JP5143812B2 - Thermoelectric hydrogen supply system - Google Patents

Thermoelectric hydrogen supply system Download PDF

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JP5143812B2
JP5143812B2 JP2009259349A JP2009259349A JP5143812B2 JP 5143812 B2 JP5143812 B2 JP 5143812B2 JP 2009259349 A JP2009259349 A JP 2009259349A JP 2009259349 A JP2009259349 A JP 2009259349A JP 5143812 B2 JP5143812 B2 JP 5143812B2
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hydrogen
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cogeneration system
lng
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英人 黒川
義則 白崎
勇 安田
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Tokyo Gas Co Ltd
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
    • F25J3/0605—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the feed stream
    • F25J3/0625—H2/CO mixtures, i.e. synthesis gas; Water gas or shifted synthesis gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0204—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the feed stream
    • F25J3/0223—H2/CO mixtures, i.e. synthesis gas; Water gas or shifted synthesis gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0252—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of hydrogen
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    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
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    • F25J3/0271—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of H2/CO mixtures, i.e. of synthesis gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
    • F25J3/063—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream
    • F25J3/0655—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream separation of hydrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
    • F25J3/063—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream
    • F25J3/067—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream separation of carbon dioxide
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00—Processes characterised by the type or other details of the feed stream
    • F25J2210/62—Liquefied natural gas [LNG]; Natural gas liquids [NGL]; Liquefied petroleum gas [LPG]
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2215/00—Processes characterised by the type or other details of the product stream
    • F25J2215/04—Recovery of liquid products
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
    • F25J2230/30—Compression of the feed stream
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
    • F25J2270/904—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration by liquid or gaseous cryogen in an open loop
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00—Combustion technologies with mitigation potential
    • Y02E20/14—Combined heat and power generation [CHP]

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Description

本発明は、熱電気水素供給システムに関し、より詳しくは、液化天然ガス（ＬＮＧ）を利用したコジェネレーションシステム及び水素分離型水蒸気改質器を含み、熱、電気及び水素を供給するシステムに関する。   The present invention relates to a thermoelectric hydrogen supply system, and more particularly to a system for supplying heat, electricity and hydrogen, including a cogeneration system using liquefied natural gas (LNG) and a hydrogen separation steam reformer.

特許文献１には、燃焼器を備える、メンブレンリアクターなどの水素分離型水素製造装置において、水素が分離された高圧のオフガスを燃焼器へ戻すオフガス流路と、当該オフガス流路にオフガスが保有するエネルギーを回収する回収手段、例えば発電機を設けた水素製造装置が開示されている。   In Patent Document 1, in a hydrogen separation type hydrogen production apparatus such as a membrane reactor equipped with a combustor, an offgas passage for returning high-pressure offgas from which hydrogen has been separated to the combustor, and the offgas is held in the offgas passage. A hydrogen production apparatus provided with a recovery means for recovering energy, for example, a generator is disclosed.

従来の水素分離型水素製造システムにおいて、水素分離型水蒸気改質器のオフガスについては、特許文献１のように、そのオフガスを全て燃焼器に送ることで可燃ガス分を再利用することにより、水素製造効率を高めているが、燃焼排ガスはそのまま外気に放出しているのが現状である。しかし、燃焼排ガスの主成分は、地球温暖化ガスである二酸化炭素であることから、外気への放出は回避する必要がある。   In the conventional hydrogen separation-type hydrogen production system, as for the off-gas of the hydrogen separation-type steam reformer, as in Patent Document 1, all the off-gas is sent to the combustor to recycle the combustible gas, Although the production efficiency is increased, the combustion exhaust gas is released to the outside as it is. However, since the main component of the combustion exhaust gas is carbon dioxide, which is a global warming gas, it is necessary to avoid release to the outside air.

そのような観点から、例えば、特許文献２には、液化天然ガスを気化したガス（＝天然ガス）を水蒸気改質器に供給して水素を製造し、分離したオフガス中に含まれる二酸化炭素を回収するようにした水素製造装置及び水素製造方法が提案されている。特許文献３には、改質器において、含酸素炭化水素または炭化水素と酸素及び水蒸気により生成した改質ガスから水素を分離し、併せて二酸化炭素を高純度で含むガスを分離し、残りのガスの一部をパージするとともに、残部を改質器に高温の状態で再循環させるラインを備える水素製造システムが提案されている。   From such a viewpoint, for example, Patent Document 2 discloses that gas obtained by vaporizing liquefied natural gas (= natural gas) is supplied to a steam reformer to produce hydrogen, and carbon dioxide contained in the separated off-gas is supplied. A hydrogen production apparatus and a hydrogen production method that have been recovered have been proposed. In Patent Document 3, in a reformer, hydrogen is separated from a reformed gas generated by oxygen-containing hydrocarbons or hydrocarbons and oxygen and steam, and a gas containing carbon dioxide with high purity is separated, and the remaining gas is separated. A hydrogen production system has been proposed that includes a line that purges part of the gas and recirculates the remainder to the reformer at a high temperature.

ここで、特許文献４には、液化ＣＯ2回収を伴う水素製造方法として、天然ガスを水蒸気改質して改質ガスを生成すること、生成改質ガスをＣＯシフト反応器を経てＰＳＡ装置に供給して水素を分離精製すること、精製工程で分離された可燃物を含むオフガスを高濃度酸素または純酸素を酸化剤として燃焼すること、燃焼により発生する燃焼排ガス中の二酸化炭素を深冷蒸留・分離により高濃度にすること、高濃度二酸化炭素を液化炭酸あるいは固体炭酸として回収を行うことが開示されている。 Here, in Patent Document 4, as a method for producing hydrogen with liquefied CO 2 recovery, natural gas is steam reformed to produce reformed gas, and the produced reformed gas is passed through a CO shift reactor to a PSA apparatus. Supplying and purifying hydrogen, burning off-gas containing combustibles separated in the purification process using high-concentration oxygen or pure oxygen as oxidant, and deep-distilling carbon dioxide in combustion exhaust gas generated by combustion -It is disclosed that the concentration is increased by separation, and the high concentration carbon dioxide is recovered as liquefied carbonic acid or solid carbonic acid.

しかし、特許文献４の技術は、後述する本発明とは水蒸気改質器で製造した改質ガスから水素を分離したオフガスの燃焼に高濃度酸素を利用する点では共通するが、本発明の水素分離型改質システムのように、水素分離型改質システムで生じる二酸化炭素の全量もしくは大部分を回収するものではなく、水素分離型改質システムで生じる水分の全量もしくは大部分を回収するものではない。また、この技術は、本発明のように、その前提として、水素分離型水蒸気改質器を用いることを必須とするものではない。   However, the technique of Patent Document 4 is common to the present invention described later in that high-concentration oxygen is used for off-gas combustion in which hydrogen is separated from reformed gas produced by a steam reformer. It is not intended to recover all or most of the carbon dioxide generated in the hydrogen separation reforming system, as in the case of the separation reforming system, but to recover all or most of the water generated in the hydrogen separation reforming system. Absent. In addition, this technique does not necessarily require the use of a hydrogen separation steam reformer as a premise as in the present invention.

