JP2003081605A - Hydrogen producing method accompanying recovery of liquefied co2 - Google Patents

Hydrogen producing method accompanying recovery of liquefied co2

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Publication number
JP2003081605A
JP2003081605A JP2001268396A JP2001268396A JP2003081605A JP 2003081605 A JP2003081605 A JP 2003081605A JP 2001268396 A JP2001268396 A JP 2001268396A JP 2001268396 A JP2001268396 A JP 2001268396A JP 2003081605 A JP2003081605 A JP 2003081605A
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Japan
Prior art keywords
gas
hydrogen
liquefied
combustion
carbon dioxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP2001268396A
Other languages
Japanese (ja)
Other versions
JP3670229B2 (en
Inventor
Yoshiaki Takatani
芳明 高谷
Seiichi Nakanishi
誠一 中西
Eiji Kawagoe
英司 川越
Kenjiro Haraguchi
憲次郎 原口
Shoji Kamiya
祥二 神谷
Masaru Ogawa
賢 小川
Hiroshi Honda
宏 本田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kansai Electric Power Co Inc
Kawasaki Heavy Industries Ltd
Original Assignee
Kansai Electric Power Co Inc
Kawasaki Heavy Industries Ltd
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Priority to JP2001268396A priority Critical patent/JP3670229B2/en
Publication of JP2003081605A publication Critical patent/JP2003081605A/en
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Publication of JP3670229B2 publication Critical patent/JP3670229B2/en
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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
    • F25J3/02—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
    • F25J3/04—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 for air
    • F25J3/04521—Coupling of the air fractionation unit to an air gas-consuming unit, so-called integrated processes
    • F25J3/04527—Integration with an oxygen consuming unit, e.g. glass facility, waste incineration or oxygen based processes in general
    • F25J3/04539—Integration with an oxygen consuming unit, e.g. glass facility, waste incineration or oxygen based processes in general for the H2/CO synthesis by partial oxidation or oxygen consuming reforming processes of fuels
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    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0005—Light or noble gases
    • F25J1/001—Hydrogen
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    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
    • F25J1/0027—Oxides of carbon, e.g. CO2
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    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
    • F25J1/0032—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration"
    • F25J1/0035—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by gas expansion with extraction of work
    • F25J1/0037—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by gas expansion with extraction of work of a return stream
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    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
    • F25J1/0032—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration"
    • F25J1/004—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by flash gas recovery
    • 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
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
    • F25J1/0032—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration"
    • F25J1/0045—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using the feed stream itself or separated fractions from it, i.e. "internal refrigeration" by vaporising a liquid return 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
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0221—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using the cold stored in an external cryogenic component in an open refrigeration loop
    • F25J1/0224—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using the cold stored in an external cryogenic component in an open refrigeration loop in combination with an internal quasi-closed refrigeration loop
    • 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
    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0228—Coupling of the liquefaction unit to other units or processes, so-called integrated processes
    • 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
    • F25J3/04—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 for air
    • F25J3/04248—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion
    • F25J3/04254—Generation of cold for compensating heat leaks or liquid production, e.g. by Joule-Thompson expansion using the cold stored in external cryogenic fluids
    • F25J3/0426—The cryogenic component does not participate in the fractionation
    • F25J3/04266—The cryogenic component does not participate in the fractionation and being liquefied hydrocarbons
    • 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
    • F25J2205/00—Processes or apparatus using other separation and/or other processing means
    • F25J2205/60—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
    • 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
    • F25J2210/42—Nitrogen
    • 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
    • F25J2220/00—Processes or apparatus involving steps for the removal of impurities
    • F25J2220/02—Separating impurities in general from the feed stream
    • 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
    • F25J2245/00—Processes or apparatus involving steps for recycling of process streams
    • F25J2245/90—Processes or apparatus involving steps for recycling of process streams the recycled stream being boil-off gas from storage
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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
    • F25J2250/00—Details related to the use of reboiler-condensers
    • F25J2250/02—Bath type boiler-condenser using thermo-siphon effect, e.g. with natural or forced circulation or pool boiling, i.e. core-in-kettle heat exchanger
    • 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
    • F25J2270/00—Refrigeration techniques used
    • F25J2270/04—Internal refrigeration with work-producing gas expansion loop
    • F25J2270/06—Internal refrigeration with work-producing gas expansion loop with multiple gas expansion loops
    • 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

Abstract

PROBLEM TO BE SOLVED: To perform hydrogen production and CO2 recovery at the same time and to effectively utilize LNG cold. SOLUTION: In a method of producing hydrogen by steam reforming using liquefied natural gas (LNG) as a raw material to obtain purified hydrogen, the separation/recovery and the liquefaction of CO2 are facilitated by utilizing unrecovered combustible gas (PSA off-gas) produced in the purification process of hydrogen as fuel for heating a reformer and using high concentration oxygen preferably pure oxygen as an oxidizing agent for the combustion to obtain high concentration CO2 in the produced combustion gas. High concentration oxygen or pure oxygen is produced by the low-temperature separation process using the LNG cold effectively to be used as the oxidizing agent for a combustion furnace of the reformer and liquefied nitrogen is used for the liquefaction of pure hydrogen. Further, carbon dioxide is recovered in a liquefied state by using the LNG cold effectively.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は、天然ガスを水蒸気
改質して水素を製造する方法において、原料である液化
天然ガス（ＬＮＧ）が保有する冷熱を有効利用するとと
もに、改質器からの燃焼排ガスから容易に液化ＣＯ2を
回収することができる水素製造方法に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for steam-reforming natural gas to produce hydrogen, by effectively utilizing the cold heat of liquefied natural gas (LNG), which is a raw material, and from a reformer. The present invention relates to a hydrogen production method capable of easily recovering liquefied CO 2 from combustion exhaust gas.

【０００２】[0002]

【従来の技術】天然ガスを水蒸気改質して水素を製造す
るプロセスは、従来、化成品（メタノール、アンモニ
ア）製造などで広く工業化された技術である。このよう
な水素製造プラントは、海外立地の場合が多く、これら
の国で原料となる天然ガスはガスで供給されるのが通例
である。2. Description of the Related Art The process of steam-reforming natural gas to produce hydrogen has hitherto been a widely industrialized technique for producing chemical products (methanol, ammonia). Such hydrogen production plants are often located in overseas locations, and natural gas, which is a raw material in these countries, is usually supplied by gas.

【０００３】一方、日本では天然ガスの輸入は、液化し
てタンカー輸送されるのが通例であり、液化天然ガス
（ＬＮＧ）の保有する冷熱は、一部は、冷熱発電、深冷
空気分離、ＬＮＧボイルオフガスの再冷却熱源として利
用され、周辺コンビナートの冷凍倉庫などへの冷熱供給
にも利用されるが、高々５０％程度の利用率に留まって
いる。有効利用されていない冷熱は、海水や大気に無為
に捨てられている。また、海水でＬＮＧを暖めるという
熱交換方法が、末端ユーザーへの天然ガス配送のために
採られるＬＮＧガス化の手段であるが、冷却された海水
を沿岸にそのまま放出すると沿岸漁場への環境影響があ
る。このようにＬＮＧ冷熱は有効利用されないばかり
か、むしろ、その冷熱の処分に窮しているというのが本
質的な問題であった。On the other hand, in Japan, imports of natural gas are usually liquefied and transported by tankers, and some of the cold heat of liquefied natural gas (LNG) is cold power generation, deep air separation, It is used as a heat source for re-cooling LNG boil-off gas and is also used for supplying cold heat to the frozen warehouses in the peripheral complex, but the utilization rate is at most about 50%. Cold heat that is not effectively used is dumped wastefully into seawater and the atmosphere. In addition, the heat exchange method of warming LNG with seawater is a means of LNG gasification that is used to deliver natural gas to end users. However, if cooled seawater is discharged directly to the coast, it will have an environmental impact on coastal fishing grounds. There is. As described above, the essential problem is that the LNG cold heat is not effectively utilized, but rather, the cold heat is poorly disposed.

