會被液化回收的二氧化碳的比例(以下，簡單稱為「液化回收率」)會反而下降。例如，設定溫度在-20℃左右，壓力在1.87MPaG左右的冷卻加壓條件，將壓力 控制閥24的廢氣的外部排放設定壓設定在2.1MPaG以上的情況下，當原料氣體的二氧化碳濃度為約99.9%時，液化回收率在95%以上。又，當原料氣體的二氧化碳濃度為約99%時，液化回收率變為約80%。當原料氣體的二氧化碳濃度為約90%時，液化回收率變為約40%。這邊的液化回收率是不使用PSA氣體分離裝置6的狀態下的液化回收率。相對於此，使用PSA氣體分離裝置6的情況下，以90%以上的高二氧化碳回收率，濃縮成比原來的原料氣體的二氧化碳濃度更高的濃度的氣體(二氧化碳濃縮氣體)會回到原料氣體線(配管11)。因此，藉由使用PSA氣體分離裝置6來進行氣體分離的處理，能夠有效率地提高液化二氧化碳的全體的回收率。 As described above, when the concentration of carbon dioxide in the exhaust gas is lowered, since the partial pressure of carbon dioxide is lowered, liquefaction becomes difficult. When the amount of exhaust gas is increased, the concentration of carbon dioxide will increase, but the proportion of carbon dioxide that will be recovered by liquefaction (hereinafter, simply referred to as "liquefaction recovery rate") will decrease. For example, set the temperature to about -20 ° C, and the pressure is about 1.87 MPaG. When the external discharge set pressure of the exhaust gas of the control valve 24 is set to 2.1 MPaG or more, when the carbon dioxide concentration of the material gas is about 99.9%, the liquefaction recovery rate is 95% or more. Further, when the carbon dioxide concentration of the material gas is about 99%, the liquefaction recovery rate becomes about 80%. When the carbon dioxide concentration of the material gas is about 90%, the liquefaction recovery rate becomes about 40%. The liquefaction recovery rate here is the liquefaction recovery rate in a state where the PSA gas separation device 6 is not used. On the other hand, when the PSA gas separation device 6 is used, the gas (carbon dioxide concentrated gas) which is concentrated to a concentration higher than the carbon dioxide concentration of the original material gas at a high carbon dioxide recovery rate of 90% or more returns to the material gas. Line (pipe 11). Therefore, by performing the gas separation treatment using the PSA gas separation device 6, the overall recovery rate of the liquefied carbon dioxide can be efficiently increased.

本實施型態的二氧化碳分離回收系統X1具備液化回收裝置5及PSA氣體分離裝置6。關於供給到二氧化碳分離回收系統X1的原料氣體，隨著時間經過，該原料氣體中的二氧化碳濃度會變動。在液化回收裝置5中，會持續地從原料氣體中液化回收二氧化碳。另一方面，在PSA氣體分離裝置6中，會因應於原料氣體中的二氧化碳濃度的變動，變更PSA氣體分離步驟中進行的氣體分離處理。 The carbon dioxide separation and recovery system X1 of the present embodiment includes a liquefaction recovery device 5 and a PSA gas separation device 6. Regarding the raw material gas supplied to the carbon dioxide separation and recovery system X1, the concentration of carbon dioxide in the raw material gas changes as time passes. In the liquefaction recovery device 5, carbon dioxide is continuously recovered from the raw material gas. On the other hand, in the PSA gas separation device 6, the gas separation process performed in the PSA gas separation step is changed in accordance with the fluctuation of the carbon dioxide concentration in the material gas.

