JP5733974B2 - CO shift conversion system and method, coal gasification power plant - Google Patents

CO shift conversion system and method, coal gasification power plant Download PDF

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JP5733974B2
JP5733974B2 JP2010283811A JP2010283811A JP5733974B2 JP 5733974 B2 JP5733974 B2 JP 5733974B2 JP 2010283811 A JP2010283811 A JP 2010283811A JP 2010283811 A JP2010283811 A JP 2010283811A JP 5733974 B2 JP5733974 B2 JP 5733974B2
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gas
shift conversion
hydrogen sulfide
product gas
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佳彦 土山
佳彦 土山
小山　智規
智規 小山
貴 藤井
貴 藤井
絵莉 羽有
絵莉 羽有
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Mitsubishi Heavy Industries Ltd
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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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00—Combustion technologies with mitigation potential
    • Y02E20/16—Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00—Combustion technologies with mitigation potential
    • Y02E20/16—Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
    • Y02E20/18—Integrated gasification combined cycle [IGCC], e.g. combined with carbon capture and storage [CCS]
    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Description

本発明は、ＣＯシフト反応を効率よく行うことができるＣＯシフト変換システム及び方法、石炭ガス化発電プラントに関する。   The present invention relates to a CO shift conversion system and method capable of efficiently performing a CO shift reaction, and a coal gasification power plant.

石炭の有効利用は近年のエネルギー問題での切り札の一つとして注目されている。一方、石炭を付加価値の高いエネルギー媒体として、変換するためには石炭ガス化技術、ガス精製技術など高度な技術が必要とされる。このガス化ガスを用いて発電する石炭ガス化複合発電システムが提案されている（特許文献１）。   Effective use of coal has attracted attention as one of the trump cards in recent energy problems. On the other hand, advanced technology such as coal gasification technology and gas purification technology is required to convert coal as an energy medium with high added value. A coal gasification combined power generation system that generates power using this gasification gas has been proposed (Patent Document 1).

この石炭ガス化複合発電（Ｉｎｔｅｇｒａｔｅｄ ｃｏａｌ． Ｇａｓｉｆｉｃａｔｉｏｎ Ｃｏｍｂｉｎｅｄ Ｃｙｃｌｅ：ＩＧＣＣ）とは、石炭を高温高圧のガス化炉で可燃性ガスに転換し、そのガス化ガスを燃料としてガスタービンと蒸気タービンとによる複合発電を行うシステムをいう。   This integrated coal gasification combined cycle (IGCC) is a combination of a gas turbine and a steam turbine that converts coal into combustible gas in a high-temperature and high-pressure gasification furnace and uses the gasification gas as fuel. A system that generates electricity.

石炭ガス化ガス（生成ガス）中に存在する炭化水素化合物は、殆どが一酸化炭素（ＣＯ）であり、二酸化炭素（ＣＯ2）、炭化水素（ＣＨ4、ＣnＨm）は数パーセントに過ぎない。この結果、ＣＯ2を回収するためには、生成ガス中に存在するＣＯをＣＯ2に転換する必要があり、水蒸気（Ｈ2Ｏ）を添加しつつ、シフト触媒により下記反応によってＣＯ2に転換することが提案されている。
ＣＯ＋Ｈ2Ｏ⇔ ＣＯ2＋Ｈ2＋４０．９ｋＪ／ｍｏｌ (発熱反応) ・・・（１） Most of the hydrocarbon compounds present in the coal gasification gas (product gas) are carbon monoxide (CO), and carbon dioxide (CO 2 ) and hydrocarbons (CH 4 , CnHm) are only a few percent. As a result, in order to recover the CO 2 is converted to CO present in the product gas must be converted to CO 2, while adding water vapor (H 2 O), the shift catalyst to CO 2 by the following reaction It has been proposed to do.
CO + H 2 O⇔CO 2 + H 2 +40.9 kJ / mol (exothermic reaction) (1)

これまで、化学工業分野でのシフト反応に対する知見より、ＣＯシフト反応器入口での水蒸気添加割合（Ｈ2Ｏ／ＣＯ）を十分に高くすることにより、上記（１）の反応を進めた上で、希望するＣＯ→ＣＯ2転換率を得ることができることとなる。 Up to now, based on the knowledge of shift reaction in the chemical industry, the reaction (1) has been advanced by sufficiently increasing the steam addition ratio (H 2 O / CO) at the CO shift reactor inlet. Thus, the desired CO → CO 2 conversion rate can be obtained.