【０００４】また、天然ガスを改質して水素を製造した
場合、地球温暖化物質として二酸化炭素が発生する。従
来、二酸化炭素の大気放出に対する環境規制は特にはな
かったが、今後、ＣＯ2放出に関する規制やＣＯ2の処理
義務が伴う社会情勢の到来が予想される。When hydrogen is produced by reforming natural gas, carbon dioxide is generated as a global warming substance. Conventionally, environmental regulations against atmospheric discharge of carbon dioxide was not particularly future advent of social conditions with the processing duties of the regulations and CO 2 about CO 2 emission is expected.

【０００５】[0005]

【発明が解決しようとする課題】従来、天然ガスを改質
して水素に富む改質ガスとし、改質ガスはＰＳＡ吸着分
離法などで水素を分離精製し、分離された可燃物を含む
オフガスを主燃料として改質器の加熱炉に用いる方法に
おいては、オフガス燃焼の酸化剤として空気が使用され
ている。しかし、空気で燃焼させると燃焼排ガス中の二
酸化炭素濃度は窒素で薄まってしまっているので、二酸
化炭素の分離回収が難しい。特に、ＬＮＧ冷熱で冷却し
ても二酸化炭素分圧が低いと液化せずに固相域の状態、
つまりドライアイスにしかならず、回収した二酸化炭素
のハンドリングがやっかいになる。Conventionally, natural gas is reformed into a hydrogen-rich reformed gas, and the reformed gas is an offgas containing combustibles separated and purified by separating and refining hydrogen by a PSA adsorption separation method or the like. In the method of using as a main fuel in a heating furnace of a reformer, air is used as an oxidant for off-gas combustion. However, when burning with air, the concentration of carbon dioxide in the flue gas has been diluted with nitrogen, making it difficult to separate and collect carbon dioxide. In particular, even if it is cooled with LNG cold heat, if the carbon dioxide partial pressure is low, it will not liquefy and will be in the solid phase region,
In other words, it is not only dry ice, but the handling of the collected carbon dioxide is troublesome.

【０００６】本発明は上記の点に鑑みなされたもので、
本発明の目的は、純酸素（又は高濃度の酸素）をオフガ
ス燃焼の酸化剤として使用し、天然ガスを酸素燃焼加熱
により改質して水素を製造するシステムとすることによ
り、高濃度の二酸化炭素を含んだ燃焼排ガスが得られ、
加圧してＬＮＧ冷熱で冷却すれば容易に液化ＣＯ2とし
て回収でき、貯蔵や販売のための輸送など取り扱いが容
易になる水素製造方法を提供することにある。また、本
発明の目的は、ＬＮＧから天然ガス改質によって水素を
製造するシステムにおいて、ＬＮＧ冷熱を利用した深冷
空気分離で製造した純酸素を天然ガスの改質プロセスで
有効利用するとともに、ＬＮＧ冷熱を有効利用して燃焼
排ガスから液化ＣＯ2を回収することにより、ＬＮＧ冷
熱のさらなる有効利用が実現できる水素製造方法を提供
することにある。The present invention has been made in view of the above points,
An object of the present invention is to use pure oxygen (or a high concentration of oxygen) as an oxidizer for off-gas combustion, and to provide a system for producing hydrogen by reforming natural gas by oxygen combustion heating to produce a high concentration of dioxide. Combustion exhaust gas containing carbon is obtained,
An object of the present invention is to provide a hydrogen production method which can be easily recovered as liquefied CO 2 by pressurizing and cooling with LNG cold heat, and which can be easily handled such as storage and transportation for sale. Further, an object of the present invention is to effectively utilize pure oxygen produced by deep-air separation using LNG cold heat in a reforming process of natural gas in a system for producing hydrogen from LNG by reforming natural gas. It is an object of the present invention to provide a hydrogen production method capable of realizing more effective utilization of LNG cold heat by recovering liquefied CO 2 from combustion exhaust gas by effectively utilizing cold heat.

【０００７】なお、特開平１１−１１１３２０号公報に
は、ＬＮＧを原料として水蒸気改質により水素を製造
し、得られた水素を燃料電池で利用して電力を発生させ
るシステムにおいて、発電後の燃料電池からの窒素濃縮
ガスをＰＳＡ法により酸素と窒素に分離し、燃料電池か
らの炭酸ガスと未反応燃料はＬＮＧ冷熱で炭酸ガスを液
化して分離し、分離された酸素と未反応燃料は熱回収部
から抜き出した水蒸気とともに改質器に循環するという
構成が開示されているが、上記公報に記載された発明
は、燃料電池本体で発電後の排ガスを対象にしており、
また、本発明とは、目的、構成、機能・作用及び効果等
が全く異なっている。Japanese Patent Laid-Open No. 11-113120 discloses a system in which hydrogen is produced by steam reforming using LNG as a raw material, and the obtained hydrogen is used in a fuel cell to generate electric power. Nitrogen-enriched gas from the cell is separated into oxygen and nitrogen by the PSA method, carbon dioxide gas and unreacted fuel from the fuel cell are separated by liquefying carbon dioxide gas with LNG cold heat, and separated oxygen and unreacted fuel are heated. Although a configuration is disclosed in which it is circulated to the reformer together with the steam extracted from the recovery unit, the invention described in the above publication is directed to the exhaust gas after power generation in the fuel cell body,
Further, the present invention is completely different from the present invention in the purpose, constitution, function / action, effect and the like.

【０００８】[0008]

【課題を解決するための手段】上記の目的を達成するた
めに、本発明の液化ＣＯ2回収を伴う水素製造方法は、
天然ガスを水蒸気改質して水素に富む改質ガスとし、こ
の改質ガスから水素を分離精製し、水素の精製工程で分
離された可燃物を含むオフガスを主燃料として改質工程
での燃焼加熱に用いる水素製造方法において、改質工程
でのオフガス燃焼のための酸化剤として高濃度の酸素、
好ましくは純酸素を導入し、この燃焼で発生する燃焼排
ガス中の炭酸ガスを高濃度にして、燃焼排ガスから炭酸
ガスを容易に液体状態で分離・回収するように構成され
ている。In order to achieve the above object, the method for producing hydrogen with recovery of liquefied CO 2 of the present invention comprises:
Natural gas is steam reformed into hydrogen-rich reformed gas, hydrogen is separated and purified from this reformed gas, and the off-gas containing combustibles separated in the hydrogen purification process is used as the main fuel for combustion in the reforming process. In the hydrogen production method used for heating, high concentration oxygen as an oxidant for off-gas combustion in the reforming step,
Preferably, pure oxygen is introduced, the carbon dioxide gas in the combustion exhaust gas generated by this combustion is made to have a high concentration, and the carbon dioxide gas is easily separated and recovered from the combustion exhaust gas in a liquid state.