特開２００３−１８３００６号公報JP 2003-183006 A 特開２０００−２４７６０４号公報JP 2000-247604 A 特開２００５−１４５７６０号公報JP 2005-145760 A 特開２００３−０８１６０５号公報JP 2003-081605 A

また、メンブレンリアクターなどの水素分離型水素製造装置は、従来型の水蒸気改質装置と比較して高効率かつシンプル、コンパクトであることが知られている。水素自動車用等の水素ステーションの所在地において、メンブレンリアクターなどの水素分離型水素製造装置を使用し、天然ガスや都市ガスなどの炭化水素系燃料の改質による水素製造から貯蔵、供給まで行う、いわゆる炭化水素系燃料改質オンサイト方式の水素ステーションでの実用化を目指して開発が進められている。   In addition, it is known that a hydrogen separation type hydrogen production apparatus such as a membrane reactor is highly efficient, simple and compact compared to a conventional steam reforming apparatus. At the location of a hydrogen station for hydrogen vehicles, etc., a hydrogen separation type hydrogen production device such as a membrane reactor is used to carry out everything from hydrogen production to storage and supply by reforming hydrocarbon fuels such as natural gas and city gas. Development is being promoted with the aim of putting it into practical use in a hydrocarbon-based fuel reforming on-site hydrogen station.

そのような、オンサイト方式の水素ステーションにおいても、水素製造装置からのオフガスについてはもちろん、二酸化炭素が主成分である燃焼排ガスについても、地球温暖化ガスである二酸化炭素であることから、外気への放出を回避する必要がある。   Even in such an on-site hydrogen station, not only off-gas from the hydrogen production equipment but also combustion exhaust gas mainly composed of carbon dioxide is carbon dioxide, which is a global warming gas. It is necessary to avoid the release of.

そのほか、都市ガスを利用するコジェネレーションシステム（ＣＧＳ）を用いた、熱（温水・蒸気）と電気の供給は産業用及びホテル、病院などの大型施設向けに普及しており、広く一般に行われている。   In addition, supply of heat (hot water / steam) and electricity using a cogeneration system (CGS) that uses city gas is widespread for industrial use and large facilities such as hotels and hospitals. Yes.

それらの各分野における地球温暖化ガス排出量の削減への取り組みが進む中、化石燃料の利用そのものへの厳しさが増大してくることから、これまで、クリーンと言われてきた天然ガスを利用するＣＧＳにおいても高効率化に加え、排出されるＣＯ2の積極的な回収、固定化、またその有効利用が必要になってくると考えられる。 As efforts to reduce global warming gas emissions in each of these fields are progressing, the severity of fossil fuel use itself will increase, so natural gas that has been said to be clean will be used. In CGS, it is considered that in addition to increasing efficiency, it is necessary to actively collect, fix, and effectively use the emitted CO 2 .

本発明は、液化天然ガスを原料とする水素分離型水素製造装置において、天然ガスから高効率に水素製造を行うとともに、効率的な二酸化炭素回収によって天然ガス由来の二酸化炭素の全量もしくは大部分を回収し、且つ、水分の全量もしくは大部分を回収するようにしてなる、ＬＮＧを用いたコジェネレーションシステムと水素分離型水蒸気改質器による熱電気水素供給システムを提供することを目的とするものである。   The present invention is a hydrogen separation-type hydrogen production apparatus that uses liquefied natural gas as a raw material to produce hydrogen from natural gas with high efficiency, and to recover all or most of the carbon dioxide derived from natural gas through efficient carbon dioxide recovery. The purpose of this invention is to provide a thermoelectric hydrogen supply system using a cogeneration system using LNG and a hydrogen separation type steam reformer that recovers and collects all or most of the water. is there.

本発明（１）は、ＬＮＧを気化した天然ガスを燃料とするコジェネレーションシステムと、前記天然ガスの水蒸気改質による水素分離型水蒸気改質器と、前記水蒸気改質用加熱源である燃焼器とを有する熱、電気および水素を供給するシステムであって、
（ａ）前記コジェネレーションシステムからの排ガスと前記水素分離型水蒸気改質器からのオフガスを合流させ、
（ｂ）前記排ガス及びオフガスをその流れ方向でみて、順次、圧縮機、冷却熱交換器及び気液分離槽を含む二酸化炭素回収装置を備えてなり、
（ｃ）前記冷却熱交換器の冷熱として前記ＬＮＧを使用し、
（ｄ）前記コジェネレーションシステム及び前記水蒸気改質用加熱源である燃焼器には酸素富化空気を使用するようにしてなる、ことを特徴とする熱電気水素供給システムである。 The present invention (1) includes a cogeneration system using natural gas obtained by vaporizing LNG as a fuel, a hydrogen separation type steam reformer by steam reforming of the natural gas, and a combustor which is the heat source for steam reforming A system for supplying heat, electricity and hydrogen having:
(A) combining the exhaust gas from the cogeneration system and the off-gas from the hydrogen separation steam reformer,
(B) Looking at the exhaust gas and off-gas in the flow direction, and sequentially comprising a carbon dioxide recovery device including a compressor, a cooling heat exchanger and a gas-liquid separation tank,
(C) using the LNG as the cooling heat of the cooling heat exchanger;
(D) The thermoelectric hydrogen supply system is characterized in that oxygen-enriched air is used in the cogeneration system and the combustor as the steam reforming heating source.

本発明（１）においては、上記（ａ）〜（ｂ）のとおり、コジェネレーションシステムからの排ガスと水素分離型水蒸気改質器からのオフガスを合流させ、それら排ガス及びオフガスについて、その流れ方向に順次配置された圧縮機、冷却熱交換器及び気液分離槽を含む二酸化炭素回収装置を備えることにより、二酸化炭素を液化炭酸として高効率に回収するものである。また、前記コジェネレーションシステムにおいて生成した水蒸気を前記水素分離型水蒸気改質器の水蒸気改質器での天然ガスの水蒸気改質用に使用するようにすることができる。   In the present invention (1), as described above (a) to (b), the exhaust gas from the cogeneration system and the off-gas from the hydrogen separation steam reformer are merged, and the exhaust gas and the off-gas are flown in the flow direction. By providing a carbon dioxide recovery device including a compressor, a cooling heat exchanger, and a gas-liquid separation tank that are sequentially arranged, carbon dioxide is recovered as liquefied carbon dioxide with high efficiency. The steam generated in the cogeneration system can be used for steam reforming of natural gas in the steam reformer of the hydrogen separation steam reformer.

