JP2007163070A - Method for liquefying carbon dioxide - Google Patents

Method for liquefying carbon dioxide Download PDF

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JP2007163070A
JP2007163070A JP2005361832A JP2005361832A JP2007163070A JP 2007163070 A JP2007163070 A JP 2007163070A JP 2005361832 A JP2005361832 A JP 2005361832A JP 2005361832 A JP2005361832 A JP 2005361832A JP 2007163070 A JP2007163070 A JP 2007163070A
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carbon dioxide
containing gas
gas
refrigerant
cooling
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JP4648180B2 (en
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Koji Kobayashi
宏二 小林
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SEKIYU COMBINAT KODO TOGO UNEI
Research Association of Refinery Integration for Group Operation
Eneos Corp
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SEKIYU COMBINAT KODO TOGO UNEI
Nippon Petroleum Refining Co Ltd
Research Association of Refinery Integration for Group Operation
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for liquefying carbon dioxide, which can more stably liquefy carbon dioxide by suppressing solidification of the carbon dioxide, even if the carbon dioxide concentration in carbon dioxide-containing gas fluctuates. <P>SOLUTION: The carbon dioxide liquefaction method, which cools and liquefies carbon dioxide in carbon dioxide containing gas by means of cold heat from liquefied natural gas, includes the steps of (a) preparing carbon dioxide containing gas of a carbon dioxide partial pressure of 1 MPa or higher; (b) cooling the carbon dioxide containing gas prepared in step a by means of a refrigerant to liquefy the carbon dioxide in the carbon dioxide containing gas; and (c) cooling the refrigerant from step b by means of liquefied natural gas. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、液化天然ガスの冷熱を利用して、二酸化炭素を含有するガス中の二酸化炭素を液化する方法に関する。   The present invention relates to a method for liquefying carbon dioxide in a gas containing carbon dioxide using the cold heat of liquefied natural gas.

石油精製では、製品中の硫黄分除去用に大量の水素を製造、消費している。この水素を製造する際に、大量の炭酸ガスが副生される。例えば、水素製造装置の原料炭化水素をC512(ナフサ留分)で代表し、水蒸気改質にて水素を製造する場合、次式に示すように、製造水素比で約1/3倍容積の炭酸ガスが副生される。 In oil refining, a large amount of hydrogen is produced and consumed to remove sulfur in products. When producing this hydrogen, a large amount of carbon dioxide is by-produced. For example, when the raw material hydrocarbons of hydrogen production equipment are represented by C 5 H 12 (naphtha fraction) and hydrogen is produced by steam reforming, the production hydrogen ratio is about 1/3 times as shown in the following formula. A volume of carbon dioxide is by-produced.

Figure 2007163070
Figure 2007163070

水素製造装置の目的は、高純度水素を得るためであり、副生ガスである炭酸ガスは利用されずに大気放出されているが、昨今の地球温暖化防止の流れの中で、この炭酸ガスを回収し有効に活用することのニーズは高まっている。   The purpose of the hydrogen production equipment is to obtain high-purity hydrogen, and carbon dioxide, which is a by-product gas, is released to the atmosphere without being used. There is a growing need to recover and effectively use the waste.

一方、コンビナートへの液化天然ガス(LNG)基地の設置等に伴い、有効に活用できる冷熱が、比較的容易に利用できる環境が整いつつある。   On the other hand, with the installation of a liquefied natural gas (LNG) base in a complex, an environment in which cold heat that can be effectively used can be used relatively easily is being prepared.

特許文献1には、LNGの冷熱を利用して炭酸ガスを液化炭酸ガスに変換し、これを移送した後に再び炭酸ガスに変換し、さらにこれを移送する技術が開示される。
特開2003−161574号公報
Patent Document 1 discloses a technique for converting carbon dioxide gas into liquefied carbon dioxide gas by using the cold heat of LNG, transferring it to carbon dioxide gas, transferring it again, and further transferring it.
JP 2003-161574 A

二酸化炭素(ガス)が冷却されると、条件によっては液体の状態を経ずに固体になる。二酸化炭素が固化すると、その取り扱いが難しくなり、管路閉塞等が発生する可能性もある。二酸化炭素を回収するうえでは、二酸化炭素を固化させずに液体として回収することが望まれる。   When carbon dioxide (gas) is cooled, it becomes a solid without passing through a liquid state depending on conditions. When carbon dioxide is solidified, it becomes difficult to handle, and there is a possibility that pipe blockage or the like may occur. In collecting carbon dioxide, it is desired to collect the carbon dioxide as a liquid without solidifying it.