【０００９】上記の方法において、天然ガスの供給形態
が液化天然ガス（ＬＮＧ）であり、その液化冷熱を利用
した深冷空気分離により純酸素又は高濃度の酸素を製造
し、この酸素を改質工程でのオフガス燃焼のための酸化
剤として使用し、深冷空気分離で得られた液化窒素を精
製した水素の液化に利用することが好ましい。また、Ｌ
ＮＧ冷熱を有効利用して、オフガス燃焼で発生する燃焼
排ガスから炭酸ガスを液体状態で分離・回収することが
好ましい。In the above method, the supply form of natural gas is liquefied natural gas (LNG), and pure oxygen or high-concentration oxygen is produced by cryogenic air separation using the liquefied cold heat, and this oxygen is reformed. It is preferable to use it as an oxidant for off-gas combustion in the process and utilize the liquefied nitrogen obtained by the cryogenic air separation for the liquefaction of purified hydrogen. Also, L
It is preferable to effectively utilize NG cold heat to separate and recover carbon dioxide gas in a liquid state from combustion exhaust gas generated by off-gas combustion.

【００１０】また、上記の方法においては、高濃度の炭
酸ガスを含んだ燃焼排ガスから液化ＣＯ2を分離・回収
するに際し、前処理として燃焼排ガス中に含まれる水分
を除去した後、炭酸ガスの液化が可能な圧力に昇圧し、
液化天然ガスの冷熱を用いて冷却することにより液化Ｃ
Ｏ2を得ることが好ましい。この場合、水分除去のため
の前処理として、水分を選択的に吸着する合成ゼオライ
ト３Ａ型を用いて燃焼排ガス中に含まれる水分を除去す
ることが好ましい。Further, in the above method, when the liquefied CO 2 is separated and recovered from the combustion exhaust gas containing a high concentration of carbon dioxide gas, after removing the water contained in the combustion exhaust gas as a pretreatment, Increase the pressure to liquefy,
Liquefied C by liquefying natural gas
It is preferred to obtain O 2 . In this case, as a pretreatment for removing water, it is preferable to remove the water contained in the combustion exhaust gas by using a synthetic zeolite 3A type that selectively adsorbs water.

【００１１】[0011]

【発明の実施の形態】以下、本発明の実施の形態につい
て説明するが、本発明は下記の実施の形態に何ら限定さ
れるものではなく、適宜変更して実施することが可能な
ものである。図１は、本発明の実施の第１形態による液
化ＣＯ2回収を伴う水素製造方法を実施する装置の全体
システムの概要を示している。本実施の形態では、ＬＮ
Ｇから天然ガス改質によって水素を製造するシステムを
想定している。ＬＮＧ基地全体での冷熱利用としては、
水素製造システムの系外に深冷空気分離設備１０が設置
されているが、「深冷空気分離」の存在は何ら無理のな
い条件設定である。例えば、既存のＬＮＧ基地の冷熱利
用の現状は、最も進んだＬＮＧ冷熱利用の場合でも、そ
の利用率は高々５０％である。一例として、その主な用
途は以下のような内訳になっている。冷熱発電；５９．
５％、空気分離への冷熱利用；１７．７％、ＬＮＧタン
クのボイルオフガス（ＢＯＧ）再液化；１７．５％、液
化炭酸製造；０．７％BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments, and can be appropriately modified and implemented. . FIG. 1 shows an outline of an entire system of an apparatus for carrying out a hydrogen production method with liquefied CO 2 recovery according to a first embodiment of the present invention. In this embodiment, the LN
A system for producing hydrogen from G by natural gas reforming is assumed. For the use of cold heat at the entire LNG base,
Although the deep air separation facility 10 is installed outside the hydrogen production system, the existence of "deep air separation" is a reasonable condition setting. For example, at present, the utilization of cold heat at existing LNG bases is 50% at most even in the most advanced use of LNG cold heat. As an example, the main uses are as follows. Cold heat generation; 59.
5%, utilization of cold heat for air separation; 17.7%, LNG tank boil-off gas (BOG) reliquefaction; 17.5%, liquefied carbon dioxide production; 0.7%

【００１２】深冷空気分離設備１０で生産される純酸素
を天然ガス改質器１２の加熱炉（燃焼炉）の酸化剤とし
て利用する。ＬＮＧ冷熱を利用した深冷空気分離で製造
した純酸素を天然ガスの改質プロセスで有効利用するこ
とによって、２次的なＬＮＧ冷熱の有効利用の需要プロ
セスを創出する。また、天然ガスを改質器１２及びＣＯ
シフト反応器１４によって水素に富む改質ガスとし、水
素精製設備１６でＰＳＡ吸着分離法により水素を分離精
製し、分離された可燃物を含むオフガスを改質器１２の
加熱燃料として使用する。このように、改質器１２の加
熱炉の主燃料は、ＰＳＡのオフガスであるが、従来の化
学工業用の水素製造法でのバランスは、補助燃料として
天然ガスを加えた燃料との混合ガスが燃料となる。しか
し、純酸素燃焼するならば、空気で燃焼する場合と異な
り、排ガス中に窒素が含まれないので、言い換えれば、
燃焼排ガスの窒素成分の持ち去り顕熱が少なくて済み、
結果的に天然ガス補助燃料の消費量を抑えるか、無くす
効果も期待できる。Pure oxygen produced in the cryogenic air separation facility 10 is used as an oxidizer for the heating furnace (combustion furnace) of the natural gas reformer 12. By effectively using the pure oxygen produced by the deep air separation using LNG cold heat in the reforming process of natural gas, a demand process for effective use of secondary LNG cold heat is created. In addition, the natural gas is supplied to the reformer 12 and CO
The shift reactor 14 produces a reformed gas rich in hydrogen, and the hydrogen purification facility 16 separates and purifies the hydrogen by the PSA adsorption separation method, and the off gas containing the separated combustible material is used as a heating fuel for the reformer 12. As described above, the main fuel of the heating furnace of the reformer 12 is the off gas of PSA, but the balance in the conventional hydrogen production method for the chemical industry is a mixed gas with the fuel to which natural gas is added as an auxiliary fuel. Becomes fuel. However, in the case of pure oxygen combustion, unlike in the case of combustion with air, nitrogen is not contained in the exhaust gas, in other words,
The nitrogen component of the combustion exhaust gas is carried away and less sensible heat is required.
As a result, the effect of suppressing or eliminating the consumption of natural gas auxiliary fuel can be expected.

【００１３】また、純酸素をオフガス燃焼の酸化剤とし
て使用することにより、燃焼排ガスは二酸化炭素、水
分、酸素だけになるので、この燃焼排ガスをＬＮＧ冷熱
を利用したＣＯ2の深冷分離プロセス（ＣＯ2液化設備１
８）で処理すれば、水分は除湿器２０での前処理で凝縮
・吸着除去されているので、燃焼用の過剰酸素と二酸化
炭素だけの排ガスとなって、分離プロセスに必要なエネ
ルギーが少なくて済む。さらに都合良く、二酸化炭素が
高濃度となるので、二酸化炭素の相平衡の状態図の関係
から、それほど全圧を高くしなくても液相となる分圧に
することができる。つまり、少ない処理ガス量を低い圧
力で圧縮・冷却すれば良いため、容易に液化ＣＯ2を製
造することができる。Further, when pure oxygen is used as an oxidant for off-gas combustion, the combustion exhaust gas is only carbon dioxide, water and oxygen. Therefore, this combustion exhaust gas is subjected to a deep cooling separation process of CO 2 using LNG cold heat ( CO 2 liquefaction facility 1
If treated in 8), the water is condensed and adsorbed and removed by the pretreatment in the dehumidifier 20, so it becomes exhaust gas of only excess oxygen and carbon dioxide for combustion, and the energy required for the separation process is small. I'm done. More conveniently, since the carbon dioxide has a high concentration, it is possible to set the partial pressure to a liquid phase even if the total pressure is not so high from the relationship of the phase diagram of the phase equilibrium of carbon dioxide. That is, since it is sufficient to compress and cool a small amount of processing gas at a low pressure, it is possible to easily produce liquefied CO 2 .