根據PSA氣體分離步驟中進行的氣體分離處理的第1控制態樣，以二氧化碳感測器21檢測出原料氣體中的二氧化碳濃度，當該檢測出的濃度在既定值以上的情況下(原料氣體中的二氧化碳濃度相對較高的情況下)，停止PSA氣體分離裝置6的處理。另一方面，當二氧化碳感測器21檢測出的二氧化碳濃度在既定值之下的情況下(原料氣體中的二氧化碳濃度 相對較低的情況下)，就執行PSA分離裝置6的處理。也就是，在PSA氣體分離裝置6中，會因應原料氣體的二氧化碳濃度來控制PSA氣體分離處理的開與關，實行間歇運轉。根據這樣的架構，利用PSA氣體分離裝置6來處理液化回收裝置5(液化步驟)中的廢氣即可，因此比起對全部的原料氣體進行PSA處理，能夠縮小PSA氣體分離裝置6的規模。因此，能夠削減PSA氣體分離裝置6(二氧化碳分離回收系統X1)的設備成本。 According to the first control aspect of the gas separation process performed in the PSA gas separation step, the carbon dioxide sensor 21 detects the concentration of carbon dioxide in the material gas, and when the detected concentration is equal to or higher than the predetermined value (in the raw material gas) When the carbon dioxide concentration is relatively high, the treatment of the PSA gas separation device 6 is stopped. On the other hand, when the carbon dioxide concentration detected by the carbon dioxide sensor 21 is below a predetermined value (the concentration of carbon dioxide in the raw material gas) In the relatively low case, the processing of the PSA separating device 6 is performed. That is, in the PSA gas separation device 6, the opening and closing of the PSA gas separation treatment is controlled in accordance with the carbon dioxide concentration of the material gas, and the intermittent operation is performed. According to such a configuration, the exhaust gas in the liquefaction recovery device 5 (liquefaction step) can be treated by the PSA gas separation device 6, and therefore the PSA gas separation device 6 can be downsized compared to the PSA treatment of all the material gases. Therefore, the equipment cost of the PSA gas separation device 6 (carbon dioxide separation and recovery system X1) can be reduced.

如上述，當原料氣體的二氧化碳濃度下降時，液化回收率會下降，因此原料氣體的二氧化碳濃度下降時廢氣量相對變多。在這個廢氣量較多的時候，因為會以PSA氣體分離裝置6對廢氣進行氣體分離處理(二氧化碳濃縮氣體的回收)，所以能夠有效地提高整體的液化二氧化碳的回收率。 As described above, when the carbon dioxide concentration of the material gas is lowered, the liquefaction recovery rate is lowered, so that the amount of the exhaust gas is relatively increased when the carbon dioxide concentration of the material gas is lowered. When the amount of exhaust gas is large, the exhaust gas is subjected to gas separation treatment (recovery of carbon dioxide concentrated gas) by the PSA gas separation device 6, so that the overall recovery rate of liquefied carbon dioxide can be effectively improved.

根據PSA氣體分離步驟的氣體分離處理的第2控制態樣，以二氧化碳感測器21檢測出原料氣體中的二氧化碳濃度，當該檢測出的濃度在既定值以上的情況下(原料氣體中的二氧化碳濃度相對較高的情況下)，減少PSA氣體分離裝置6的氣體分離處理。另一方面，當二氧化碳感測器21檢測出的二氧化碳濃度在既定值之下的情況下(原料氣體中的二氧化碳濃度相對較低的情況下)，就增加PSA分離裝置6的氣體分離處理。也就是，在PSA氣體分離裝置6中，也可因應原料氣體的二氧化碳濃度來增減調整氣體分離的處理量。該處理量的調整能夠藉由根據二氧化碳感測器21的二氧化碳濃度的檢測結果，控制流量調整閥25來實行。又，上述氣體分離的處理量的調整也可以因應原料氣體的二氧化碳的濃度檢出值而多階段地進行。 According to the second control aspect of the gas separation process in the PSA gas separation step, the carbon dioxide sensor 21 detects the concentration of carbon dioxide in the material gas, and when the detected concentration is equal to or higher than the predetermined value (carbon dioxide in the material gas) In the case where the concentration is relatively high, the gas separation treatment of the PSA gas separation device 6 is reduced. On the other hand, when the concentration of carbon dioxide detected by the carbon dioxide sensor 21 is below a predetermined value (in the case where the concentration of carbon dioxide in the material gas is relatively low), the gas separation process of the PSA separation device 6 is increased. That is, in the PSA gas separation device 6, the amount of treatment for adjusting the gas separation may be increased or decreased depending on the carbon dioxide concentration of the material gas. The adjustment of the amount of treatment can be performed by controlling the flow rate adjustment valve 25 based on the detection result of the carbon dioxide concentration of the carbon dioxide sensor 21. Further, the adjustment of the treatment amount of the gas separation may be performed in multiple stages in accordance with the concentration detection value of the carbon dioxide of the material gas.