一方、水素製造装置で得られる水素および二酸化炭素を含むガスにおいては、運転条件等の変動により、二酸化炭素濃度が変動することがある。この変動によって、二酸化炭素の固化が生じ、運転に支障が出ることが考えられる。   On the other hand, in the gas containing hydrogen and carbon dioxide obtained by the hydrogen production apparatus, the carbon dioxide concentration may fluctuate due to fluctuations in operating conditions and the like. It is thought that this fluctuation causes solidification of carbon dioxide and hinders operation.

本発明の目的は、二酸化炭素含有ガス中の二酸化炭素濃度が変動したとしても、二酸化炭素の固化を抑制し、より安定して二酸化炭素を液化することのできる二酸化炭素の液化方法を提供することである。   An object of the present invention is to provide a carbon dioxide liquefaction method that can suppress solidification of carbon dioxide and liquefy carbon dioxide more stably even if the concentration of carbon dioxide in the carbon dioxide-containing gas varies. It is.

本発明により、二酸化炭素含有ガス中の二酸化炭素を、液化天然ガスの冷熱を利用して冷却して液化する二酸化炭素の液化方法であって、
a)二酸化炭素分圧が1MPa以上である二酸化炭素含有ガスを用意する工程;
b)工程aで用意した二酸化炭素含有ガスを冷媒により冷却して、該二酸化炭素含有ガス中の二酸化炭素を液化する工程;
c)工程bから得られる冷媒を、液化天然ガスにより冷却する工程
を有する二酸化炭素の液化方法が提供される。
According to the present invention, a method for liquefying carbon dioxide in which carbon dioxide in a carbon dioxide-containing gas is liquefied by cooling using the cold heat of liquefied natural gas,
a) preparing a carbon dioxide-containing gas having a carbon dioxide partial pressure of 1 MPa or more;
b) a step of cooling the carbon dioxide-containing gas prepared in step a with a refrigerant to liquefy the carbon dioxide in the carbon dioxide-containing gas;
c) A method for liquefying carbon dioxide is provided which comprises a step of cooling the refrigerant obtained from step b with liquefied natural gas.

本発明により、二酸化炭素含有ガス中の二酸化炭素濃度が変動したとしても、二酸化炭素の固化を抑制し、より安定して二酸化炭素を液化することのできる二酸化炭素の液化方法が提供される。   The present invention provides a carbon dioxide liquefaction method that can suppress solidification of carbon dioxide and liquefy carbon dioxide more stably even if the concentration of carbon dioxide in the carbon dioxide-containing gas varies.

以下図面を用いて本発明の一形態について説明するが、本発明はこれによって限定されるものではない。   Hereinafter, an embodiment of the present invention will be described with reference to the drawings, but the present invention is not limited thereto.

図1は本発明の方法を行うに好適な装置の主要部を示すプロセスフロー図である。   FIG. 1 is a process flow diagram showing the main parts of an apparatus suitable for carrying out the method of the present invention.

本形態では、LNGにより冷媒を介して炭酸ガス含有ガスを冷却して二酸化炭素を液化する。LNGは約−160℃という極低温であるため、LNGによって直接二酸化炭素含有ガスを冷却した場合、二酸化炭素の固化が発生しやすい。しかし、LNGの冷熱を一旦冷媒に移し、その冷媒によって二酸化炭素含有ガスを冷却することにより、より高い温度レベルの冷媒によって冷却を行い得るため、炭酸ガスの固化を防止することがより容易となる。   In this embodiment, carbon dioxide is liquefied by cooling the carbon dioxide-containing gas through a refrigerant with LNG. Since LNG is an extremely low temperature of about −160 ° C., solidification of carbon dioxide tends to occur when the carbon dioxide-containing gas is directly cooled by LNG. However, it is easier to prevent solidification of the carbon dioxide gas because the cold heat of the LNG is once transferred to the refrigerant and the carbon dioxide-containing gas is cooled by the refrigerant so that the cooling can be performed by the refrigerant at a higher temperature level. .