【００１４】精製した水素は、ガス貯蔵される場合と、
液化して貯蔵する場合とがある。精製水素を液化する場
合は、予冷却器２２でＬＮＧ冷熱を用いて予冷した後、
前述の深冷空気分離によって得られた液体窒素を水素液
化のための冷媒として利用して冷却器２４で水素を液化
する。従来の水素の製造だけを目的とした生産システム
では、二酸化炭素の回収を目的とした余分なプロセスを
付加することは、設備コストがかさむので、水素の製造
コストが上昇することになる。しかし、ＣＯ2処理を前
提としたような社会情勢、すなわち、ＣＯ2に対する課
税処置等が施行されるような国際的合意が整えば、水素
とある意味で付加価値を有する二酸化炭素がＬＮＧ冷熱
を有効利用して、同時に製造できるため、システム全体
のコストとしては、低減されることになる。Purified hydrogen is stored in gas and
It may be liquefied and stored. When liquefying purified hydrogen, after precooling with LNG cold heat in the precooler 22,
The liquid nitrogen obtained by the above-described deep-air separation is used as a refrigerant for hydrogen liquefaction to liquefy hydrogen in the cooler 24. In a conventional production system only for producing hydrogen, adding an extra process for the purpose of recovering carbon dioxide increases the facility cost, resulting in an increase in hydrogen production cost. However, if there is a social situation on the premise of CO 2 treatment, that is, if there is an international agreement to implement tax treatment for CO 2 , hydrogen and carbon dioxide, which has a certain added value, will generate LNG cold heat. Since it can be effectively used and manufactured at the same time, the cost of the entire system is reduced.

【００１５】図２は、本発明の実施の第２形態による液
化ＣＯ2回収を伴う水素製造方法を実施する装置を示し
ている。 改質ユニット 天然ガスから水素を製造するプロセスとしては、一般に
は水蒸気改質（スチームリフォーミング）と呼ばれる下
記の反応が適用される。 ＣＨ4＋２Ｈ2Ｏ＝ＣＯ2＋４Ｈ2 …（１） ただし、上記の反応式（１）は、実際には下記の
（２）、（３）の反応式の平衡関係で反応率、組成が決
まる。 ＣＨ4＋Ｈ2Ｏ＝ＣＯ＋３Ｈ2 …（２） ＣＯ＋Ｈ2Ｏ＝ＣＯ2＋Ｈ2 …（３） つまり、操作圧力、温度、スチームカーボン比によっ
て、到達平衡条件が決定する。（２）式が吸熱反応、
（３）式が発熱反応であるから、温度が高いほど（２）
式は進行するのでメタンの反応率は向上するが、逆に温
度が高いと（３）式は逆方向に有利となるので、改質ガ
スのＣＯ濃度は高くなる。一例として、改質器出口の改
質ガス温度で８００℃となる設定でプロセスを構成す
る。FIG. 2 shows an apparatus for carrying out the method for producing hydrogen with liquefied CO 2 recovery according to the second embodiment of the present invention. Reforming unit As a process for producing hydrogen from natural gas, the following reaction generally called steam reforming (steam reforming) is applied. CH 4 + 2H 2 O = CO 2 + 4H 2 (1) However, in the above reaction formula (1), the reaction rate and composition are actually determined by the equilibrium relationship of the following reaction formulas (2) and (3). . CH 4 + H 2 O = CO + 3H 2 (2) CO + H 2 O = CO 2 + H 2 (3) That is, the reaching equilibrium condition is determined by the operating pressure, temperature, and steam carbon ratio. Equation (2) is an endothermic reaction,
Since the equation (3) is an exothermic reaction, the higher the temperature, the (2)
Since the equation progresses, the reaction rate of methane improves, but on the contrary, if the temperature is high, the equation (3) is advantageous in the opposite direction, so that the CO concentration of the reformed gas increases. As an example, the process is configured such that the reformed gas temperature at the reformer outlet is 800 ° C.

【００１６】操作圧力については、（２）式を見てわか
るようにモル数が増加するので、圧力が高くなるほど反
応は進みにくくなる。改質反応だけで言えば、大気圧で
操作する方が好ましいが、今回のシステムのように改質
プロセスの後流に水素精製のＰＳＡであるとか、化学合
成プロセス等の加圧条件で操作するプロセスがつながる
場合には、システム全体の経済性を考えると改質圧力を
高圧系で操作することになることが多い。本実施の形態
では、一例として、１６．９３kg／cm2の改質ガス出口
圧力の設定を行う。As for the operating pressure, since the number of moles increases as can be seen from the equation (2), the reaction becomes more difficult to proceed as the pressure increases. Speaking of the reforming reaction alone, it is preferable to operate at atmospheric pressure, but like this system, PSA for hydrogen purification is used in the downstream of the reforming process, or it is operated under pressure conditions such as chemical synthesis process. When the processes are connected, it is often the case that the reforming pressure is operated by a high pressure system in consideration of the economy of the entire system. In the present embodiment, as an example, the reformed gas outlet pressure of 16.93 kg / cm 2 is set.

【００１７】この改質反応の副反応で、従来からあるト
ラブルの主要なものとして、カーボン析出反応の併発が
ある。 ２ＣＯ＝Ｃ＋ＣＯ2 …（４） ＣＨ4＝Ｃ＋２Ｈ2 …（５） こういったカーボン析出反応はスチームの添加量を増加
させることで回避できる。ただし、スチーム消費量は、
熱損失、使用水量の増大に直結するため、少ない方が経
済性は向上するので、実績ベースで安全操業可能な範囲
で設定される。このカーボン析出反応は、触媒の種類に
よって異なるが、工業的に実績のあるニッケル系触媒で
は、通例、スチームカーボン比（Ｈ2Ｏと原料ガス中の
Ｃのモル比）は３〜４前後で設定される。本実施の形態
では、一例として、実績を基に３．３で設定する。以上
が、天然ガスのスチームリフォーミングの反応原理と本
実施形態の概念設計の主要な設定条件との関係である。As a side reaction of this reforming reaction, a major problem that has existed in the past is the simultaneous occurrence of a carbon deposition reaction. 2CO = C + CO 2 (4) CH 4 = C + 2H 2 (5) Such a carbon deposition reaction can be avoided by increasing the addition amount of steam. However, steam consumption is
Since it is directly linked to heat loss and increase in the amount of water used, the smaller the amount, the better the economic efficiency. This carbon deposition reaction varies depending on the type of catalyst, but in a nickel-based catalyst that has an industrial track record, the steam carbon ratio (molar ratio of H 2 O and C in the raw material gas) is usually set to around 3 to 4. To be done. In the present embodiment, as an example, the value is set to 3.3 based on the actual result. The above is the relationship between the reaction principle of steam reforming of natural gas and the main setting conditions of the conceptual design of the present embodiment.