特開２００４−３３１７０１号公報Japanese Patent Laid-Open No. 2004-331701

一方、ＣＯ2回収設備を備えたＩＧＣＣプラントは、発電プラントであり、環境（ＣＯ2排出量の低減）に配慮すると共に、プラント発電効率にも重点を置く必要がある。
つまり、シフト反応器入口における水蒸気添加割合（Ｈ2Ｏ／ＣＯ）のための水蒸気添加源に計画されているＨＲＳＧ（排熱回収ボイラ）よりの抽気中圧蒸気量の低減がプラント効率向上を図る上で重要な要素であるため、ＨＲＳＧからの中圧蒸気をなるべく減らすことが、発電効率上昇の点から求められている。 On the other hand, an IGCC plant equipped with a CO 2 recovery facility is a power plant, and it is necessary to give consideration to the environment (reduction of CO 2 emissions) and to emphasize plant power generation efficiency.
That is, the reduction of the amount of steam extracted from the HRSG (exhaust heat recovery boiler) planned as the steam addition source for the steam addition ratio (H 2 O / CO) at the shift reactor inlet improves the plant efficiency. Since it is an important factor above, it is required to reduce the medium-pressure steam from HRSG as much as possible from the viewpoint of increasing the power generation efficiency.

また、シフト変換装置におけるシフト反応にはＣＯシフト触媒（例えば硫化モリブデン（ＭｏＳ3）が用いられるが、外部から補給する水蒸気量が少ない場合、触媒表面にコーキング（炭素析出）が発生して触媒劣化を引き起こし、変換効率が低下するという問題がある。 A CO shift catalyst (for example, molybdenum sulfide (MoS 3 )) is used for the shift reaction in the shift converter, but when the amount of water replenished from the outside is small, coking (carbon deposition) occurs on the catalyst surface and the catalyst deteriorates. Cause the conversion efficiency to decrease.

本発明は、前記問題に鑑み、水蒸気量が少ない場合でも触媒劣化がなく、ＣＯシフト反応を効率よく行うことができるＣＯシフト変換システム及び方法、石炭ガス化発電プラントを提供することを課題とする。   In view of the above problems, an object of the present invention is to provide a CO shift conversion system and method, and a coal gasification power plant capable of efficiently performing a CO shift reaction without catalyst deterioration even when the amount of water vapor is small. .

上述した課題を解決するための本発明の第１の発明は、硫化モリブデンを用いたＣＯシフト触媒を有し、生成ガス中のＣＯをＣＯ2に変換するＣＯシフト変換装置と、該ＣＯシフト変換装置の上流側に設けられ、生成ガス中のＣＯをＣＯ2へ変換するために要する水蒸気を供給する水蒸気供給手段と、水蒸気を供給した生成ガスに水スプレを混合器を介して供給する水スプレ供給手段とを具備するＣＯシフト変換部を備え、前記ＣＯシフト変換部が少なくとも２以上直列に多段連結され、生成ガス中の硫化水素濃度が１００ｐｐｍ以下の場合に、水スプレを混合器に供給することを特徴とするＣＯシフト変換システムにある。 A first invention of the present invention for solving the above-mentioned problems includes a CO shift conversion device that has a CO shift catalyst using molybdenum sulfide and converts CO in the product gas into CO 2 , and the CO shift conversion A water vapor supply means provided on the upstream side of the apparatus for supplying water vapor required for converting CO in the generated gas into CO 2; and a water spray for supplying water spray to the generated gas supplied with water vapor via a mixer. includes a CO shift conversion unit having a supply means, the CO shift converter unit is multistage connected in series at least two supplies when hydrogen sulfide concentration in the product gas is 100ppm or less, a water spray into the mixer It is in the CO shift conversion system characterized by this.

第２の発明は、第１の発明において、生成ガス中の硫化水素濃度が１００ｐｐｍ以下の場合に、硫化水素を供給する硫化水素供給手段を有することを特徴とするＣＯシフト変換システムにある。 A second invention is the CO shift conversion system according to the first invention, further comprising hydrogen sulfide supply means for supplying hydrogen sulfide when the concentration of hydrogen sulfide in the product gas is 100 ppm or less .