本発明（２）は、ＬＮＧを気化した天然ガスを燃料とするコジェネレーションシステムと、前記天然ガスの水蒸気改質による水素分離型水蒸気改質器と、前記水蒸気改質用加熱源であるヒーターとを有する熱、電気および水素を供給するシステムであって、
（ａ）前記コジェネレーションシステムからの排ガスを前記ヒーターの熱源として使用した後、
（ｂ）前記排ガスと前記水素分離型水蒸気改質器からのオフガスを合流させ、
（ｃ）前記排ガス及びオフガスをその流れ方向でみて、順次、圧縮機、冷却熱交換器及び気液分離槽を含む二酸化炭素回収装置を備えてなり、
（ｄ）前記冷却熱交換器の冷熱として前記ＬＮＧを使用し、
（ｅ）前記コジェネレーションシステムには酸素富化空気を使用し、
（ｆ）前記コジェネレーションシステムにて生成した水蒸気を前記水蒸気改質器で使用するようにしてなる、ことを特徴とする熱電気水素供給システムである。 The present invention (2) includes a cogeneration system using natural gas vaporized LNG as a fuel, a hydrogen separation type steam reformer by steam reforming of the natural gas, and a heater as the heat source for steam reforming, A system for supplying heat, electricity and hydrogen having
(A) After using the exhaust gas from the cogeneration system as a heat source for the heater,
(B) combining the off-gas from the exhaust gas and the hydrogen separation steam reformer,
(C) Looking at the exhaust gas and off-gas in the flow direction, and sequentially comprising a carbon dioxide recovery device including a compressor, a cooling heat exchanger and a gas-liquid separation tank,
(D) using the LNG as the cooling heat of the cooling heat exchanger;
(E) The cogeneration system uses oxygen-enriched air,
(F) The thermoelectric hydrogen supply system, wherein the steam generated by the cogeneration system is used in the steam reformer.

本発明（２）においては、上記（ａ）〜（ｃ）のとおり、コジェネレーションシステムからの排ガスをヒーターの熱源として使用した後、排ガスと水素分離型水蒸気改質器からのオフガスを合流させ、排ガス及びオフガスをその流れ方向でみて、順次、圧縮機、冷却熱交換器及び気液分離槽を含む二酸化炭素回収装置を備えてなることにより、二酸化炭素を液化炭酸として高効率に回収するものである。また、前記コジェネレーションシステムにおいて生成した水蒸気を前記水素分離型水蒸気改質器の水蒸気改質器での天然ガスの水蒸気改質用に使用するようにすることができる。   In the present invention (2), as described in the above (a) to (c), after using the exhaust gas from the cogeneration system as a heat source of the heater, the exhaust gas and the off-gas from the hydrogen separation type steam reformer are combined, By looking at the exhaust gas and off-gas in the flow direction, and sequentially equipped with a carbon dioxide recovery device including a compressor, a cooling heat exchanger and a gas-liquid separation tank, carbon dioxide is recovered as liquefied carbon dioxide with high efficiency. is there. The steam generated in the cogeneration system can be used for steam reforming of natural gas in the steam reformer of the hydrogen separation steam reformer.

本発明（１）〜（２）の熱電気水素供給システムは、水素ステーションの所在地で水素製造から貯蔵・供給まで行うオンサイト方式の水素ステーションにおけるＬＮＧを用いたコジェネレーションシステムと水素分離型水蒸気改質器よる熱電気水素供給システムとして利用することができる。この熱電気水素供給システムによると、熱と電気と水素を同時に供給し、二酸化炭素も回収して有効に利用することができる。   The thermoelectric hydrogen supply system of the present invention (1) to (2) is a cogeneration system using LNG and a hydrogen separation type steam reformer in an on-site type hydrogen station that performs from hydrogen production to storage and supply at the location of the hydrogen station. It can be used as a thermoelectric hydrogen supply system by a quality device. According to this thermoelectric hydrogen supply system, heat, electricity and hydrogen can be supplied simultaneously, and carbon dioxide can also be recovered and used effectively.

本発明の熱電水素供給システムによれば（１）〜（４）の効果を得られる。
（１）ＬＮＧターミナル、ＬＮＧサテライトにおいて、熱（温水、水蒸気）、電気、水素、二酸化炭素を高効率に供給することができる。
（２）ＬＮＧターミナル、ＬＮＧサテライトにおけるコジェネレーションシステムからの天然ガス由来の二酸化炭素の全量もしくは大部分を回収することができる。
（３）ＬＮＧの冷熱と水素分離型水蒸気改質器のオフガスとの効率的な熱交換によってＬＮＧ気化プロセスとＣＯ2圧縮液化回収プロセスの効率向上を図ることができる。
（４）コジェネレーションシステムにおいてＬＮＧ気化器が省略でき、また水素分離型水蒸気改質器を用いた水素製造装置における脱硫器、都市ガス圧縮機、ボイラーを省略することができる。 According to the thermoelectric hydrogen supply system of the present invention, the effects (1) to (4) can be obtained.
(1) In the LNG terminal and the LNG satellite, heat (warm water, water vapor), electricity, hydrogen, and carbon dioxide can be supplied with high efficiency.
(2) The total or most of the natural gas-derived carbon dioxide from the cogeneration system at the LNG terminal and LNG satellite can be recovered.
(3) The efficiency of the LNG vaporization process and the CO 2 compression liquefaction recovery process can be improved by efficient heat exchange between the cold heat of LNG and the off-gas of the hydrogen separation steam reformer.
(4) In the cogeneration system, the LNG vaporizer can be omitted, and the desulfurizer, city gas compressor, and boiler in the hydrogen production apparatus using the hydrogen separation type steam reformer can be omitted.

図１は本発明の前提となる従来技術を説明する図である。FIG. 1 is a diagram for explaining the prior art as a premise of the present invention. 図２は本発明の前提となる従来技術を説明する図である。FIG. 2 is a diagram for explaining the prior art as a premise of the present invention. 図３は本発明（１）を説明する図である。FIG. 3 is a diagram for explaining the present invention (1). 図４は本発明（２）を説明する図である。FIG. 4 is a diagram for explaining the present invention (2).

コジェネレーションシステムは、石炭、石油、天然ガスなどの一次エネルギーから電力と熱を同時に発生し、エネルギーの有効利用を図るシステムであり、熱電併給システムとも称される。本発明は、ＬＮＧを出発原料とし、電力と熱に加えて、水素を同時に発生させて、さらにエネルギーの有効利用を図る熱電気水素供給システムである。また、本発明は、それら構成に加えて、副生二酸化炭素の全量もしくは大部分を回収するようにしてなる熱電気水素供給システムである。   A cogeneration system is a system that generates electric power and heat from primary energy such as coal, oil, and natural gas at the same time to effectively use energy, and is also referred to as a combined heat and power system. The present invention is a thermoelectric hydrogen supply system in which LNG is used as a starting material, and hydrogen is simultaneously generated in addition to electric power and heat to further effectively use energy. Further, the present invention is a thermoelectric hydrogen supply system that collects all or most of the by-product carbon dioxide in addition to those components.