【００１８】次に、改質器の物質の流れを説明する。後
述のＣＯ2液化ユニットに設置されたエアフィン型の気
化・昇温器で大気温度となった天然ガスは、改質器４２
の加熱炉２６に設置される予熱器２８で加熱される。一
方の反応原料のスチームは、ボイラ給水を加熱炉２６に
設置された予熱器３０で予熱した後、改質ガスの余熱を
回収するスチーム発生器（廃熱ボイラ）３２でスチーム
を製造し、このスチームが天然ガスと混合される。３４
は純水製造設備、３６はボイラ用薬注設備、３８は脱気
器、４０は蒸気ドラムである。天然ガスとスチームの混
合ガスは、さらに加熱炉２６で予熱され、５００℃程度
に昇温して改質器４２の触媒層に供給される。４４はバ
ーナーである。この予熱温度５００℃という設定は、使
用する触媒にもよるが、ニッケル系の触媒の反応開始温
度が４００℃程度であるので、それ以上に昇温して供給
するためである。なお、触媒としては、ニッケル系触媒
（Ｎｉ／Ａｌ2Ｏ3、Ｎｉ／ＺｒＯ2等）の他に、ロジウ
ム系触媒（Ｒｈ／Ａｌ2Ｏ3、Ｒｈ／ＺｒＯ2等）、ルテ
ニウム系触媒（Ｒｕ／Ａｌ2Ｏ3、Ｒｕ／ＺｒＯ2等）な
どを用いることができる。Next, the flow of substances in the reformer will be described. The air fin type vaporizer / heater installed in the CO 2 liquefaction unit, which will be described later, brings the natural gas to atmospheric temperature to the reformer 42.
It is heated by a preheater 28 installed in the heating furnace 26 of FIG. The steam of one of the reaction raw materials, after preheating the boiler feed water with the preheater 30 installed in the heating furnace 26, produces steam with the steam generator (waste heat boiler) 32 that recovers the residual heat of the reformed gas. Steam is mixed with natural gas. 34
Is a pure water production facility, 36 is a boiler chemical injection facility, 38 is a deaerator, and 40 is a steam drum. The mixed gas of natural gas and steam is further preheated in the heating furnace 26, heated to about 500 ° C., and supplied to the catalyst layer of the reformer 42. 44 is a burner. The setting of the preheating temperature of 500 ° C. depends on the catalyst used, but since the reaction start temperature of the nickel-based catalyst is about 400 ° C., the temperature is raised more than that and supplied. As the catalyst, in addition to nickel-based catalysts (Ni / Al 2 O 3 , Ni / ZrO 2, etc.), rhodium-based catalysts (Rh / Al 2 O 3 , Rh / ZrO 2 etc.), ruthenium-based catalysts (Ru) are used. / Al 2 O 3 , Ru / ZrO 2, etc.) can be used.

【００１９】改質器４２の加熱炉は、後述のＰＳＡ（水
素精製設備４６）で水素を約７８％分離した後の未回収
水素、ＣＯ及び微量の未反応メタンを含むＰＳＡオフガ
スを主燃料とし、補助燃料として天然ガスを使用する。
加熱炉内の高温燃焼ガス温度分布を均一にして改質器に
熱供給するところがプロセスの重要な工夫点である。そ
の主要な特徴は、バーナー４４の取付位置（加熱炉の側
壁に付けたり、底部にバーナーを設置するなど）や輻射
加熱を主体とするバーナー構造などである。The heating furnace of the reformer 42 uses PSA off-gas containing unrecovered hydrogen, CO and a trace amount of unreacted methane as the main fuel after hydrogen is separated by about 78% in PSA (hydrogen purification equipment 46) described later. , Use natural gas as an auxiliary fuel.
An important point of the process is to make the temperature distribution of high temperature combustion gas in the heating furnace uniform and supply heat to the reformer. The main features are the mounting position of the burner 44 (attached to the side wall of the heating furnace or installing the burner at the bottom), the burner structure mainly including radiant heating, and the like.

【００２０】再度、プロセスフローの改質ガスの流れに
戻って説明する。改質器４２を出た改質ガスは、前述の
スチーム発生器（廃熱ボイラ）３２でスチーム発生の熱
源として利用され、自身は温度を下げて次の反応工程で
ある一酸化炭素変成器（ＣＯシフト反応器）４８に移
る。シフト反応は、改質反応のところで記載した反応式
と同じであるが、 ＣＯ＋Ｈ2Ｏ＝ＣＯ2＋Ｈ2 …（３） の反応により、ＣＯを水素に変成（シフト）すること
で、水素の収率を高めるために設定される。前述の通
り、発熱反応なので、低温であるほど平衡上は反応が有
利になるが、触媒の活性はある程度以上の温度を必要と
する。一般に、高温シフトと呼ばれるＦｅ系触媒を用い
る３５０℃程度の反応温度の反応器が用いられる。場合
によって、さらに水素収率を高める必要がある場合は、
もう一段低温にして、２００℃程度の反応温度でＣｕ系
触媒を用いた低温シフトを組み合わせることもある。本
実施の形態では、既存の実績に基づき、高温シフト１段
で構成している。The process gas reforming gas flow will be described again. The reformed gas discharged from the reformer 42 is used as a heat source for steam generation in the above-mentioned steam generator (waste heat boiler) 32, and the temperature of the reformed gas itself is lowered to form the carbon monoxide shift converter ( CO shift reactor) 48. The shift reaction is the same as the reaction formula described in the reforming reaction, but by converting (shifting) CO into hydrogen by the reaction of CO + H 2 O = CO 2 + H 2 (3) Set to increase the rate. As mentioned above, since the reaction is exothermic, the reaction becomes more advantageous in equilibrium at lower temperatures, but the activity of the catalyst requires a certain temperature or higher. Generally, a reactor having a reaction temperature of about 350 ° C. using an Fe-based catalyst called a high temperature shift is used. In some cases, if it is necessary to further increase the hydrogen yield,
There is also a case where the temperature is lowered to another step and a low temperature shift using a Cu-based catalyst is combined at a reaction temperature of about 200 ° C. In the present embodiment, one high temperature shift is used based on the existing results.