第３の発明は、石炭をガス化して生成ガスを得るガス化炉と、生成ガス中のＣＯをＣＯ2に変換する第１又は２の発明のＣＯシフト変換システムと、ＣＯシフトガス中のＣＯ2を回収するＣＯ2吸収塔と吸収液を再生する吸収液再生塔とを備えたＣＯ2回収装置と、精製ガスを燃焼する燃焼器を備えたガスタービン設備と、ガスタービン設備の燃焼排ガスの熱エネルギーを回収する排熱回収ボイラ（ＨＲＳＧ）と、排熱回収ボイラで回収した蒸気を用いて発電する蒸気タービン設備とを具備することを特徴とする石炭ガス化発電プラントにある。
A third invention is a gasification furnace to obtain a product gas of coal is gasified, the CO shift conversion system of the first or second invention for converting CO in the product gas to CO 2, CO 2 in the CO shifted gas CO 2 recovery device having a CO 2 absorption tower for recovering gas and an absorption liquid regeneration tower for regenerating the absorption liquid, gas turbine equipment having a combustor for burning purified gas, and heat of combustion exhaust gas of the gas turbine equipment A coal gasification power plant comprising an exhaust heat recovery boiler (HRSG) that recovers energy and a steam turbine facility that generates power using steam recovered by the exhaust heat recovery boiler.

第４の発明は、第１又は第２の発明のＣＯシフト変換システムを用い、請求項１又は２のＣＯシフト変換システムを用い、生成ガス中の硫化水素濃度が１００ｐｐｍ以下の場合に、水スプレを混合器に供給してＣＯシフト触媒の温度上昇を抑制することを特徴とするＣＯシフト変換方法にある。 A fourth invention uses the CO shift conversion system according to the first or second invention, and uses the CO shift conversion system according to claim 1 or 2, and when the hydrogen sulfide concentration in the product gas is 100 ppm or less, the supplied to the mixer in the CO shift conversion method characterized by suppressing the temperature increase of the CO shift catalyst.

第５の発明は、第４の発明において、生成ガス中の硫化水素濃度が１００ｐｐｍ以下の場合に、硫化水素を供給する硫化水素供給手段を有することを特徴とするＣＯシフト変換方法にある。 A fifth invention is the CO shift conversion method according to the fourth invention, further comprising hydrogen sulfide supply means for supplying hydrogen sulfide when the concentration of hydrogen sulfide in the product gas is 100 ppm or less .

本発明によれば、水スプレを供給することにより、水蒸気量が少ない場合でも触媒劣化がなく、ＣＯシフト反応を効率よく行うことができる。よって、水蒸気の供給量を増大させることなくＣＯシフト反応を効率よく行うことができる。これにより従来ＨＲＳＧから供給していた抽気中圧蒸気の供給量を低減することができる。この結果、発電効率が向上し、プラント全体のエネルギー効率を向上させることができる。   According to the present invention, by supplying water spray, even when the amount of water vapor is small, there is no catalyst deterioration and the CO shift reaction can be performed efficiently. Therefore, the CO shift reaction can be performed efficiently without increasing the supply amount of water vapor. Thereby, supply_amount | feed_rate of the extraction intermediate pressure steam conventionally supplied from HRSG can be reduced. As a result, the power generation efficiency is improved and the energy efficiency of the entire plant can be improved.

図１は、実施例１に係るＣＯシフト変換システムの概略図である。FIG. 1 is a schematic diagram of a CO shift conversion system according to the first embodiment. 図２は、ＣＯシフト変換装置の触媒温度と、（Ｈ2Ｓ／Ｈ2Ｏ）3との関係図である。FIG. 2 is a relationship diagram between the catalyst temperature of the CO shift converter and (H 2 S / H 2 O) 3 . 図３は、実施例２に係るエネルギー回収装置を備えた石炭ガス化発電プラントの概略図である。FIG. 3 is a schematic diagram of a coal gasification power plant including the energy recovery device according to the second embodiment. 図４は、実施例３に係るＣＯシフト変換システムの概略図である。FIG. 4 is a schematic diagram of a CO shift conversion system according to the third embodiment.

以下、この発明につき図面を参照しつつ詳細に説明する。なお、この実施例によりこの発明が限定されるものではない。また、下記実施例における構成要素には、当業者が容易に想定できるもの、あるいは実質的に同一のものが含まれる。   Hereinafter, the present invention will be described in detail with reference to the drawings. Note that the present invention is not limited to the embodiments. In addition, constituent elements in the following embodiments include those that can be easily assumed by those skilled in the art or those that are substantially the same.