以下、本発明について、従来技術との関連を含めて順次説明する。   Hereinafter, the present invention will be sequentially described including the relation with the prior art.

〈従来技術について〉
図１〜２は従来技術を説明する図である。図１はＬＮＧサテライトシステムを説明する図であり、図２は「水素分離型水蒸気改質器を用いた水素製造装置＋二酸化炭素（ＣＯ2）回収装置」、すなわち水素分離型水蒸気改質器を用いた水素製造装置に二酸化炭素（ＣＯ2）回収装置を組み合わせたシステムを説明する図である。 <Conventional technology>
1 and 2 are diagrams for explaining the prior art. FIG. 1 is a diagram for explaining an LNG satellite system, and FIG. 2 shows a “hydrogen production apparatus using a hydrogen separation steam reformer + carbon dioxide (CO 2 ) recovery apparatus”, that is, a hydrogen separation steam reformer. the hydrogen production apparatus using a diagram illustrating a system that combines carbon dioxide (CO 2) recovery apparatus.

図１のとおり、従来のＬＮＧサテライトシステムにおいては、ＬＮＧタンク１中のＬＮＧは導管２を介して熱交換器３に供給される。ＬＮＧは熱交換器３で加熱されて気化し、コジェネレーションシステム（ＣＧＳ）４に天然ガスとして供給される。コジェネレーションシステム（ＣＧＳ）４には電力発生装置であるタービン発電機や燃料電池などが配置されており、天然ガスはタービン発電機あるいは燃料電池に供給されて電気と熱（排熱）を発生する。電気は需要者に供給され、排熱は給湯、冷暖房等の用途に供される。また、ＬＮＧタンク１からのボイルガスは排出導管５を介してパイプライン６によりサテライトステーション周辺の需要に供される。   As shown in FIG. 1, in the conventional LNG satellite system, the LNG in the LNG tank 1 is supplied to the heat exchanger 3 through the conduit 2. LNG is heated and vaporized in the heat exchanger 3 and supplied to the cogeneration system (CGS) 4 as natural gas. The cogeneration system (CGS) 4 includes a turbine generator or a fuel cell that is a power generation device, and natural gas is supplied to the turbine generator or the fuel cell to generate electricity and heat (exhaust heat). . Electricity is supplied to the consumer, and the exhaust heat is used for hot water supply, air conditioning and the like. Further, the boil gas from the LNG tank 1 is supplied to the demand around the satellite station by the pipeline 6 through the discharge conduit 5.

また、従来の水素分離型水蒸気改質器を用いた水素製造装置＋二酸化炭素（ＣＯ2）回収装置については、燃料が都市ガスである場合を例にすると、以下のとおりである。図２のとおり、水素分離型改質器での水素製造用の燃料とする方の都市ガスは、導管１１を介して脱硫器１３に通して硫黄化合物を除去した後、水蒸気（スチーム）を添加、混合して水素分離型水蒸気改質器１７に供給する。水素分離型水蒸気改質器において、脱硫済み都市ガスは水蒸気による改質により改質ガスとなり、改質ガス中の水素が水素分離膜つまり例えばＰｄ系合金膜等の水素透過膜を選択的に透過して分離されて取り出される。 In addition, a hydrogen production apparatus + carbon dioxide (CO 2 ) recovery apparatus using a conventional hydrogen separation type steam reformer is as follows when the fuel is city gas. As shown in FIG. 2, the city gas used as the fuel for hydrogen production in the hydrogen separation reformer is passed through the desulfurizer 13 via the conduit 11 to remove sulfur compounds, and then added with steam (steam). , Mixed and supplied to the hydrogen separation steam reformer 17. In the hydrogen separation type steam reformer, the desulfurized city gas becomes reformed gas by reforming with steam, and hydrogen in the reformed gas selectively permeates a hydrogen separation membrane, that is, a hydrogen permeable membrane such as a Pd-based alloy membrane. And separated and taken out.

ボイラー１５で燃焼して水蒸気発生用の燃料とする方の都市ガスは、導管１１の分岐管１２を介してボイラー１５へ供給される。ボイラー１５へ供給された都市ガスは、空気供給管１４からボイラー１５に供給される空気により燃焼し、水を加熱して水蒸気を発生させる。符号１６はボイラー１５への水供給管である。ボイラー１５で発生した水蒸気は、脱硫器１３で脱硫され圧縮機Ｐ１を経た都市ガスに混合され、水素分離型水蒸気改質器１７に供給される。   The city gas burned in the boiler 15 and used as fuel for generating water vapor is supplied to the boiler 15 through the branch pipe 12 of the conduit 11. The city gas supplied to the boiler 15 is combusted by the air supplied from the air supply pipe 14 to the boiler 15, and heats the water to generate water vapor. Reference numeral 16 denotes a water supply pipe to the boiler 15. The steam generated in the boiler 15 is desulfurized by the desulfurizer 13, mixed with the city gas that has passed through the compressor P <b> 1, and supplied to the hydrogen separation steam reformer 17.

水素分離型水蒸気改質器１７からのオフガスは圧縮機Ｐ２により圧縮した後、熱交換器１９で冷却することによりオフガス中に含まれる二酸化炭素（ＣＯ2）を液化炭酸とする。液化炭酸は気液分離器２１により分離し、導出管２３により取り出され回収される。液化炭酸を分離したオフガス中にはＣＯ、Ｈ2、ＣＨ4、ＣＯ2が含まれているので、水素分離型水蒸気改質器１７の燃焼器１８に供給してその可燃分を燃焼し、水蒸気改質器での水蒸気改質用の熱に利用される。 The off-gas from the hydrogen separation type steam reformer 17 is compressed by the compressor P2, and then cooled by the heat exchanger 19 to convert carbon dioxide (CO 2 ) contained in the off-gas into liquefied carbon dioxide. The liquefied carbon dioxide is separated by the gas-liquid separator 21 and taken out by the outlet pipe 23 and collected. Since the off-gas from which the liquefied carbon dioxide has been separated contains CO, H 2 , CH 4 , and CO 2 , it is supplied to the combustor 18 of the hydrogen separation-type steam reformer 17 to burn the combustible component, and steam Used for heat for steam reforming in the reformer.

〈本発明（１）の態様〉
図３は本発明（１）を説明する図である。 <Aspect of the present invention (1)>
FIG. 3 is a diagram for explaining the present invention (1).