【００２１】水素精製ユニット ＣＯシフト反応器（高温シフト反応器）４８を出た改質
ガスは、スチーム発生のためのボイラ給水の予熱器５０
で熱回収した後、凝縮器５２と水冷の冷却器５４で改質
ガス中に含まれる過剰水分を飽和凝縮させる。これは、
後流のＰＳＡ吸着剤への負荷を低減するという目的があ
る。このように過剰な水分をドレンとして回収した後、
４０℃程度の常温付近のガス温度で、改質ガスは水素精
製設備４６、すなわち、ＰＳＡの吸着塔に供給される。
ＰＳＡはＰｒｅｓｓｕｒｅ Ｓｗｉｎｇ Ａｄｓｏｒｐ
ｔｉｏｎの略称であり、広く工業界で普及しており、今
や工業規模にとどまらず、少量の窒素発生のＰＳＡも普
及している。操作原理の基本は、吸着剤へのガス吸着容
量が高圧で多く、低圧で少ないという吸着容量の差を利
用したものである。つまり、複数の塔で構成し、ある塔
を加圧で吸着工程に置き、別の塔では減圧して吸着した
ガスを脱着させる。このサイクルを循環することによっ
て、連続プロセスとしてガスの分離が可能になるという
ものである。The reformed gas discharged from the hydrogen purifying unit CO shift reactor (high temperature shift reactor) 48 is a boiler feed water preheater 50 for generating steam.
After the heat is recovered by, the condenser 52 and the water-cooled cooler 54 saturate the excess water contained in the reformed gas. this is,
The purpose is to reduce the load on the downstream PSA adsorbent. After collecting excess water as drain like this,
The reformed gas is supplied to the hydrogen purification equipment 46, that is, the adsorption tower of the PSA at a gas temperature of about 40 ° C. near room temperature.
PSA is Pressure Swing Adsorb
It is an abbreviation of “ion” and is widely used in the industrial field. Now, PSA for generating a small amount of nitrogen is not only limited to the industrial scale. The operating principle is based on the fact that the gas adsorption capacity of the adsorbent is large at high pressure and small at low pressure. That is, it is composed of a plurality of columns, one column is placed under pressure in the adsorption step, and another column is decompressed to desorb the adsorbed gas. By circulating this cycle, it is possible to separate the gas as a continuous process.

【００２２】本実施の形態では、４塔式の水素精製用の
ＰＳＡを採用している。なお、基本原理的には吸着と脱
着の２塔でも構成できるが、昇圧、減圧時のガスをプロ
セス内で利用して、均圧、パージなどの中間工程を盛り
込んで水素純度向上、収率向上を図ったものが４塔式Ｐ
ＳＡであり、水素精製用としては最も一般的な形式であ
る。すなわち、図３に示すように、本実施形態の水素精
製設備４６は、吸着塔５６を４基設置したＰＳＡユニッ
トであり、精製水素は精製水素・中間タンク５８を経由
して回収され、ＰＳＡオフガス（二酸化炭素と未回収水
素）はＰＳＡオフガスタンク６０を経由して改質器のバ
ーナーに送られる。精製水素の一部は、脱着後の吸着塔
５６内の残留不純物（ＣＯ2）のパージ及び吸着圧まで
の昇圧のために、精製水素・中間タンク５８からリサイ
クルされる。In the present embodiment, a 4-column PSA for hydrogen purification is adopted. In principle, it can be configured with two columns, one for adsorption and the other for desorption, but by using the gas at the time of pressurization and depressurization in the process, intermediate steps such as pressure equalization and purging are included to improve hydrogen purity and yield. 4 tower type P
SA, which is the most common format for hydrogen purification. That is, as shown in FIG. 3, the hydrogen purification equipment 46 of the present embodiment is a PSA unit in which four adsorption towers 56 are installed, and the purified hydrogen is recovered via the purified hydrogen / intermediate tank 58 and PSA off-gas. (Carbon dioxide and unrecovered hydrogen) are sent to the burner of the reformer via the PSA off-gas tank 60. Part of the purified hydrogen is recycled from the purified hydrogen / intermediate tank 58 in order to purge residual impurities (CO 2 ) in the adsorption tower 56 after desorption and increase the pressure up to the adsorption pressure.

【００２３】上記のように、ＰＳＡで改質ガス中の水素
以外の成分は、オフガスとして除去され、前述の通り改
質器４２の加熱炉の主燃料として有効利用される。例え
ば、精製水素の回収率は７８％、純度は９９．９９９％
以上となる。本発明では、従来の水素製造法のＰＳＡを
用いたプロセスを基本とし、改質器４２の加熱炉２６の
酸化剤として純酸素を用いて高濃度ＣＯ2の燃焼排ガス
を製造する。このような純酸素燃焼の効果として、物質
収支を検討してみると、燃焼排ガス中の窒素などの持ち
去りによる熱損失が少なくなるので助燃用の天然ガスが
不要となって、ＰＳＡのオフガスのみで加熱炉の熱源が
まかなえる結果となる。また、燃焼排ガス中の二酸化炭
素は、除湿後は約９６％の高濃度になるので、後述のＣ
Ｏ2液化ユニットで加圧・冷却することにより比較的用
に液化炭酸ガスが製造できるシステムを構成できる。As described above, the PSA removes the components other than hydrogen in the reformed gas as off-gas, and as described above, it is effectively used as the main fuel of the heating furnace of the reformer 42. For example, the recovery rate of purified hydrogen is 78%, and the purity is 99.999%.
That is all. In the present invention, a process using PSA of the conventional hydrogen production method is basically used, and pure oxygen is used as an oxidant of the heating furnace 26 of the reformer 42 to produce a combustion exhaust gas having a high concentration of CO 2 . As an effect of such pure oxyfuel combustion, when examining the mass balance, heat loss due to removal of nitrogen etc. in the combustion exhaust gas is reduced, so natural gas for supporting combustion becomes unnecessary, and only PSA off gas is required. The result is that the heat source of the heating furnace can be covered. Further, the carbon dioxide in the combustion exhaust gas has a high concentration of about 96% after dehumidification.
By pressurizing and cooling with the O 2 liquefaction unit, it is possible to construct a system in which liquefied carbon dioxide gas can be relatively produced.

【００２４】水素貯蔵・出荷ユニット 水素ガスの貯蔵工程を説明する。ガス貯蔵の場合と水素
を液化して貯蔵する場合の２ケースについて説明する。 ａ．高圧水素ガス貯蔵、出荷システム 図２では一般的な高圧水素ガスの貯蔵、出荷システム例
を示す。水素精製設備４６で精製された水素ガスは水素
ガスホルダー６２に貯蔵し、圧縮機６４で昇圧し高圧水
素ガストレーラに充填出荷される。６６は充填設備であ
る。Hydrogen Storage / Shipping Unit The hydrogen gas storage process will be described. Two cases will be described, one in the case of gas storage and the other in the case of liquefying and storing hydrogen. a. High-Pressure Hydrogen Gas Storage / Shipping System FIG. 2 shows an example of a general high-pressure hydrogen gas storage / shipping system. The hydrogen gas purified by the hydrogen purification equipment 46 is stored in the hydrogen gas holder 62, the pressure is increased by the compressor 64, and the high pressure hydrogen gas trailer is filled and shipped. 66 is a filling facility.

【００２５】ｂ．水素液化、貯蔵、出荷システム 水素を液化するためには水素ガスを液化温度まで冷却す
る設備が必要となる。水素液化プロセスには各種の方式
があるが、一般的な水素液化方法は以下のとおりであ
る。精製された水素ガスを圧縮機で昇圧し、アンモニア
冷凍機等による予冷段にて約−４０℃まで冷却され、さ
らに液体窒素により約−１９６℃まで冷却される。その
後、膨張タービンと断熱膨張弁による冷却系により水素
が液化する温度まで冷却され液体水素が生成される。水
素液化機の液化能力が大きくなると、使用する液体窒素
量も多くなり、窒素再液化機が併設されるのが通例であ
る。B. Hydrogen liquefaction, storage, and shipping system In order to liquefy hydrogen, equipment for cooling hydrogen gas to the liquefaction temperature is required. There are various types of hydrogen liquefaction processes, and the general hydrogen liquefaction method is as follows. The purified hydrogen gas is pressurized by a compressor, cooled to about -40 ° C in a precooling stage such as an ammonia refrigerator, and further cooled to about -196 ° C with liquid nitrogen. Thereafter, the cooling system including the expansion turbine and the adiabatic expansion valve cools the hydrogen to a temperature at which hydrogen is liquefied, and liquid hydrogen is generated. When the liquefaction capacity of the hydrogen liquefaction machine increases, the amount of liquid nitrogen used also increases, and it is customary to install a nitrogen reliquefaction machine side by side.