如上述，當原料氣體的二氧化碳濃度下降時，液化回收率會下降，因此原料氣體的二氧化碳濃度下降時廢氣量相對變多。在這個廢氣量較多的時候，因為會增加以PSA氣體分離裝置6對廢氣進行氣體分離的處理量(二氧化碳濃縮氣體的回收量)，所以能夠有效地提高整體的液化二氧化碳的回收率。 As described above, when the carbon dioxide concentration of the material gas is lowered, the liquefaction recovery rate is lowered, so that the amount of the exhaust gas is relatively increased when the carbon dioxide concentration of the material gas is lowered. When the amount of the exhaust gas is large, the amount of treatment for recovering the exhaust gas by the PSA gas separation device 6 (the amount of recovery of the carbon dioxide concentrated gas) is increased, so that the overall recovery rate of the liquefied carbon dioxide can be effectively improved.

根據PSA氣體分離步驟中進行的氣體分離處理的第3控制態樣，以壓力計23檢測出廢氣的壓力，當該檢測出的壓力在既定值以下的情況下，停止PSA氣體分離裝置6的處理。另一方面，當壓力計23檢測出的廢氣的壓力超過既定值的情況下，就執行PSA分離裝置6的處理。在此，當原料氣體中的二氧化碳濃度下降，精餾塔51的氣相的不純物氣體的分壓增加，廢氣的檢出壓力上升。另一方面，當原料氣體的二氧化碳濃度上升，精餾塔51的氣相的不純物氣體的分壓下降，若二氧化碳被液化，塔壓力容易下降，因而廢氣的檢出壓力下降。像這樣，在PSA氣體分離裝置6中，會因應廢氣的壓力來控制PSA氣體分離處理的開與關，實行間歇運轉。根據第3控制態樣，與上述第1控制態樣同樣地，利用PSA氣體分離裝置6來處理液化回收裝置5(液化步驟)中的廢氣即可，因此比起對全部的原料氣體進行PSA處理，能夠縮小PSA氣體分離裝置6的規模。因此，能夠削減PSA氣體分離裝置6(二氧化碳分離回收系統X1)的設備成本。 According to the third control aspect of the gas separation process performed in the PSA gas separation step, the pressure of the exhaust gas is detected by the pressure gauge 23, and when the detected pressure is equal to or lower than the predetermined value, the processing of the PSA gas separation device 6 is stopped. . On the other hand, when the pressure of the exhaust gas detected by the pressure gauge 23 exceeds a predetermined value, the processing of the PSA separating apparatus 6 is performed. Here, when the concentration of carbon dioxide in the material gas is lowered, the partial pressure of the impurity gas in the gas phase of the fractionator 51 is increased, and the detection pressure of the exhaust gas is increased. On the other hand, when the carbon dioxide concentration of the material gas increases, the partial pressure of the impurity gas in the gas phase of the fractionator 51 decreases, and if the carbon dioxide is liquefied, the column pressure is liable to lower, and thus the detection pressure of the exhaust gas is lowered. As described above, in the PSA gas separation device 6, the PSA gas separation process is controlled to be turned on and off in response to the pressure of the exhaust gas, and the intermittent operation is performed. According to the third control aspect, the exhaust gas in the liquefaction recovery device 5 (liquefaction step) can be treated by the PSA gas separation device 6 in the same manner as in the first control aspect described above, and therefore PSA treatment is performed on all the raw material gases. The scale of the PSA gas separation device 6 can be reduced. Therefore, the equipment cost of the PSA gas separation device 6 (carbon dioxide separation and recovery system X1) can be reduced.