図３のとおり、本発明（１）の熱電気水素供給システムにおいては、ＬＮＧを気化して天然ガスとして燃料とするコジェネレーションシステム（ＣＧＳ）３８を備える。ＬＮＧタンク３１中のＬＮＧは導管３２を介して熱交換器３３に供給される。ＬＮＧは熱交換器３３で加熱されて気化し、天然ガスとしてコジェネレーションシステム（ＣＧＳ）３８に供給される。その天然ガスの一部は、導管３４を介してパイプライン３５によりサテライトステーション周辺の需要に供される。   As shown in FIG. 3, the thermoelectric hydrogen supply system of the present invention (1) includes a cogeneration system (CGS) 38 that vaporizes LNG and uses it as natural gas as fuel. The LNG in the LNG tank 31 is supplied to the heat exchanger 33 via the conduit 32. The LNG is heated and vaporized by the heat exchanger 33 and supplied to the cogeneration system (CGS) 38 as natural gas. Part of the natural gas is provided to demand around the satellite station by a pipeline 35 via a conduit 34.

コジェネレーションシステム（ＣＧＳ）３８には電力発生装置であるタービン発電機などが配置されている。天然ガスはガスタービン発電機に供給され、空気供給管３９から供給され、酸素富化器４０で酸素富化された空気で燃焼して電気と熱（排熱）を発生する。電気は需要者に供給され、排熱は給湯、冷暖房等の用途に供される。その排熱の一部は水素分離型水蒸気改質器４５における天然ガスの水蒸気改質反応に供する水蒸気発生用に利用する。符号４４は水素分離型水蒸気改質器４５への水蒸気供給管である。   The cogeneration system (CGS) 38 is provided with a turbine generator that is a power generation device. Natural gas is supplied to a gas turbine generator, supplied from an air supply pipe 39, and burned with air enriched with oxygen in an oxygen enricher 40 to generate electricity and heat (exhaust heat). Electricity is supplied to the consumer, and the exhaust heat is used for hot water supply, air conditioning and the like. A part of the exhaust heat is used for steam generation for use in the steam reforming reaction of natural gas in the hydrogen separation steam reformer 45. Reference numeral 44 denotes a steam supply pipe to the hydrogen separation steam reformer 45.

本発明（１）の熱電水素供給システムにおいては、コジェネレーションシステム（ＣＧＳ）３８及び、水素分離型水蒸気改質器４５における水蒸気改質用の加熱源である燃焼器での燃焼用には酸素富化空気を使用する。供給管３９を介して供給される空気は、酸素富化器４０で酸素が富化される。供給管３９中を流れる酸素富化空気は分岐管４１を介してコジェネレーションシステム（ＣＧＳ）３８に供給され、電力発生装置であるガスタービン発電機に供給される天然ガスの燃焼用に使用される。   In the thermoelectric hydrogen supply system of the present invention (1), oxygen is enriched for combustion in a combustor which is a heating source for steam reforming in a cogeneration system (CGS) 38 and a hydrogen separation steam reformer 45. Use chemical air. The air supplied through the supply pipe 39 is enriched with oxygen by the oxygen enricher 40. Oxygen-enriched air flowing in the supply pipe 39 is supplied to a cogeneration system (CGS) 38 via a branch pipe 41 and used for combustion of natural gas supplied to a gas turbine generator which is a power generation device. .

酸素富化空気のうち分岐管４１で分岐されない分は、供給管３９を介して水素分離型水蒸気改質器４５における天然ガスの水蒸気改質反応用加熱源である燃焼器４６に供給される。コジェネレーションシステム（ＣＧＳ）３８で発生した排熱により水蒸気を生成し、水素分離型水蒸気改質器４５での改質反応用に利用する。符号４４は、水素分離型水蒸気改質器４５への改質反応用水蒸気の供給管である。   A portion of the oxygen-enriched air that is not branched by the branch pipe 41 is supplied via a supply pipe 39 to a combustor 46 that is a heat source for steam reforming reaction of natural gas in the hydrogen separation type steam reformer 45. Steam is generated by exhaust heat generated in the cogeneration system (CGS) 38 and used for the reforming reaction in the hydrogen separation steam reformer 45. Reference numeral 44 is a steam supply pipe for reforming reaction to the hydrogen separation steam reformer 45.

水素分離型水蒸気改質器４５からのオフガスは導出管４８を介して導出され、圧縮機Ｐ１により圧縮した後、熱交換器３３で冷却することによりオフガス中に含まれる二酸化炭素（ＣＯ2）を液化炭酸とする。液化炭酸は気液分離器４９により分離し、導出管５０により取り出され回収される。回収液化炭酸は溶接用、冷却用、食品用、製鋼用、化学用などの用途に利用される。 The off-gas from the hydrogen separation type steam reformer 45 is led out through the lead-out pipe 48, compressed by the compressor P1, and then cooled by the heat exchanger 33, whereby carbon dioxide (CO 2 ) contained in the off-gas is cooled. Use liquefied carbonic acid. The liquefied carbon dioxide is separated by the gas-liquid separator 49 and taken out by the outlet pipe 50 and collected. The recovered liquefied carbonic acid is used for applications such as welding, cooling, food, steelmaking, and chemicals.

コジェネレーションシステム（ＣＧＳ）３８で発生した燃焼排ガスと、水素分離型水蒸気改質器４５における天然ガスの水蒸気改質反応用加熱源である燃焼器４６からの燃焼排ガスと、水素分離型水蒸気改質器４５からのオフガスの全部と、を一つに合流させた後、熱交換器３３で冷却し、気液分離器４９に導入する。   Combustion exhaust gas generated in the cogeneration system (CGS) 38, combustion exhaust gas from the combustor 46 which is a heating source for steam reforming reaction of natural gas in the hydrogen separation steam reformer 45, and hydrogen separation steam reforming After all of the off-gas from the vessel 45 is merged, it is cooled by the heat exchanger 33 and introduced into the gas-liquid separator 49.

このように、熱交換器３３において、その冷却源はＬＮＧタンク３１から導管３２を介して供給されるＬＮＧであり、ＬＮＧの冷熱を二酸化炭素の液化回収に利用するとともに、コジェネレーションシステム（ＣＧＳ）３８、水素分離型水蒸気改質器４５からの排熱をＬＮＧの気化に利用するものである。   Thus, in the heat exchanger 33, the cooling source is LNG supplied from the LNG tank 31 via the conduit 32, and the cold heat of the LNG is used for liquefying and recovering carbon dioxide, and a cogeneration system (CGS). 38, the exhaust heat from the hydrogen separation steam reformer 45 is used for the vaporization of LNG.