【００２６】これに対して、本実施形態の採用例として
水素クロードサイクル方式の水素液化プロセスでの実施
例を図２に示す。精製後の原料水素ガスは常温にて水素
液化機６８に導入された後、圧縮機７０で昇圧され、つ
いで、ＬＮＧ冷熱を利用して予冷却器７２、７４により
原料水素を予冷するシステムであり、アンモニア冷凍機
による予冷段をＬＮＧ冷熱にて予冷する予冷却器にする
ことにより、ＬＮＧ冷熱の有効利用を図るものである。
さらに、隣接する空気深冷分離施設（図示略）より安価
な液体窒素を導入できることから、この液体窒素を利用
して冷却器７６にて水素を冷却することができ、窒素再
液化機は設置する必要がない。冷却した水素は、膨張タ
ービン７８と断熱膨張弁による冷却系により水素が液化
する温度まで冷却される。これらの改良法によって、水
素液化動力を従来法に比べて約４０％低減することがで
きる。On the other hand, FIG. 2 shows an example of a hydrogen liquefaction process of the hydrogen Claude cycle system as an example of adoption of this embodiment. The purified raw material hydrogen gas is introduced into the hydrogen liquefier 68 at room temperature, then pressurized by the compressor 70, and then the raw hydrogen is precooled by the precoolers 72 and 74 using LNG cold heat. By using a precooler for precooling the LNG cold heat as the precooling stage of the ammonia refrigerator, the LNG cold heat is effectively used.
Furthermore, since cheaper liquid nitrogen can be introduced from the adjacent air-cooling separation facility (not shown), hydrogen can be cooled by the cooler 76 using this liquid nitrogen, and a nitrogen reliquefaction machine is installed. No need. The cooled hydrogen is cooled to a temperature at which the hydrogen is liquefied by the cooling system including the expansion turbine 78 and the adiabatic expansion valve. With these improved methods, the hydrogen liquefaction power can be reduced by about 40% as compared with the conventional method.

【００２７】なお、水素のオルソ・パラ変換は熱交換器
に触媒を充填した連続方式が採用されている。さらに、
不純物対策のため原料水素系とリサイクル系には切替式
の低温吸着器８０が設けられている。８２はリサイクル
圧縮機、８４はボイルオフガス圧縮機である。液化され
た水素は、液体水素貯槽に貯蔵され、液体水素コンテナ
または液体水素タンクローリー等に充填し出荷される。For the ortho-para conversion of hydrogen, a continuous system in which a heat exchanger is filled with a catalyst is adopted. further,
As a countermeasure against impurities, a low temperature adsorber 80 of a switching type is provided in the raw material hydrogen system and the recycle system. Reference numeral 82 is a recycle compressor, and 84 is a boil-off gas compressor. The liquefied hydrogen is stored in a liquid hydrogen storage tank, filled in a liquid hydrogen container or a liquid hydrogen tank truck, and shipped.

【００２８】二酸化炭素液化ユニット 本実施の形態では、改質器４２からの燃焼排ガスから二
酸化炭素を分離回収することを想定しており、上述した
ように純酸素をオフガス燃焼の酸化剤として使用するこ
とにより、二酸化炭素リッチな原料ガスとなる。図２の
二酸化炭素液化ユニットのプロセスフローに示すよう
に、改質器４２からの燃焼排ガスは、冷却器（図２で
は、水冷の冷却器８６及び低温天然ガスによる冷却器８
８）、除湿塔９０、圧縮機９２を経由して、一例とし
て、次のような組成と温度・圧力条件にされてＣＯ2液
化器９４に導入される。なお、ガス温度は１５℃であ
り、ガスの全圧は７．１４kg／cm2である。 ＣＯ2ガス １０２．０kmol／h（４４９０kg／h）分圧
６．８３kg／cm2 Ｏ2ガス ４．２９kmol／h（１３７kg／h）分圧０．
２９kg／cm2 Ｎ2ガス ０．０４kmol／h（０．９８kg／h）分圧
０．００２kg／cm2 なお、除湿塔９０には、水分を選択的に吸着する吸着剤
が充填されており、例えば、合成ゼオライト３Ａ型など
が用いられる。Carbon dioxide liquefaction unit In the present embodiment, it is assumed that carbon dioxide is separated and recovered from the combustion exhaust gas from the reformer 42, and pure oxygen is used as an oxidant for off-gas combustion as described above. As a result, carbon dioxide-rich raw material gas is obtained. As shown in the process flow of the carbon dioxide liquefaction unit in FIG. 2, the combustion exhaust gas from the reformer 42 is cooled by a cooler (in FIG. 2, a water-cooled cooler 86 and a cooler 8 using low-temperature natural gas).
8), via the dehumidifying tower 90 and the compressor 92, as an example, the composition, temperature, and pressure conditions as described below are introduced into the CO 2 liquefier 94. The gas temperature is 15 ° C. and the total gas pressure is 7.14 kg / cm 2 . CO 2 gas 102.0 kmol / h (4490 kg / h) partial pressure 6.83 kg / cm 2 O 2 gas 4.29 kmol / h (137 kg / h) partial pressure 0.
29 kg / cm 2 N 2 gas 0.04 kmol / h (0.98 kg / h) partial pressure 0.002 kg / cm 2 The dehumidifying tower 90 is filled with an adsorbent that selectively adsorbs water, For example, synthetic zeolite 3A type is used.

【００２９】この燃焼排ガス中のＣＯ2ガス分圧はＣＯ2
の３重点（気・液・固体共存温度／圧力点、５．２８kg
／cm2，−５６．６℃）の圧力よりも高いので、このま
まＣＯ2液化器９４内でのＣＯ2液化運転が可能である。
従来のＣＯ2液化方式はＬＮＧ冷熱によって一旦、中間
熱媒体を液化し、さらに液化中間熱媒体でＣＯ2を液化
する方式であるのに対して、本発明ではＬＮＧ冷熱の直
接利用によるＣＯ2液化方式である。ガス流はＣＯ2液化
器９４内入口側で予冷されて液化域に至る。ＣＯ2液化
器９４において６．８３kg／cm2のＣＯ2ガス分圧に対応
する液化温度は−５１．０℃であり、この温度でＣＯ2
液化が始まる。このような方法によって、二酸化炭素が
ドライアイス化されることなく、ほぼ全量液化が可能と
なる。液化ＣＯ2は液化ＣＯ2タンク９６に貯蔵され、必
要に応じて搬出される。The partial pressure of CO 2 gas in this combustion exhaust gas is CO 2
Of three points (gas / liquid / solid coexisting temperature / pressure point, 5.28 kg
/ Cm 2, is higher than the pressure of -56.6 ° C.), it is possible to CO 2 liquefaction operation in this state CO 2 liquefier 94..
In the conventional CO 2 liquefaction method, the intermediate heat medium is once liquefied by LNG cold heat, and then CO 2 is liquefied by the liquefied intermediate heat medium, whereas in the present invention, CO 2 liquefaction is made by directly utilizing LNG cold heat. It is a method. The gas flow is precooled at the inlet side of the CO 2 liquefier 94 and reaches the liquefaction region. In the CO 2 liquefier 94, the liquefaction temperature corresponding to a CO 2 gas partial pressure of 6.83 kg / cm 2 is −51.0 ° C., and at this temperature CO 2
Liquefaction begins. By such a method, almost all of the carbon dioxide can be liquefied without being converted to dry ice. The liquefied CO 2 is stored in the liquefied CO 2 tank 96 and is carried out if necessary.