本発明による実施例に係るＣＯシフト変換システムについて、図面を参照して説明する。図１は、実施例１に係るＣＯシフト変換システムの概略図である。
図１に示すように、本実施例に係るＣＯシフト変換システム１０Ａは、ＣＯシフト触媒１１を有し、生成ガス１２中のＣＯをＣＯ2に変換するＣＯシフト変換装置１３と、該ＣＯシフト変換装置１３の上流側に設けられ、生成ガス１２中に水蒸気１４を供給する水蒸気供給手段１５と、水蒸気１４を供給した後に、水スプレ１６を混合器１７により供給する水スプレ供給手段１８と、を具備するＣＯシフト変換部２０とからなり、前記ＣＯシフト変換部２０が少なくとも２以上直列に多段連結されている。図１中、符号２１はＨ2Ｓ濃度計、２２は温度計、２３はＣＯシフトガス、Ｖ1、Ｖ2はバルブを図示する。 A CO shift conversion system according to an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a schematic diagram of a CO shift conversion system according to the first embodiment.
As shown in FIG. 1, a CO shift conversion system 10A according to the present embodiment includes a CO shift catalyst 11, a CO shift conversion device 13 that converts CO in the product gas 12 into CO 2 , and the CO shift conversion A water vapor supply means 15 provided upstream of the apparatus 13 for supplying the water vapor 14 into the product gas 12, and a water spray supply means 18 for supplying the water spray 16 by the mixer 17 after the water vapor 14 is supplied. The CO shift conversion unit 20 is provided, and at least two or more CO shift conversion units 20 are connected in series in series. In FIG. 1, reference numeral 21 denotes an H 2 S concentration meter, 22 denotes a thermometer, 23 denotes a CO shift gas, and V 1 and V 2 denote valves.

本発明では、生成ガス１２中の硫化水素（Ｈ2Ｓ）濃度が低い場合でも、水スプレ供給手段１８から水スプレ１６を十分供給することにより、ＣＯシフト反応の発熱反応に起因する温度上昇を抑えることができ、触媒劣化を抑制することができる。なお、水スプレ１６を直接生成ガス１２中に供給することなく、混合器１７を用いて混合しているのは、後流側に設けた触媒劣化を防止するために、水滴が十分気化するために設けている。 In the present invention, even when the hydrogen sulfide (H 2 S) concentration in the product gas 12 is low, by sufficiently supplying the water spray 16 from the water spray supply means 18, the temperature rise caused by the exothermic reaction of the CO shift reaction can be reduced. It is possible to suppress the deterioration of the catalyst. The mixing of the water spray 16 using the mixer 17 without supplying it directly into the product gas 12 is because water droplets are sufficiently vaporized to prevent deterioration of the catalyst provided on the downstream side. Provided.

これは、硫化モリブデン濃度が低い場合には、ＣＯシフト変換装置１３内の温度が例えば２５０℃程度の場合、そのＣＯシフト変換反応に起因する発熱反応により、触媒温度が上昇し、触媒不安定領域から、酸化モリブデン（ＭｏＯ3）に変化し、その後コーキングが発生して、触媒機能が発揮されなかった。 This is because when the molybdenum sulfide concentration is low, when the temperature in the CO shift conversion device 13 is about 250 ° C., for example, the catalyst temperature rises due to the exothermic reaction resulting from the CO shift conversion reaction. To molybdenum oxide (MoO 3 ), and then coking occurred and the catalytic function was not exhibited.