気液分離器４９において、熱交換器３３を経た合流ガス中の二酸化炭素は液化炭酸として分離する。液化炭酸は導出管５０により取り出し回収され、溶接用、冷却用、食品用、製鋼用、化学用などの用途に利用される。また、気液分離槽４９で分離されたガス（気相分）にはＣＯ、Ｈ2、ＣＨ4、ＣＯ2などが含まれている。そのうちＣＯ、Ｈ2、ＣＨ4は燃料となるので、気相分は導管５１、５２を介して導出され、燃焼器４６での燃焼用燃料に利用する。また、気相分にはＣＯ、Ｈ2が含まれているので、気相分の一部を導管５３により導出し、浸炭などに利用する。 In the gas-liquid separator 49, carbon dioxide in the combined gas that has passed through the heat exchanger 33 is separated as liquefied carbon dioxide. The liquefied carbonic acid is taken out and collected by the lead-out pipe 50 and used for applications such as welding, cooling, food, steelmaking, and chemicals. The gas (gas phase component) separated in the gas-liquid separation tank 49 contains CO, H 2 , CH 4 , CO 2 and the like. Of these, CO, H 2 , and CH 4 serve as fuel, and the gas phase component is led out through conduits 51 and 52 and used as fuel for combustion in the combustor 46. Further, since CO and H 2 are contained in the gas phase, a part of the gas phase is led out through the conduit 53 and used for carburizing and the like.

このように、本発明（１）においては、酸素富化空気を用い、ＬＮＧの冷熱を利用することにより、熱、電気を生成し、水素を製造するとともに、天然ガス由来の二酸化炭素の全量もしくは大部分を分離回収し、有効利用することができる。これにより、熱と電気だけでなく、水素や二酸化炭素を必要とする産業用施設、水素ステーションを併設する大型施設への適用が可能であり、エネルギーの効率的な利用と、二酸化炭素排出量の大幅削減が可能である。   Thus, in the present invention (1), by using oxygen-enriched air and utilizing the cold heat of LNG, heat and electricity are generated to produce hydrogen, and the total amount of carbon dioxide derived from natural gas or The majority can be separated and recovered for effective use. As a result, it can be applied not only to heat and electricity, but also to industrial facilities that require hydrogen and carbon dioxide, and large facilities with hydrogen stations. Significant reduction is possible.

また、従来技術においては、図２のとおり、ボイラーが必須であるが、本発明（１）においては、コジェネレーションシステム（ＣＧＳ）３８において発生する余剰熱を利用して水蒸気を生成するのでボイラーは不要である。   In the prior art, as shown in FIG. 2, a boiler is indispensable. However, in the present invention (1), steam is generated using surplus heat generated in the cogeneration system (CGS) 38. It is unnecessary.

〈本発明（２）の態様〉
図４は本発明（２）を説明する図である。 <Aspect of the present invention (2)>
FIG. 4 is a diagram for explaining the present invention (2).

図４のとおり、本発明（２）の熱電気水素供給システムにおいては、ＬＮＧを気化して天然ガスとして燃料とするコジェネレーションシステム（ＣＧＳ）６７を備える。ＬＮＧタンク６１中のＬＮＧは導管６２を介して熱交換器６３に供給される。ＬＮＧは熱交換器６３で加熱されて気化し、天然ガスとしてコジェネレーションシステム（ＣＧＳ）６７に供給される。その天然ガスの一部は、導管６４を介してパイプライン６５によりサテライトステーション周辺の需要に供される。   As shown in FIG. 4, the thermoelectric hydrogen supply system of the present invention (2) includes a cogeneration system (CGS) 67 that vaporizes LNG and uses it as fuel as natural gas. The LNG in the LNG tank 61 is supplied to the heat exchanger 63 via the conduit 62. The LNG is heated and vaporized by the heat exchanger 63 and supplied to a cogeneration system (CGS) 67 as natural gas. Part of the natural gas is provided to demand around the satellite station by a pipeline 65 via a conduit 64.

コジェネレーションシステム（ＣＧＳ）６７には電力発生装置であるガスタービン発電機などが配置されている。コジェネレーションシステム（ＣＧＳ）６７において、天然ガスはガスタービン発電機に供給され、空気供給管６８から供給され、酸素富化器６９で酸素富化された空気で燃焼して電気と熱（排熱）を発生する。電気は需要者に供給され、排熱は給湯、冷暖房等の用途に供される。その排熱の一部は水素分離型水蒸気改質器７２における天然ガスの水蒸気改質反応に供する水蒸気発生用に利用する。   The cogeneration system (CGS) 67 is provided with a gas turbine generator that is a power generation device. In a cogeneration system (CGS) 67, natural gas is supplied to a gas turbine generator, supplied from an air supply pipe 68, and combusted with air enriched with oxygen in an oxygen enricher 69 to generate electricity and heat (exhaust heat). ). Electricity is supplied to the consumer, and the exhaust heat is used for hot water supply, air conditioning and the like. Part of the exhaust heat is used for steam generation for use in the steam reforming reaction of natural gas in the hydrogen separation steam reformer 72.

符号７１は、水素分離型水蒸気改質器７２への水蒸気供給管である。水素分離型水蒸気改質器７２では原燃料である天然ガスを水蒸気改質反応により改質する。天然ガスは、熱交換器６３で気化し、導管６２を流れる天然ガスを分岐管６６で分岐し、水蒸気供給管７１を流れる水蒸気と合流して水素分離型水蒸気改質器７２へ供給される。   Reference numeral 71 is a steam supply pipe to the hydrogen separation steam reformer 72. The hydrogen separation steam reformer 72 reforms natural gas, which is a raw fuel, by a steam reforming reaction. The natural gas is vaporized by the heat exchanger 63, the natural gas flowing through the conduit 62 is branched by the branch pipe 66, merged with the steam flowing through the steam supply pipe 71, and supplied to the hydrogen separation steam reformer 72.

本発明（２）の熱電水素供給システムにおいては、コジェネレーションシステム（ＣＧＳ）６７での排熱を水素分離型水蒸気改質器７２における水蒸気改質用の加熱に利用する。符号６９は、そのためのコジェネレーションシステム（ＣＧＳ）６７から水素分離型水蒸気改質器７２への排ガス供給管である。   In the thermoelectric hydrogen supply system of the present invention (2), the exhaust heat from the cogeneration system (CGS) 67 is used for heating for steam reforming in the hydrogen separation steam reformer 72. Reference numeral 69 denotes an exhaust gas supply pipe from the cogeneration system (CGS) 67 for that purpose to the hydrogen separation steam reformer 72.

供給管６８を介して供給される空気は、酸素富化器６９で酸素が富化される。供給管６８中を流れる酸素富化空気はコジェネレーションシステム（ＣＧＳ）６７に供給され、電力発生装置であるガスタービン発電機に供給される天然ガスの燃焼用に使用される。   The air supplied through the supply pipe 68 is enriched with oxygen by the oxygen enricher 69. The oxygen-enriched air flowing through the supply pipe 68 is supplied to a cogeneration system (CGS) 67 and used for combustion of natural gas supplied to a gas turbine generator that is a power generation device.