如上述，當原料氣體的二氧化碳濃度下降時，液化回收率會下降，因此原料氣體的二氧化碳濃度下降時廢氣量相對變多。在這個廢氣量較多的時候，因為會以PSA氣體分離 裝置6對廢氣進行氣體分離處理(二氧化碳濃縮氣體的回收)，所以能夠有效地提高整體的液化二氧化碳的回收率。 As described above, when the carbon dioxide concentration of the material gas is lowered, the liquefaction recovery rate is lowered, so that the amount of the exhaust gas is relatively increased when the carbon dioxide concentration of the material gas is lowered. When this amount of exhaust gas is large, it will be separated by PSA gas. Since the apparatus 6 performs gas separation treatment (recovery of carbon dioxide concentrated gas) on the exhaust gas, the recovery rate of the entire liquefied carbon dioxide can be effectively improved.

根據PSA氣體分離步驟的氣體分離處理的第4控制態樣，以壓力計23檢測出廢氣的壓力，當該檢測出的壓力在既定值以下的情況下，減少PSA氣體分離裝置6的氣體分離處理。另一方面，當壓力計23檢測出的廢氣的壓力超過既定值的情況下，就增加PSA分離裝置6的氣體分離處理量。也就是，在PSA氣體分離裝置6中，可因應廢氣的壓力高低來增減調整氣體分離的處理量。該處理量的調整能夠藉由根據壓力計23檢測出的廢氣的壓力，控制流量調整閥25來實行。又，上述氣體分離的處理量的調整也可以因應廢氣的壓力的檢出值而多階段地進行。 According to the fourth control aspect of the gas separation process in the PSA gas separation step, the pressure of the exhaust gas is detected by the pressure gauge 23, and when the detected pressure is below a predetermined value, the gas separation process of the PSA gas separation device 6 is reduced. . On the other hand, when the pressure of the exhaust gas detected by the pressure gauge 23 exceeds a predetermined value, the amount of gas separation processing of the PSA separation device 6 is increased. That is, in the PSA gas separation device 6, the amount of treatment for adjusting the gas separation can be increased or decreased depending on the pressure of the exhaust gas. The adjustment of the amount of treatment can be performed by controlling the flow rate adjustment valve 25 based on the pressure of the exhaust gas detected by the pressure gauge 23. Further, the adjustment of the treatment amount of the gas separation may be performed in multiple stages in accordance with the detection value of the pressure of the exhaust gas.

如上述，當原料氣體的二氧化碳濃度下降時，液化回收率會下降，因此原料氣體的二氧化碳濃度下降時廢氣量相對變多。在這個廢氣量較多的時候，因為會增加以PSA氣體分離裝置6對廢氣進行氣體分離的處理量(二氧化碳濃縮氣體的回收量)，所以能夠有效地提高整體的液化二氧化碳的回收率。 As described above, when the carbon dioxide concentration of the material gas is lowered, the liquefaction recovery rate is lowered, so that the amount of the exhaust gas is relatively increased when the carbon dioxide concentration of the material gas is lowered. When the amount of the exhaust gas is large, the amount of treatment for recovering the exhaust gas by the PSA gas separation device 6 (the amount of recovery of the carbon dioxide concentrated gas) is increased, so that the overall recovery rate of the liquefied carbon dioxide can be effectively improved.