ここで、図２にＣＯシフト変換装置の触媒温度と、（Ｈ2Ｓ／Ｈ2Ｏ）3との関係図を示す。図２によれば、硫化水素濃度が低いほど、触媒温度が低い領域で、硫化モリブデン（ＭｏＳ3）が酸化モリブデン（ＭｏＯ3）に変化するのが確認される。そこで、本発明では、硫化モリブデン（ＭｏＳ3）の濃度が例えば１００ｐｐｍ以下と低い場合において、ＣＯシフト変換装置１３における温度を求め、ＣＯシフト変換装置１３内に導入する生成ガス１２中の硫化水素の濃度をＨ2Ｓ濃度計２１により求めることで、図２に示す（Ｈ2Ｓ／Ｈ2Ｏ）3が計算より求められ、この結果、硫化モリブデンの安定領域となるような水の投入量を求めることができる。これにより、硫化モリブデンは安定に存在することとなるので、ＣＯシフト変換が効率よく行うことができる。 Here, FIG. 2 shows a relationship diagram between the catalyst temperature of the CO shift converter and (H 2 S / H 2 O) 3 . According to FIG. 2, it is confirmed that molybdenum sulfide (MoS 3 ) changes to molybdenum oxide (MoO 3 ) in a region where the catalyst temperature is lower as the hydrogen sulfide concentration is lower. Therefore, in the present invention, when the concentration of molybdenum sulfide (MoS 3 ) is as low as 100 ppm or less, for example, the temperature in the CO shift converter 13 is obtained, and the hydrogen sulfide in the product gas 12 introduced into the CO shift converter 13 is obtained. By calculating the concentration with the H 2 S densitometer 21, (H 2 S / H 2 O) 3 shown in FIG. 2 can be obtained by calculation. As a result, the amount of water input to be a stable region of molybdenum sulfide is determined. Can be sought. Thereby, since molybdenum sulfide exists stably, CO shift conversion can be performed efficiently.

ここで、本発明では、硫化水素（Ｈ2Ｓ）の濃度について、１００ｐｐｍ以下を低い場合としているのは、図２より、水を１とした場合、１×１０-12となり、これに対応する温度が３２５℃であるので、それ以下の場合には、触媒安定領域が極めて少なくなり、触媒表面にコーキング（炭素析出）が発生し触媒劣化を引き起こすこととなるからである。よって、本発明では硫化モリブデン濃度が低い場合とは１００ｐｐｍとしている。
なお、ＭｏＳ3安定領域とＭｏＯ3安定領域の境界線は触媒の粒子径等で若干変化する。 Here, in the present invention, the case where the concentration of hydrogen sulfide (H 2 S) is as low as 100 ppm or less is 1 × 10 −12 when water is 1, as shown in FIG. 2, corresponding to this. This is because the temperature is 325 ° C., and if the temperature is lower than that, the catalyst stable region becomes extremely small, and coking (carbon deposition) occurs on the catalyst surface, causing catalyst deterioration. Therefore, in the present invention, the case where the molybdenum sulfide concentration is low is 100 ppm.
Note that the boundary line between the MoS 3 stable region and the MoO 3 stable region slightly changes depending on the particle diameter of the catalyst.

多段に連結するのは、触媒を分散させて少しずつＣＯシフト変換を行うことで、温度上昇を抑制するようにしている。   The multi-stage connection is made by suppressing the temperature rise by dispersing the catalyst and performing CO shift conversion little by little.

なお、本実施例ではＣＯシフト変換部２０を２段のものを例示するが、必要に応じて２段、３段・・・と設けるようにすればよい。よって、生成ガス１２中の硫化水素濃度が例えば１０ｐｐｍと更に低いような場合には、多段連結の数を多くするようにすればよい。ここで、生成ガス１２中の硫化水素の濃度は、例えば石炭ガス化発電プラント（ＩＧＣＣ）のガス火炉に供給する原炭の生産地、生産ロット等により大きく左右するので、供給する原炭の種類の変更の際には、特にＣＯシフト変換部２０の段数についての選定について留意するようにすればよい。   In the present embodiment, the CO shift conversion unit 20 is illustrated as having two stages, but may be provided with two stages, three stages, etc. as necessary. Therefore, when the concentration of hydrogen sulfide in the product gas 12 is even lower, for example, 10 ppm, the number of multistage connections may be increased. Here, the concentration of hydrogen sulfide in the product gas 12 greatly depends on the production location, production lot, etc. of the raw coal supplied to the gas furnace of the coal gasification power plant (IGCC), for example. When changing the above, it is sufficient to pay attention to the selection of the number of stages of the CO shift conversion unit 20 in particular.

本実施例によれば、生成ガス１２中の硫化水素の濃度が低く、触媒温度が上昇する場合においては、水蒸気１４の温度を変更することなく、水スプレ１６を供給することにより、水蒸気量が少ないままでも触媒劣化がなく、ＣＯシフト反応を効率よく行うことができる。よって、水蒸気１４の供給量を増大させることなくＣＯシフト反応を効率よく行うことができる。   According to this embodiment, when the concentration of hydrogen sulfide in the product gas 12 is low and the catalyst temperature rises, the amount of water vapor is reduced by supplying the water spray 16 without changing the temperature of the water vapor 14. Even if the amount is small, the catalyst is not deteriorated and the CO shift reaction can be performed efficiently. Therefore, the CO shift reaction can be efficiently performed without increasing the supply amount of the water vapor 14.