LNGは、約−160℃程度の温度とされ、その気化温度は約−147℃である。また炭酸ガスの固化温度は約−56℃である(炭酸ガスの液化温度は例えば−20℃である)。これらの温度を考慮し、LNGの気化に好適で、炭酸ガスの固化を防止するにも好適な冷媒として、エチレンおよびCHF3(フロンR23)がある。フロンR23はエチレンより蒸気圧が低く、より操作圧を低くすることができるため、冷媒としてフロンR23が好ましい。フロンR23の気化温度は例えば−45℃である。フロンR23を冷媒として用いた場合、例えば、冷媒ガス(第一の気化器出口)温度を−47℃、冷媒液(第一の気化器入口)温度を−60℃とすることができる。 LNG has a temperature of about −160 ° C., and its vaporization temperature is about −147 ° C. The solidification temperature of carbon dioxide is about −56 ° C. (the liquefaction temperature of carbon dioxide is, for example, −20 ° C.). Considering these temperatures, there are ethylene and CHF 3 (Freon R23) as refrigerants suitable for vaporizing LNG and also suitable for preventing solidification of carbon dioxide. Since Freon R23 has a lower vapor pressure than ethylene and can lower the operating pressure, Freon R23 is preferred as the refrigerant. The vaporization temperature of Freon R23 is, for example, −45 ° C. When Freon R23 is used as the refrigerant, for example, the refrigerant gas (first vaporizer outlet) temperature can be set to −47 ° C., and the refrigerant liquid (first vaporizer inlet) temperature can be set to −60 ° C.

図1に示した形態では、冷媒としてフロンR23を採用している。また、二酸化炭素含有ガスとして、水素製造装置から得られるガスを用いる。このガスは二酸化炭素に加え、水素を含む。   In the form shown in FIG. 1, Freon R23 is adopted as the refrigerant. Moreover, the gas obtained from a hydrogen production apparatus is used as a carbon dioxide containing gas. This gas contains hydrogen in addition to carbon dioxide.

二酸化炭素含有ガスが多量の水蒸気を含む場合など、必要に応じて予め水蒸気を分離しておくことができる。例えば、冷却水で二酸化炭素含有ガスを冷却し、水蒸気を凝縮させ、凝縮水を気液分離により分離することができる。   In the case where the carbon dioxide-containing gas contains a large amount of water vapor, the water vapor can be separated in advance as necessary. For example, the carbon dioxide-containing gas can be cooled with cooling water, water vapor can be condensed, and the condensed water can be separated by gas-liquid separation.

二酸化炭素含有ガスは、圧縮機1により、二酸化炭素の分圧が1MPa(絶対圧)以上となるように昇圧される。   The carbon dioxide-containing gas is pressurized by the compressor 1 so that the partial pressure of carbon dioxide is 1 MPa (absolute pressure) or more.

昇圧された二酸化炭素含有ガスは、必要に応じ、乾燥器2にて乾燥させることができる。乾燥器としては、吸着剤式の乾燥器などを適宜利用できる。   The pressure-increased carbon dioxide-containing gas can be dried in the dryer 2 as necessary. As the dryer, an adsorbent dryer can be used as appropriate.

乾燥器を経た二酸化炭素含有ガスは、二酸化炭素含有ガス冷却器3にて冷媒(フロンR23の液)によって冷却され、二酸化炭素が凝縮する。二酸化炭素含有ガス冷却器は、熱交換器であり、例えば、縦型のシェルアンドチューブ型熱交換器を採用し、シェル側にフロンR23液を導入し、チューブ側に下向きに二酸化炭素含有ガスを流すことができる。   The carbon dioxide-containing gas that has passed through the dryer is cooled by the refrigerant (liquid of Freon R23) in the carbon dioxide-containing gas cooler 3, and the carbon dioxide is condensed. The carbon dioxide-containing gas cooler is a heat exchanger. For example, a vertical shell-and-tube heat exchanger is adopted, the CFC R23 liquid is introduced into the shell side, and the carbon dioxide-containing gas is introduced downward into the tube side. It can flow.

二酸化炭素含有ガス冷却器3から二酸化炭素含有ガス(凝縮した二酸化炭素を含む)が気液分離器4に導かれる。その液相から液化した二酸化炭素が得られ、その気相から凝縮しなかったガス(主に水素)が得られる。このガスは、適宜利用もしくはパージすることができる。   A carbon dioxide-containing gas (including condensed carbon dioxide) is introduced from the carbon dioxide-containing gas cooler 3 to the gas-liquid separator 4. The liquefied carbon dioxide is obtained from the liquid phase, and the gas (mainly hydrogen) that is not condensed is obtained from the gas phase. This gas can be used or purged as appropriate.

二酸化炭素含有ガス冷却器3から導出されたフロンR23は、気液分離器4のジャケット部に供給され、気液分離器を冷却する。気液分離器にジャケットを設けてフロンR23により気液分離器を冷却することにより、二酸化炭素が再び気化することを防止することが容易となる。   Freon R23 led out from the carbon dioxide-containing gas cooler 3 is supplied to the jacket portion of the gas-liquid separator 4 to cool the gas-liquid separator. By providing a jacket in the gas-liquid separator and cooling the gas-liquid separator with Freon R23, it becomes easy to prevent the carbon dioxide from vaporizing again.