根據PSA氣體分離步驟中進行的氣體分離處理的第5控制態樣，以流量計22檢測出原料氣體的流量，當該原料氣體的流量在既定值以下的情況下(原料氣體的流量相對較少的情況下)，停止PSA氣體分離裝置6的處理。另一方面，當流量計22檢測出的原料氣體的流量超過既定值的情況下(原料氣體的流量相對較多的情況下)，就執行PSA分離裝置6的處理。在此，原料氣體的流量少的情況下，廢氣量相對變少， 因此也可以停止PSA分離裝置6的處理。另一方面，原料氣體的流量多的情況下，廢氣量相對變多，因此PSA氣體分離裝置6的處理的必要性也增加。像這樣，在PSA氣體分離裝置6中，會因應原料氣體的流量來控制PSA氣體分離處理的開與關，實行間歇運轉。根據第5控制態樣，與上述第1控制態樣相同地，利用PSA氣體分離裝置6來處理液化回收裝置5(液化步驟)中的廢氣即可，因此比起對全部的原料氣體進行PSA處理，能夠縮小PSA氣體分離裝置6的規模。因此，能夠削減PSA氣體分離裝置6(二氧化碳分離回收系統X1)的設備成本。 According to the fifth control aspect of the gas separation process performed in the PSA gas separation step, the flow rate of the material gas is detected by the flow meter 22, and when the flow rate of the material gas is below a predetermined value (the flow rate of the material gas is relatively small) In the case of the process, the processing of the PSA gas separation device 6 is stopped. On the other hand, when the flow rate of the material gas detected by the flow meter 22 exceeds a predetermined value (when the flow rate of the material gas is relatively large), the processing of the PSA separation device 6 is executed. Here, when the flow rate of the material gas is small, the amount of the exhaust gas is relatively small. Therefore, the processing of the PSA separating device 6 can also be stopped. On the other hand, when the flow rate of the material gas is large, the amount of the exhaust gas is relatively increased, and therefore the necessity of the treatment of the PSA gas separation device 6 is also increased. As described above, in the PSA gas separation device 6, the PSA gas separation process is controlled to be turned on and off in accordance with the flow rate of the material gas, and the intermittent operation is performed. According to the fifth control aspect, the exhaust gas in the liquefaction recovery device 5 (liquefaction step) can be treated by the PSA gas separation device 6 in the same manner as in the first control aspect described above, and therefore PSA treatment is performed on all the raw material gases. The scale of the PSA gas separation device 6 can be reduced. Therefore, the equipment cost of the PSA gas separation device 6 (carbon dioxide separation and recovery system X1) can be reduced.

如上述，當原料氣體的二氧化碳濃度下降時，液化回收率會下降，因此原料氣體的二氧化碳濃度下降時廢氣量相對變多。在這個廢氣量較多的時候，因為會以PSA氣體分離裝置6對廢氣進行氣體分離處理(二氧化碳濃縮氣體的回收)，所以能夠有效地提高整體的液化二氧化碳的回收率。 As described above, when the carbon dioxide concentration of the material gas is lowered, the liquefaction recovery rate is lowered, so that the amount of the exhaust gas is relatively increased when the carbon dioxide concentration of the material gas is lowered. When the amount of exhaust gas is large, the exhaust gas is subjected to gas separation treatment (recovery of carbon dioxide concentrated gas) by the PSA gas separation device 6, so that the overall recovery rate of liquefied carbon dioxide can be effectively improved.

根據PSA氣體分離步驟的氣體分離處理的第6控制態樣，以流量計22檢測出原料氣體的流量，當該原料氣體的流量在既定值以下的情況下(原料氣體的流量相對少的情況下)，減少PSA氣體分離裝置6的氣體分離處理。另一方面，當流量計22檢測出的原料氣體的流量超過既定值的情況下(原料氣體的流量相對多的情況下)，就增加PSA分離裝置6的氣體分離處理量。也就是，在PSA氣體分離裝置6中，可因應原料氣體的流量來增減調整氣體分離的處理量。該處理量的調整能夠藉由根據流量計22檢測出的原料氣體的流量，控制流量調整閥25來實行。又，上述氣體分離的處理量的調整也可以 因應原料氣體的流量的檢出值而多階段地進行。 According to the sixth control aspect of the gas separation process in the PSA gas separation step, the flow rate of the material gas is detected by the flow meter 22, and when the flow rate of the material gas is equal to or less than a predetermined value (when the flow rate of the material gas is relatively small) The gas separation treatment of the PSA gas separation device 6 is reduced. On the other hand, when the flow rate of the material gas detected by the flow meter 22 exceeds a predetermined value (when the flow rate of the material gas is relatively large), the gas separation processing amount of the PSA separation device 6 is increased. That is, in the PSA gas separation device 6, the amount of treatment for adjusting the gas separation can be increased or decreased depending on the flow rate of the material gas. The adjustment of the amount of treatment can be performed by controlling the flow rate adjustment valve 25 based on the flow rate of the material gas detected by the flow meter 22. Moreover, the adjustment of the processing amount of the gas separation described above may also be performed. The multi-stage operation is performed in accordance with the detection value of the flow rate of the material gas.