本発明による実施例に係るエネルギー回収装置を備えた石炭ガス化発電プラントについて、図面を参照して説明する。図３は、実施例２に係るエネルギー回収装置を備えた石炭ガス化発電プラントの概略図である。
図３に示すように、エネルギー回収装置を備えた石炭ガス化発電プラント５０は、石炭５１をガス化して生成ガス１２を得るガス化炉５２と、生成ガス１２中のＣＯをＣＯ2に変換するＣＯシフト変換システム１０Ａと、ＣＯシフトガス２３中の硫黄（Ｓ）分を回収する脱硫装置５３と、ＣＯ2を回収するＣＯ2回収装置５４と、ＣＯ2回収装置５４からの精製ガス５５を用いて複合発電する複合発電設備（精製燃焼する燃焼器を備えたガスタービン設備及びガスタービン設備の燃焼排ガスの熱エネルギーを回収する排熱回収ボイラ（ＨＲＳＧ）と、排熱回収ボイラで回収した蒸気を用いて発電機６７を発電する蒸気タービン設備）５６とを具備するものである。図３中、符号６０は空気、６１は空気分離装置、６２は空気分離装置６１で得られた酸素、６３は窒素、６４は脱硫装置５３で回収された回収Ｈ2Ｓガス、６５は硫黄（Ｓ）分回収装置、６６は回収ＣＯ2ガス、６７はＣＯ2圧縮装置、６８はスラグを各々図示する。 A coal gasification power plant including an energy recovery device according to an embodiment of the present invention will be described with reference to the drawings. FIG. 3 is a schematic diagram of a coal gasification power plant including the energy recovery device according to the second embodiment.
As shown in FIG. 3, a coal gasification power plant 50 equipped with an energy recovery device converts a gasification furnace 52 that gasifies coal 51 to obtain a product gas 12 and converts CO in the product gas 12 into CO 2 . a CO shift conversion system 10A, a desulfurization unit 53 for recovering the sulfur (S) content in the CO shifted gas 23, a CO 2 recovery device 54 for recovering CO 2, with purified gas 55 from the CO 2 recovery apparatus 54 Combined power generation facilities for combined power generation (gas turbine equipment with a combustor for refining combustion, exhaust heat recovery boiler (HRSG) that recovers thermal energy of combustion exhaust gas from gas turbine equipment, and steam recovered by an exhaust heat recovery boiler) A steam turbine facility 56 for generating power from the generator 67. In FIG. 3, reference numeral 60 is air, 61 is an air separator, 62 is oxygen obtained by the air separator 61, 63 is nitrogen, 64 is recovered H2S gas recovered by the desulfurizer 53, and 65 is sulfur (S). The fraction recovery device, 66 is the recovered CO 2 gas, 67 is the CO 2 compressor, and 68 is the slag.

本実施例では、ＣＯシフト変換システムとして実施例１のＣＯシフト変換システム１０Ａを適用するので、従来複合発電設備５６の排熱回収ボイラ（ＨＲＳＧ）から供給していた抽気中圧蒸気６９の供給量の一部（約１５％）を補完することができ、その分抽気中圧蒸気６９の低減を図ることができる。この結果、発電効率が向上し、プラント全体のエネルギー効率を向上させることができる。   In the present embodiment, since the CO shift conversion system 10A of the first embodiment is applied as the CO shift conversion system, the supply amount of the extraction medium pressure steam 69 that has been supplied from the exhaust heat recovery boiler (HRSG) of the combined power generation facility 56 conventionally. Part (about 15%) can be supplemented, and the extraction medium pressure steam 69 can be reduced accordingly. As a result, the power generation efficiency is improved and the energy efficiency of the entire plant can be improved.