気液分離器のジャケット部から払い出されたフロンR23ガスは、冷媒冷却器5にてLNGと熱交換し、冷却されて液化してフロンR23液となる。一方、ここでLNGは気化して天然ガスとして払い出される。フロンR23液は再び二酸化炭素含有ガス冷却器3に戻される。   The chlorofluorocarbon R23 gas discharged from the jacket portion of the gas-liquid separator exchanges heat with LNG in the refrigerant cooler 5, is cooled and liquefied, and becomes chlorofluorocarbon R23 liquid. On the other hand, LNG is vaporized and discharged as natural gas. The Freon R23 liquid is returned to the carbon dioxide-containing gas cooler 3 again.

二酸化炭素の三重点は、−56.6℃、0.52MPaである。二酸化炭素含有ガスを冷却して二酸化炭素を液化する前に、二酸化炭素含有ガス中の二酸化炭素分圧を1MPa以上としておくことにより、多少の変動があったとしても、二酸化炭素分圧が三重点の圧力を下回ることを抑制することが容易となる。   The triple point of carbon dioxide is −56.6 ° C. and 0.52 MPa. Before the carbon dioxide-containing gas is cooled and liquefied, the partial pressure of carbon dioxide in the carbon dioxide-containing gas is set to 1 MPa or more so that the partial pressure of carbon dioxide is triple even if there is some variation. It is easy to suppress the pressure from being reduced below the pressure.

二酸化炭素含有ガスとしては、石油精製で用いられる水素製造装置から得られる二酸化炭素含有ガスを用いることができる。これ以外にも、二酸化炭素と、二酸化炭素より沸点の低いガス(例えば水素)とを含む混合ガスを用いることができる。あるいは実質的に二酸化炭素のみからなるガスを用いることもできる。   As the carbon dioxide-containing gas, a carbon dioxide-containing gas obtained from a hydrogen production apparatus used in petroleum refining can be used. In addition, a mixed gas containing carbon dioxide and a gas having a boiling point lower than that of carbon dioxide (for example, hydrogen) can be used. Or the gas which consists only of carbon dioxide substantially can also be used.

石油精製で用いられる水素製造装置では、水蒸気改質反応、高温CO変性反応、低温CO変性反応を順次行い、水素および二酸化炭素を含むガスが製造される。CO変性反応は一酸化炭素と水から二酸化炭素と水素とを生成する反応である。最終段階である低温CO変性反応は、例えば、1〜4MPa、190〜240℃で行われ、ドライベースでおおよそ70モル%の水素、おおよそ20モル%の二酸化炭素を含み、さらに少量の一酸化炭素およびメタンを含む二酸化炭素含有ガスが得られる。このため、二酸化炭素含有ガス中の二酸化炭素分圧が三重点の圧力を下回る状況があり得る。本発明によれば、このような二酸化炭素含有ガスを用いる場合でも、より安定した二酸化炭素液化が可能となる。   In a hydrogen production apparatus used in petroleum refining, a gas containing hydrogen and carbon dioxide is produced by sequentially performing a steam reforming reaction, a high temperature CO modification reaction, and a low temperature CO modification reaction. The CO modification reaction is a reaction that generates carbon dioxide and hydrogen from carbon monoxide and water. The final low-temperature CO modification reaction is performed at, for example, 1 to 4 MPa and 190 to 240 ° C., and includes approximately 70 mol% hydrogen and approximately 20 mol% carbon dioxide on a dry basis, and a smaller amount of carbon monoxide. And a carbon dioxide-containing gas containing methane. For this reason, there may be a situation in which the partial pressure of carbon dioxide in the carbon dioxide-containing gas is lower than the pressure at the triple point. According to the present invention, even when such a carbon dioxide-containing gas is used, more stable carbon dioxide liquefaction becomes possible.