如上述，當原料氣體的二氧化碳濃度下降時，液化回收率會下降，因此原料氣體的二氧化碳濃度下降時廢氣量相對變多。在這個廢氣量較多的時候，因為會增加以PSA氣體分離裝置6對廢氣進行氣體分離的處理量(二氧化碳濃縮氣體的回收量)，所以能夠有效地提高整體的液化二氧化碳的回收率。 As described above, when the carbon dioxide concentration of the material gas is lowered, the liquefaction recovery rate is lowered, so that the amount of the exhaust gas is relatively increased when the carbon dioxide concentration of the material gas is lowered. When the amount of the exhaust gas is large, the amount of treatment for recovering the exhaust gas by the PSA gas separation device 6 (the amount of recovery of the carbon dioxide concentrated gas) is increased, so that the overall recovery rate of the liquefied carbon dioxide can be effectively improved.

以上，說明了本發明的具體的實施型態，但本發明並不限定於此，在不脫離發明思想的範圍內可做各種變更。本發明的二氧化碳的分離回收方法及二氧化碳的分離回收系統的架構也能夠做各種變更。 The specific embodiments of the present invention have been described above, but the present invention is not limited thereto, and various modifications can be made without departing from the scope of the invention. The structure of the carbon dioxide separation and recovery method of the present invention and the structure of the carbon dioxide separation and recovery system can also be variously modified.

原料氣體的二氧化碳濃度變得相當低的情況下，也可以在原料氣體被送到液化回收裝置5(液化步驟)之前，追加設置用來將原料氣體的二氧化碳濃縮分離的PSA氣體分離裝置。第2圖表示追加設置PSA分離裝置7的情況下的二氧化碳分離回收系統X2的概略架構。同圖所示的二氧化碳分離回收系統X2中，原料氣體因應需要而適當地供給至PSA氣體分離裝置7，在二氧化碳的濃度提高之後再供給到液化回收裝置5。連接在PSA氣體分離裝置7的出口側的配管上設置有壓縮機8。又，在配管的適當位置，會設置用來切換是否流通到原料氣體的PSA氣體分離裝置7的開閉閥9、10。 When the carbon dioxide concentration of the material gas is relatively low, a PSA gas separation device for concentrating and separating carbon dioxide of the material gas may be additionally provided before the material gas is sent to the liquefaction recovery device 5 (liquefaction step). Fig. 2 shows a schematic configuration of the carbon dioxide separation and recovery system X2 in the case where the PSA separation device 7 is additionally provided. In the carbon dioxide separation and recovery system X2 shown in the figure, the material gas is appropriately supplied to the PSA gas separation device 7 as needed, and is supplied to the liquefaction recovery device 5 after the concentration of carbon dioxide is increased. A compressor 8 is provided on a pipe connected to the outlet side of the PSA gas separation device 7. Further, at the appropriate positions of the piping, on/off valves 9 and 10 for switching whether or not the raw material gas flows to the PSA gas separation device 7 are provided.