コジェネレーションシステム（ＣＧＳ）６７からの燃焼排ガスは、導管６９を介して水素分離型水蒸気改質器７２の加熱部７３に供給され、水素分離型水蒸気改質器７２における天然ガスの水蒸気改質反応用加熱源として利用される。コジェネレーションシステム（ＣＧＳ）６７で発生した排熱により水蒸気を生成し、水素分離型水蒸気改質器７２での改質反応用に利用する。符号７１は、水素分離型水蒸気改質器７２への改質反応用の水蒸気供給管である。   The combustion exhaust gas from the cogeneration system (CGS) 67 is supplied to the heating unit 73 of the hydrogen separation type steam reformer 72 through the conduit 69, and the steam reforming reaction of natural gas in the hydrogen separation type steam reformer 72. It is used as a heating source. Steam is generated by exhaust heat generated in the cogeneration system (CGS) 67 and used for the reforming reaction in the hydrogen separation steam reformer 72. Reference numeral 71 denotes a steam supply pipe for reforming reaction to the hydrogen separation steam reformer 72.

導管６９を介して供給され、加熱部７３を経たコジェネレーションシステム（ＣＧＳ）６７からの排ガスは、水素分離型水蒸気改質器７２における天然ガスの水蒸気改質反応用加熱源として利用することから、その排ガス自体は冷却されているが、導出管７５を流れる水素分離型水蒸気改質器７２からのオフガス導出管７５を流れるオフガスに合流させる。合流ガスは、導管７６中を流れ、圧縮機Ｐ１により圧縮した後、熱交換器６３で冷却する。   The exhaust gas supplied from the cogeneration system (CGS) 67 supplied through the conduit 69 and passed through the heating unit 73 is used as a heat source for the steam reforming reaction of natural gas in the hydrogen separation steam reformer 72. Although the exhaust gas itself is cooled, the exhaust gas is joined to the off-gas flowing through the off-gas outlet pipe 75 from the hydrogen separation type steam reformer 72 flowing through the outlet pipe 75. The combined gas flows through the conduit 76 and is cooled by the heat exchanger 63 after being compressed by the compressor P1.

熱交換器６３において、その冷却源はＬＮＧタンク６１から導管６２を介して供給されるＬＮＧであり、ＬＮＧの冷熱を二酸化炭素の液化回収に利用する。また逆に、コジェネレーションシステム（ＣＧＳ）６７、水素分離型水蒸気改質器７２からの排熱をＬＮＧの気化に利用するものである。   In the heat exchanger 63, the cooling source is LNG supplied from the LNG tank 61 through the conduit 62, and the cold heat of the LNG is used for liquefying and recovering carbon dioxide. Conversely, the exhaust heat from the cogeneration system (CGS) 67 and the hydrogen separation steam reformer 72 is used to vaporize LNG.

二酸化炭素は、（ａ）加熱部７３を経たコジェネレーションシステム（ＣＧＳ）６７からの排ガスと、（ｂ）水素分離型水蒸気改質器７２からのオフガスの合流ガスであるので、合流ガス中に含まれる二酸化炭素（ＣＯ2）をすべて液化炭酸にする。 Since carbon dioxide is a combined gas of (a) the exhaust gas from the cogeneration system (CGS) 67 that has passed through the heating unit 73 and (b) the off-gas from the hydrogen separation steam reformer 72, it is included in the combined gas. All the carbon dioxide (CO 2 ) that is generated is converted into liquefied carbonic acid.

液化炭酸は気液分離器７７により分離し、導出管７８により取り出し、回収され、その用途に利用される。気液分離器７７において、熱交換器６３を経た合流ガス中の二酸化炭素は実質上、すべて液化炭酸として分離する。気液分離槽７７で分離されたガス（気相分）にはＣＯ、Ｈ2、ＣＨ4、ＣＯ2などが含まれている。そのうちＣＯ、Ｈ2、ＣＨ4は燃料になるので、気相分は導出管７９を介して導出し、コジェネレーションシステム（ＣＧＳ）６７での燃焼用燃料に利用する。また、気相分にはＣＯ、Ｈ2が含まれているので、気相分の一部を導出管８０により導出し、浸炭などの用途に利用する。 The liquefied carbon dioxide is separated by a gas-liquid separator 77, taken out by a lead-out pipe 78, recovered, and used for its use. In the gas-liquid separator 77, substantially all of the carbon dioxide in the combined gas that has passed through the heat exchanger 63 is separated as liquefied carbon dioxide. The gas (gas phase component) separated in the gas-liquid separation tank 77 contains CO, H 2 , CH 4 , CO 2 and the like. Of these, CO, H 2 , and CH 4 become fuel, so the gas phase component is led out through the lead-out pipe 79 and used as fuel for combustion in the cogeneration system (CGS) 67. Further, since CO and H 2 are contained in the gas phase, a part of the gas phase is derived by the outlet pipe 80 and used for applications such as carburizing.

このように、本発明（２）においては、酸素富化空気とＬＮＧの冷熱を用いることにより、熱、電気を発生し、水素を製造するとともに、天然ガス由来の二酸化炭素の全量または大部分を分離回収し、有効利用することができる。これにより、熱と電気だけでなく、水素や二酸化炭素を必要とする産業用施設、水素ステーションを併設する大型施設への適用が可能であり、エネルギーの効率的な利用と、二酸化炭素排出量の大幅削減が可能である。   As described above, in the present invention (2), by using oxygen-enriched air and the cold heat of LNG, heat and electricity are generated, hydrogen is produced, and all or most of carbon dioxide derived from natural gas is produced. It can be separated and recovered for effective use. As a result, it can be applied not only to heat and electricity, but also to industrial facilities that require hydrogen and carbon dioxide, and large facilities with hydrogen stations. Significant reduction is possible.

また、従来技術においては、図２のとおり、ボイラーが必須であるが、本発明（２）においては、図４のとおり、ＣＧＳ（コジェネレーションシステム）６７において発生する余剰熱を利用して水蒸気を生成するのでボイラーは不要である。   In the prior art, a boiler is indispensable as shown in FIG. 2, but in the present invention (2), as shown in FIG. 4, steam is generated using surplus heat generated in a CGS (cogeneration system) 67 as shown in FIG. A boiler is not necessary because it generates.