このように、本実施例によれば、ＣＯシフト変換システム１０Ａにおいては、生成ガス１２中に存在する硫化水素の濃度が低い場合においても、水スプレを供給することで、触媒劣化を抑制しつつＣＯシフト変換を行うことができると共に、水スプレを供給することにより、ＣＯシフト変換システム１０ＡのＣＯシフト変換装置における抽気中圧蒸気６９の一部を補完することができ、複合発電設備５６の排熱回収ボイラ（ＨＲＳＧ）よりの抽気中圧蒸気６９の供給量の低減を図ることができ、発電効率の向上に寄与する。   Thus, according to the present embodiment, in the CO shift conversion system 10A, even when the concentration of hydrogen sulfide existing in the product gas 12 is low, the catalyst is prevented from deteriorating by supplying water spray. The CO shift conversion can be performed, and by supplying the water spray, a part of the extraction intermediate pressure steam 69 in the CO shift conversion device of the CO shift conversion system 10A can be supplemented. The supply amount of the extraction medium pressure steam 69 from the heat recovery boiler (HRSG) can be reduced, which contributes to improvement of power generation efficiency.

本発明による実施例に係るＣＯシフト変換システムについて、図面を参照して説明する。図４は、実施例３に係るＣＯシフト変換システムの概略図である。
図４に示すように、本実施例に係るＣＯシフト変換システム１０Ｂは、実施例１のＣＯシフト変換システム１０Ａにおいて、混合器１７に硫化水素（Ｈ2Ｓ）を供給するＨ2Ｓ供給手段３１を設けている。 A CO shift conversion system according to an embodiment of the present invention will be described with reference to the drawings. FIG. 4 is a schematic diagram of a CO shift conversion system according to the third embodiment.
As shown in FIG. 4, the CO shift conversion system 10B according to the present embodiment is an H 2 S supply means 31 for supplying hydrogen sulfide (H 2 S) to the mixer 17 in the CO shift conversion system 10A of the first embodiment. Is provided.

実施例１においては、水スプレ１６を供給して、ＣＯシフト触媒１１の温度上昇を抑制しているが、本実施例では、生成ガス１２中のＨ2Ｓ濃度が極めて低いとき、別途Ｈ2Ｓを追給するようにしている。供給するＨ2Ｓは、図３に示す石炭ガス化発電プラント５０における脱硫装置５３で回収した回収Ｈ2Ｓガス６４を再利用している。 In the first embodiment, the water spray 16 is supplied to suppress the temperature increase of the CO shift catalyst 11. However, in this embodiment, when the H 2 S concentration in the product gas 12 is extremely low, a separate H 2 is used. S is supplemented. The supplied H 2 S reuses the recovered H 2 S gas 64 recovered by the desulfurization device 53 in the coal gasification power plant 50 shown in FIG.

特に、ガス火炉５２に供給する石炭５１の銘柄変更等によりＨ2Ｓ濃度の急変が予測される場合は、温度及び水蒸気の変更による対応は熱容量による応答性の観点から難しい場合がある。このような場合、硫化水素濃度を所定量（例えば１００ｐｐｍ）となるように、追加することで、硫化モリブデン（ＭｏＳ3）が安定している領域から、不安定領域を通過して、ＭｏＯ3安定領域に達することが防止され、触媒機能を十分に発揮することができ、良好なＣＯシフト反応を行うことができる。 In particular, when a sudden change in the H 2 S concentration is predicted due to a change in the brand of the coal 51 supplied to the gas furnace 52, the response by changing the temperature and water vapor may be difficult from the viewpoint of responsiveness due to heat capacity. In such a case, by adding the hydrogen sulfide concentration so as to be a predetermined amount (for example, 100 ppm), the molybdenum sulfide (MoS 3 ) passes from the stable region to the unstable region to stabilize the MoO 3. Reaching the region is prevented, the catalyst function can be sufficiently exerted, and a good CO shift reaction can be performed.

以上のように、本発明に係るＣＯシフト変換システム及び方法、石炭ガス化発電プラントによれば、水蒸気量が少ない場合でも触媒劣化がなく、ＣＯシフト反応を効率よく行うことができ、発電効率の向上に寄与することができる。   As described above, according to the CO shift conversion system and method and the coal gasification power plant according to the present invention, even when the amount of water vapor is small, there is no catalyst deterioration, and the CO shift reaction can be performed efficiently. It can contribute to improvement.