二酸化炭素分圧が1MPa以上である二酸化炭素含有ガスを用意するために、上述のように二酸化炭素含有ガスを昇圧することができる。もともと確実に二酸化炭素分圧が1MPa以上であるガスが利用できる場合には、圧縮機および昇圧を省略することができる。しかしながら運転条件の不測の変動に備え、昇圧機を設置し、また二酸化炭素含有ガス中の二酸化炭素分圧をオンラインで知ることのできる機器を用い、二酸化炭素分圧が1MPa以上となるよう昇圧機を制御することが好ましい。このために、二酸化炭素含有ガス中の二酸化炭素濃度を直接もしくは間接的に検出可能なセンサー、二酸化炭素含有ガスの圧力を知るための圧力計を用い、さらにこれらセンサーおよび圧力計からの信号を基に二酸化炭素分圧を算出し、実際の二酸化炭素分圧と設定値(例えば1MPa)とを比較してその差に基づいて圧縮機を制御する制御装置などを用いることができる。   In order to prepare a carbon dioxide-containing gas having a carbon dioxide partial pressure of 1 MPa or more, the carbon dioxide-containing gas can be boosted as described above. If a gas having a carbon dioxide partial pressure of 1 MPa or more can be used with certainty, the compressor and the pressure increase can be omitted. However, in preparation for unforeseen fluctuations in operating conditions, a booster is installed, and equipment that can know the carbon dioxide partial pressure in the carbon dioxide-containing gas online is used to boost the carbon dioxide partial pressure to 1 MPa or higher. Is preferably controlled. For this purpose, a sensor capable of directly or indirectly detecting the carbon dioxide concentration in the carbon dioxide-containing gas and a pressure gauge for knowing the pressure of the carbon dioxide-containing gas are used, and the signals from these sensors and the pressure gauge are used as a basis. A control device that calculates the partial pressure of carbon dioxide, compares the actual partial pressure of carbon dioxide with a set value (for example, 1 MPa), and controls the compressor based on the difference can be used.

本発明は、例えばLNG基地と水素製造装置を備える製油所において、利用することができる。得られる液化炭酸ガスは、例えば製油所に隣接する化学プラントにおいて化学品の原料として利用できる。   The present invention can be used, for example, in a refinery including an LNG base and a hydrogen production apparatus. The obtained liquefied carbon dioxide gas can be used as a raw material for chemical products in a chemical plant adjacent to a refinery, for example.

本発明の方法を実施するに好適な装置の例を示すプロセスフロー図である。FIG. 2 is a process flow diagram illustrating an example of an apparatus suitable for performing the method of the present invention.

符号の説明Explanation of symbols

1 圧縮器
2 乾燥器
3 原料ガス冷却器
4 液化炭酸ガスドラム
5 冷媒冷却器
DESCRIPTION OF SYMBOLS 1 Compressor 2 Dryer 3 Raw material gas cooler 4 Liquefied carbon dioxide drum 5 Refrigerant cooler

Claims (1)

二酸化炭素含有ガス中の二酸化炭素を、液化天然ガスの冷熱を利用して冷却して液化する二酸化炭素の液化方法であって、
a)二酸化炭素分圧が1MPa以上である二酸化炭素含有ガスを用意する工程;
b)工程aで用意した二酸化炭素含有ガスを冷媒により冷却して、該二酸化炭素含有ガス中の二酸化炭素を液化する工程;
c)工程bから得られる冷媒を、液化天然ガスにより冷却する工程
を有する二酸化炭素の液化方法。
A method for liquefying carbon dioxide in which carbon dioxide in a carbon dioxide-containing gas is liquefied by cooling using the cold heat of liquefied natural gas,
a) preparing a carbon dioxide-containing gas having a carbon dioxide partial pressure of 1 MPa or more;
b) a step of cooling the carbon dioxide-containing gas prepared in step a with a refrigerant to liquefy the carbon dioxide in the carbon dioxide-containing gas;
c) A carbon dioxide liquefaction method comprising a step of cooling the refrigerant obtained from step b with liquefied natural gas.
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JP2009114048A (en) * 2007-11-02 2009-05-28 Metal Industries Research & Development Centre Carbon dioxide supply system
KR20160134347A (en) * 2015-05-15 2016-11-23 대우조선해양 주식회사 The System and Method for Carbon Dioxide Separation from Natural Gas before Gas Liquefaction Process

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JP2003161574A (en) * 2001-11-28 2003-06-06 Mitsubishi Chemicals Corp Cold utilizing system for liquefied natural gas

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JP2003161574A (en) * 2001-11-28 2003-06-06 Mitsubishi Chemicals Corp Cold utilizing system for liquefied natural gas

Cited By (3)

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JP2009114048A (en) * 2007-11-02 2009-05-28 Metal Industries Research & Development Centre Carbon dioxide supply system
KR20160134347A (en) * 2015-05-15 2016-11-23 대우조선해양 주식회사 The System and Method for Carbon Dioxide Separation from Natural Gas before Gas Liquefaction Process
KR102376275B1 (en) * 2015-05-15 2022-03-18 대우조선해양 주식회사 The System and Method for Carbon Dioxide Separation from Natural Gas before Gas Liquefaction Process

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