X1‧‧‧二氧化碳分離回收系統 X1‧‧‧Carbon Dioxide Separation and Recovery System

1‧‧‧升壓風機 1‧‧‧Booster fan

2‧‧‧脫臭器 2‧‧‧ Deodorizer

3‧‧‧壓縮機 3‧‧‧Compressor

4‧‧‧冷卻器 4‧‧‧ cooler

5‧‧‧液化回收裝置 5‧‧‧Liquid recovery unit

51‧‧‧精餾塔 51‧‧‧Rectifier

52‧‧‧凝縮器 52‧‧‧Condenser

6‧‧‧PSA氣體分離裝置 6‧‧‧PSA gas separation device

11~17‧‧‧配管 11~17‧‧‧Pipe

18‧‧‧配管(返回線) 18‧‧‧Pipe (return line)

21‧‧‧二氧化碳感測器(濃度檢測裝置) 21‧‧‧ Carbon dioxide sensor (concentration detection device)

22‧‧‧流量計(流量檢測裝置) 22‧‧‧Flowmeter (flow detection device)

23‧‧‧壓力計(壓力檢測裝置) 23‧‧‧ Pressure gauge (pressure detection device)

24‧‧‧壓力控制閥 24‧‧‧ Pressure Control Valve

25‧‧‧流量控制閥 25‧‧‧Flow control valve

Claims (9)