１０Ａ、１０Ｂ ＣＯシフト変換システム
１１ ＣＯシフト触媒
１２ 生成ガス
１３ ＣＯシフト変換装置
１４ 水蒸気
１５ 水蒸気供給手段
１６ 水スプレ
１７ 混合器
１８ 水スプレ供給手段
２０ ＣＯシフト変換部
10A, 10B CO shift conversion system 11 CO shift catalyst 12 Product gas 13 CO shift conversion device 14 Water vapor 15 Water vapor supply means 16 Water spray 17 Mixer 18 Water spray supply means 20 CO shift conversion section

Claims (5)

硫化モリブデンを用いたＣＯシフト触媒を有し、生成ガス中のＣＯをＣＯ2に変換するＣＯシフト変換装置と、
該ＣＯシフト変換装置の上流側に設けられ、生成ガス中のＣＯをＣＯ2へ変換するために要する水蒸気を供給する水蒸気供給手段と、
水蒸気を供給した生成ガスに水スプレを混合器を介して供給する水スプレ供給手段とを具備するＣＯシフト変換部を備え、
前記ＣＯシフト変換部が少なくとも２以上直列に多段連結され、
生成ガス中の硫化水素濃度が１００ｐｐｍ以下の場合に、水スプレを混合器に供給することを特徴とするＣＯシフト変換システム。 A CO shift conversion device having a CO shift catalyst using molybdenum sulfide and converting CO in the product gas to CO 2 ;
A water vapor supply means provided on the upstream side of the CO shift converter, for supplying water vapor required for converting CO in the produced gas into CO 2 ;
Includes a CO shift conversion unit comprising a supply water spray supply means generating gas supplied steam water spray through a mixer,
The CO shift conversion units are connected in multiple stages in series of at least two or more,
A CO shift conversion system that supplies water spray to a mixer when the concentration of hydrogen sulfide in the product gas is 100 ppm or less. 請求項１において、
生成ガス中の硫化水素濃度が１００ｐｐｍ以下の場合に、硫化水素を供給する硫化水素供給手段を有することを特徴とするＣＯシフト変換システム。 In claim 1,
A CO shift conversion system comprising hydrogen sulfide supply means for supplying hydrogen sulfide when the concentration of hydrogen sulfide in the product gas is 100 ppm or less. 石炭をガス化して生成ガスを得るガス化炉と、
生成ガス中のＣＯをＣＯ2に変換する請求項１又は２のＣＯシフト変換システムと、
ＣＯシフトガス中のＣＯ2を回収するＣＯ2吸収塔と吸収液を再生する吸収液再生塔とを備えたＣＯ2回収装置と、
精製ガスを燃焼する燃焼器を備えたガスタービン設備と、
ガスタービン設備の燃焼排ガスの熱エネルギーを回収する排熱回収ボイラ（ＨＲＳＧ）と、
排熱回収ボイラで回収した蒸気を用いて発電する蒸気タービン設備とを具備することを特徴とする石炭ガス化発電プラント。 A gasification furnace that gasifies coal to obtain product gas;
A CO shift conversion system according to claim 1 or 2 for converting CO in the product gas into CO 2 ;
A CO 2 recovery device comprising a CO 2 absorption tower for recovering CO 2 in the CO shift gas and an absorption liquid regeneration tower for regenerating the absorption liquid;
A gas turbine facility equipped with a combustor for burning purified gas;
An exhaust heat recovery boiler (HRSG) for recovering the thermal energy of the combustion exhaust gas of the gas turbine equipment,
A coal gasification power plant comprising a steam turbine facility that generates electricity using steam recovered by an exhaust heat recovery boiler. 請求項１又は２のＣＯシフト変換システムを用い、
生成ガス中の硫化水素濃度が１００ｐｐｍ以下の場合に、水スプレを混合器に供給してＣＯシフト触媒の温度上昇を抑制することを特徴とするＣＯシフト変換方法。 Using the CO shift conversion system according to claim 1 or 2,
A CO shift conversion method characterized in that when the concentration of hydrogen sulfide in the product gas is 100 ppm or less, water spray is supplied to a mixer to suppress the temperature increase of the CO shift catalyst. 請求項４において、
生成ガス中の硫化水素濃度が１００ｐｐｍ以下の場合に、硫化水素を供給する硫化水素供給手段を有することを特徴とするＣＯシフト変換方法。 In claim 4,
A CO shift conversion method comprising hydrogen sulfide supply means for supplying hydrogen sulfide when the concentration of hydrogen sulfide in the product gas is 100 ppm or less.
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