１ ＬＮＧタンク
２ 導管
３ 熱交換器
４ コジェネレーションシステム（ＣＧＳ）
５ ＬＮＧタンク１からのボイルオフガス排出導管
６ パイプライン
１１ 都市ガス導管
１２ 都市ガス導管１１からの分岐管
１３ 脱硫器
１４ 空気供給管
１５ ボイラー
１６ ボイラー１５への水供給管
１７ 水素分離型水蒸気改質器
Ｐ１、Ｐ２ 圧縮機
１８ 燃焼器
２１ 気液分離器
２３ 液化炭酸の導出管
３１ ＬＮＧタンク
３３ 熱交換器
３８ 天然ガスを燃料とするコジェネレーションシステム（ＣＧＳ）
３９ 空気供給管
４０ 酸素富化器
４１ 酸素富化空気の分岐管
４４ 水素分離型水蒸気改質器４５への水蒸気供給管
４５ 水素分離型水蒸気改質器
４６ 燃焼器
４９ 気液分離器
５２、５３ 気相分導出管
６１ ＬＮＧタンク
６２ ＬＮＧ導管
６３ 熱交換器
６４ 天然ガス導管
６５ パイプライン
６７ 天然ガスを燃料とするコジェネレーションシステム（ＣＧＳ）
６８ 空気供給管
６９ 酸素富化器
７０ 温水、水蒸気等の導出管
７１ 水素分離型水蒸気改質器７２への水蒸気供給管
７２ 水素分離型水蒸気改質器
７３ 水素分離型水蒸気改質器７２の加熱部
７５ オフガス導出管
７６ 合流ガス導管
７７ 気液分離器
７８ 液化炭酸の導出管
７９、８０ 気相分導出管
1 LNG tank 2 Conduit 3 Heat exchanger 4 Cogeneration system (CGS)
5 Boil-off gas discharge pipe from LNG tank 1 6 Pipeline 11 City gas pipe 12 Branch pipe from city gas pipe 11 13 Desulfurizer 14 Air supply pipe 15 Boiler 16 Water supply pipe to boiler 15 17 Hydrogen separation type steam reforming Units P1, P2 Compressor 18 Combustor 21 Gas-liquid separator 23 Liquefied carbonic acid outlet pipe 31 LNG tank 33 Heat exchanger 38 Cogeneration system (CGS) using natural gas as fuel
DESCRIPTION OF SYMBOLS 39 Air supply pipe 40 Oxygen enricher 41 Branch pipe of oxygen enriched air 44 Steam supply pipe to hydrogen separation type steam reformer 45 45 Hydrogen separation type steam reformer 46 Combustor 49 Gas-liquid separator 52, 53 Gas phase outlet pipe 61 LNG tank 62 LNG conduit 63 Heat exchanger 64 Natural gas conduit 65 Pipeline 67 Cogeneration system using natural gas as fuel (CGS)
68 Air supply pipe 69 Oxygen enricher 70 Derived pipe for hot water, steam, etc. 71 Steam supply pipe to the hydrogen separation steam reformer 72 72 Hydrogen separation steam reformer 73 Heating of the hydrogen separation steam reformer 72 Section 75 Off-gas outlet pipe 76 Combined gas pipe 77 Gas-liquid separator 78 Liquid carbon dioxide outlet pipe 79, 80 Gas phase outlet pipe

Claims (5)

ＬＮＧを気化した天然ガスを燃料とするコジェネレーションシステムと、前記天然ガスの水蒸気改質による水素分離型水蒸気改質器と、前記水蒸気改質用加熱源である燃焼器とを有する熱、電気および水素を供給するシステムであって、
（ａ）前記コジェネレーションシステムからの排ガスと前記水素分離型水蒸気改質器からのオフガスを合流させ、
（ｂ）前記排ガス及びオフガスをその流れ方向でみて、順次、圧縮機、冷却熱交換器及び気液分離槽を含む二酸化炭素回収装置を備えてなり、
（ｃ）前記冷却熱交換器の冷熱として前記ＬＮＧを使用し、
（ｄ）前記コジェネレーションシステム及び前記水蒸気改質用加熱源である燃焼器には酸素富化空気を使用するようにしてなる、
ことを特徴とする熱電気水素供給システム。 Cogeneration system using natural gas vaporized LNG as fuel, hydrogen separation type steam reformer by steam reforming of the natural gas, and combustor which is the steam reforming heating source, electricity, and A system for supplying hydrogen,
(A) combining the exhaust gas from the cogeneration system and the off-gas from the hydrogen separation steam reformer,
(B) Looking at the exhaust gas and off-gas in the flow direction, and sequentially comprising a carbon dioxide recovery device including a compressor, a cooling heat exchanger and a gas-liquid separation tank,
(C) using the LNG as the cooling heat of the cooling heat exchanger;
(D) Oxygen-enriched air is used for the cogeneration system and the combustor that is the heating source for steam reforming.
A thermoelectric hydrogen supply system characterized by that. 請求項１に記載の熱電気水素供給システムにおいて、前記コジェネレーションシステムにて生成した水蒸気を前記水蒸気改質器での天然ガスの水蒸気改質用に使用するようにしてなることを特徴とする熱電気水素供給システム。   2. The thermoelectric hydrogen supply system according to claim 1, wherein the steam generated by the cogeneration system is used for steam reforming of natural gas in the steam reformer. Electric hydrogen supply system. ＬＮＧを気化した天然ガスを燃料とするコジェネレーションシステムと、前記天然ガスの水蒸気改質による水素分離型水蒸気改質器と、前記水蒸気改質用加熱源であるヒーターとを有する熱、電気および水素を供給するシステムであって、
（ａ）前記コジェネレーションシステムからの排ガスを前記ヒーターの熱源として使用した後、
（ｂ）前記排ガスと前記水素分離型水蒸気改質器からのオフガスを合流させ、
（ｃ）前記排ガス及びオフガスをその流れ方向でみて、順次、圧縮機、冷却熱交換器及び気液分離槽を含む二酸化炭素回収装置を備えてなり、
（ｄ）前記冷却熱交換器の冷熱として前記ＬＮＧを使用し、
（ｅ）前記コジェネレーションシステムには酸素富化空気を使用するようにしてなる、
ことを特徴とする熱電気水素供給システム。 Heat, electricity and hydrogen comprising a cogeneration system using natural gas vaporized LNG as a fuel, a hydrogen separation type steam reformer by steam reforming of the natural gas, and a heater which is the heating source for steam reforming A system for supplying
(A) After using the exhaust gas from the cogeneration system as a heat source for the heater,
(B) combining the off-gas from the exhaust gas and the hydrogen separation steam reformer,
(C) Looking at the exhaust gas and off-gas in the flow direction, and sequentially comprising a carbon dioxide recovery device including a compressor, a cooling heat exchanger and a gas-liquid separation tank,
(D) using the LNG as the cooling heat of the cooling heat exchanger;
(E) The cogeneration system uses oxygen-enriched air.
A thermoelectric hydrogen supply system characterized by that. 請求項３に記載の熱電気水素供給システムにおいて、前記コジェネレーションシステムにて生成した水蒸気を前記水蒸気改質器での天然ガスの水蒸気改質用に使用するようにしてなることを特徴とする熱電気水素供給システム。   The thermoelectric hydrogen supply system according to claim 3, wherein the steam generated by the cogeneration system is used for steam reforming of natural gas in the steam reformer. Electric hydrogen supply system. 請求項１〜４のいずれか１項に記載の熱電気水素供給システムが、オンサイト方式の水素ステーションで設置する熱電気水素供給システムであることを特徴とする熱電気水素供給システム。
The thermoelectric hydrogen supply system according to any one of claims 1 to 4, wherein the thermoelectric hydrogen supply system is a thermoelectric hydrogen supply system installed at an on-site type hydrogen station.
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