一種二氧化碳的分離回收方法，用以對含有二氧化碳及不純物的原料氣體，在該原料氣體的二氧化碳濃度變動的狀況下分離回收二氧化碳，包括：液化步驟，在低溫高壓下從該原料氣體液化回收二氧化碳，並排出廢氣；以及PSA氣體分離步驟，藉由PSA法將該廢氣中含有的二氧化碳濃縮分離，其中因應該原料氣體的二氧化碳的濃度，變動該PSA氣體分離步驟中的氣體分離的處理量。 A method for separating and recovering carbon dioxide for separating and recovering carbon dioxide from a raw material gas containing carbon dioxide and impurities by changing a carbon dioxide concentration of the raw material gas, comprising: a liquefaction step of liquefying and recovering carbon dioxide from the raw material gas under low temperature and high pressure; And discharging the exhaust gas; and the PSA gas separation step of concentrating and separating the carbon dioxide contained in the exhaust gas by a PSA method, wherein the amount of the gas separation in the PSA gas separation step is varied depending on the concentration of the carbon dioxide of the raw material gas. 如申請專利範圍第1項所述之二氧化碳的分離回收方法，其中檢測出該原料氣體的二氧化碳濃度，當該原料氣體的二氧化碳濃度在既定值以上的情況下，減少該PSA氣體分離步驟中的氣體分離的處理量，或者是停止氣體分離的處理，當該原料氣體的二氧化碳濃度低於既定值的情況下，增加該PSA氣體分離步驟中的氣體分離的處理量，或者是實行氣體分離的處理。 The method for separating and recovering carbon dioxide according to claim 1, wherein the carbon dioxide concentration of the raw material gas is detected, and when the carbon dioxide concentration of the raw material gas is greater than or equal to a predetermined value, the gas in the PSA gas separation step is reduced. The amount of separation or the treatment for stopping the gas separation is such that when the carbon dioxide concentration of the material gas is lower than a predetermined value, the treatment amount of the gas separation in the PSA gas separation step is increased, or the treatment for gas separation is performed. 如申請專利範圍第1項所述之二氧化碳的分離回收方法，其中檢測出該廢氣的壓力，當該廢氣的壓力在既定值以下的情況下，減少該PSA氣體分離步驟中的氣體分離的處理量，或者是停止氣體分離的處理，當該廢氣的壓力超過既定值的情況下，增加該PSA氣體分 離步驟中的氣體分離的處理量，或者是實行氣體分離的處理。 The method for separating and recovering carbon dioxide according to claim 1, wherein the pressure of the exhaust gas is detected, and when the pressure of the exhaust gas is below a predetermined value, the amount of gas separation in the PSA gas separation step is reduced. Or the process of stopping the gas separation, and increasing the PSA gas fraction when the pressure of the exhaust gas exceeds a predetermined value The amount of treatment that separates the gas from the step, or the treatment that performs gas separation. 如申請專利範圍第1項所述之二氧化碳的分離回收方法，其中檢測出該原料氣體的流量，當該原料氣體的流量在既定值以下的情況下，減少該PSA氣體分離步驟中的氣體分離的處理量，或者是停止氣體分離的處理，當該原料氣體的流量超過既定值的情況下，增加該PSA氣體分離步驟中的氣體分離的處理量，或者是實行氣體分離的處理。 The method for separating and recovering carbon dioxide according to claim 1, wherein the flow rate of the raw material gas is detected, and when the flow rate of the raw material gas is below a predetermined value, the gas separation in the PSA gas separation step is reduced. The treatment amount is a treatment for stopping the gas separation, and when the flow rate of the material gas exceeds a predetermined value, the treatment amount of the gas separation in the PSA gas separation step is increased, or the treatment for gas separation is performed. 如申請專利範圍第1至4項任一項所述之二氧化碳的分離回收方法，更包括：追加的PSA氣體分離步驟，在該液化步驟之前，藉由PSA法將該原料氣體中含有的二氧化碳濃縮分離。 The method for separating and recovering carbon dioxide according to any one of claims 1 to 4, further comprising: an additional PSA gas separation step of concentrating carbon dioxide contained in the material gas by a PSA method before the liquefaction step Separation. 如申請專利範圍第1至4項任一項所述之二氧化碳的分離回收方法，其中讓該PSA氣體分離步驟中濃縮二氧化碳而得的二氧化碳濃縮氣體，與上述原料氣體合流。 The method for separating and recovering carbon dioxide according to any one of claims 1 to 4, wherein the carbon dioxide concentrated gas obtained by concentrating the carbon dioxide in the PSA gas separation step is combined with the raw material gas. 一種二氧化碳的分離回收系統，用以對含有二氧化碳及不純物的原料氣體，在該原料氣體的二氧化碳濃度變動的狀況下分離回收二氧化碳，包括：液化裝置，在低溫高壓下從該原料氣體液化回收二氧化碳，並排出廢氣；PSA分離裝置，能夠藉由PSA法將該廢氣中含有的二氧化碳濃縮分離，根據該原料氣體及該廢氣中的至少一者的狀 態變化，來變化氣體分離的處理狀態。 A carbon dioxide separation and recovery system for separating and recovering carbon dioxide from a raw material gas containing carbon dioxide and impurities under a condition that a carbon dioxide concentration of the raw material gas is changed, comprising: a liquefaction device for liquefying and recovering carbon dioxide from the raw material gas under low temperature and high pressure; And exhausting the exhaust gas; the PSA separation device can concentrate and separate the carbon dioxide contained in the exhaust gas by a PSA method, according to at least one of the raw material gas and the exhaust gas State changes to change the processing state of gas separation. 如申請專利範圍第7項所述之二氧化碳的分離回收系統，包括以下三者中的至少一者：濃度檢測裝置，檢測出該原料氣體的二氧化碳濃度；壓力檢測裝置，檢測出該廢氣的壓力；以及流量檢測裝置，檢測出該原料氣體的流量。 The separation and recovery system for carbon dioxide according to claim 7, comprising at least one of the following: a concentration detecting device that detects a carbon dioxide concentration of the raw material gas; and a pressure detecting device that detects a pressure of the exhaust gas; And a flow rate detecting device that detects the flow rate of the material gas. 如申請專利範圍第7或8項所述之二氧化碳的分離回收系統，更包括：返回線，用以讓上述PSA氣體分離裝置所濃縮分離的二氧化碳濃縮氣體，與上述原料氣體合流。 The separation and recovery system for carbon dioxide according to claim 7 or 8, further comprising: a return line for converging and separating the carbon dioxide concentrated gas separated and separated by the PSA gas separation device and the raw material gas.
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