【００３０】上記の例では、液化すべきＣＯ2量は４４
９０kg／hであり、これを全量液化する冷却熱負荷は５
３４．３kW（４５９．３Mcal／h）であり、所要のＬＮ
Ｇ量は２４３０kg／hとなる。既存のＬＮＧ利用液化炭
酸ガスプラントでは、１トンの液化ＣＯ2を得るために
約１．１トンのＬＮＧを使用しているが、本発明の方式
では１トンの液化ＣＯ2に対するＬＮＧ量は０．５４ト
ンであり、熱効率の良い液化方式といえる。分離回収さ
れた液化ＣＯ2は、液化炭酸ガスローリーで外販出荷さ
れるものとし、上記の例の場合では、例えば、液化炭酸
ガス貯蔵タンク３５０トンを２基、ローリー出荷設備を
２式設置する。In the above example, the amount of CO 2 to be liquefied is 44
90 kg / h, the cooling heat load for liquefying all of this is 5
34.3kW (459.3Mcal / h), required LN
The amount of G is 2430 kg / h. In the existing LNG utilizing liquefied carbon dioxide plant, about 1.1 tons of LNG is used to obtain 1 ton of liquefied CO 2 , but in the method of the present invention, the amount of LNG for 1 ton of liquefied CO 2 is 0. Since it is 0.54 tons, it can be said that it is a liquefaction method with good thermal efficiency. The separated and collected liquefied CO 2 is to be sold for sale outside as a liquefied carbon dioxide gas truck. In the case of the above example, for example, two liquefied carbon dioxide gas storage tanks (350 tons) and two sets of truck transportation equipment are installed.

【００３１】[0031]

【発明の効果】本発明は上記のように構成されているの
で、つぎのような効果を奏する。 （１） 純酸素（又は高濃度の酸素）をオフガス燃焼の
酸化剤として使用し、天然ガスを酸素燃焼加熱により改
質して水素を製造するシステムとすることにより、高濃
度の二酸化炭素を含んだ燃焼排ガスが得られるので、加
圧してＬＮＧ冷熱で冷却すれば容易に液化ＣＯ2として
回収でき、貯蔵や販売のための輸送など取り扱いが容易
になる。 （２） 液化天然ガス（ＬＮＧ）を原料として水蒸気改
質により水素を製造するシステムにおいて、ＬＮＧ冷熱
を利用した深冷空気分離で製造した純酸素を天然ガスの
改質プロセスで有効利用するとともに、深冷空気分離で
得られた液体窒素を精製水素の液化に利用することによ
り、２次的なＬＮＧ冷熱の有効利用の需要プロセスが創
出できる。 （３） ＬＮＧを原料として水蒸気改質により水素を製
造し、ＰＳＡ吸着分離法などで水素を分離精製し、分離
された可燃物を含むオフガスを主燃料として改質器の加
熱炉に用いる方法において、純酸素をオフガス燃焼の酸
化剤として使用することで、高濃度の二酸化炭素を含有
する燃焼排ガスが得られることから、この燃焼排ガスに
含まれる水分を除去した後、ＣＯ2液化可能な圧力に昇
圧し、ＬＮＧ冷熱を用いて冷却することにより、燃焼排
ガスから液化ＣＯ2を容易に分離回収することができ
る。 （４） 純酸素をオフガス燃焼の酸化剤として使用する
ことにより、空気で燃焼させる場合と比較して、燃焼排
ガス中の窒素などの持ち去りによる熱損失が少なくなる
ので、助燃用の天然ガスが不要となり、ＰＳＡのオフガ
スのみで改質器の加熱炉の熱源がまかなえる。 （５） 改質器で発生する燃焼排ガスから二酸化炭素を
液体状態で回収するに際し、水分除去のための前処理と
して、水分を選択的に吸着する合成ゼオライト３Ａ型を
使用して燃焼排ガス中に含まれる水分を除去する場合
は、燃焼排ガスが効率よく除湿され、ＬＮＧ冷熱の直接
利用によるＣＯ2の液化が容易になる。Since the present invention is configured as described above, it has the following effects. (1) Pure oxygen (or high-concentration oxygen) is used as an oxidant for off-gas combustion, and natural gas is reformed by oxygen combustion heating to produce hydrogen, thereby containing high-concentration carbon dioxide. Since flue gas is obtained, it can be easily recovered as liquefied CO 2 by pressurizing and cooling with LNG cold heat, and handling such as storage and transportation for sale becomes easy. (2) In a system for producing hydrogen by steam reforming using liquefied natural gas (LNG) as a raw material, pure oxygen produced by deep-air separation using LNG cold heat is effectively used in a natural gas reforming process, and By utilizing the liquid nitrogen obtained by the cryogenic air separation for the liquefaction of purified hydrogen, a demand process for effective utilization of secondary LNG cold heat can be created. (3) In a method in which hydrogen is produced by steam reforming using LNG as a raw material, hydrogen is separated and purified by a PSA adsorption separation method, etc., and offgas containing the separated combustible material is used as a main fuel in a heating furnace of a reformer. By using pure oxygen as an oxidant for off-gas combustion, a combustion exhaust gas containing a high concentration of carbon dioxide can be obtained. Therefore, after removing the water contained in this combustion exhaust gas, the CO 2 liquefaction pressure can be adjusted. By increasing the pressure and cooling with LNG cold heat, liquefied CO 2 can be easily separated and recovered from the combustion exhaust gas. (4) By using pure oxygen as an oxidant for off-gas combustion, heat loss due to removal of nitrogen and the like in combustion exhaust gas is reduced as compared with the case of combustion with air, so that natural gas for combustion support is used. It becomes unnecessary, and the heat source of the heating furnace of the reformer can be covered only by the offgas of PSA. (5) When recovering carbon dioxide in a liquid state from the combustion exhaust gas generated in the reformer, synthetic zeolite 3A that selectively adsorbs water is used in the combustion exhaust gas as a pretreatment for removing water. When removing the contained water, the combustion exhaust gas is efficiently dehumidified, and the liquefaction of CO 2 by the direct use of LNG cold heat is facilitated.

【図面の簡単な説明】[Brief description of drawings]

【図１】本発明の実施の第１形態による液化ＣＯ2回収
を伴う水素製造方法を実施する装置の全体システムを示
す概念構成説明図である。FIG. 1 is a conceptual configuration explanatory diagram showing an overall system of an apparatus for carrying out a method for producing hydrogen with liquefied CO 2 recovery according to a first embodiment of the present invention.

【図２】本発明の実施の第２形態による液化ＣＯ2回収
を伴う水素製造方法を実施する装置を示す系統的概略構
成説明図である。FIG. 2 is a systematic schematic configuration explanatory diagram showing an apparatus for carrying out a method for producing hydrogen with liquefied CO 2 recovery according to a second embodiment of the present invention.

【図３】本発明の実施の第２形態における水素精製設備
（ＰＳＡユニット）の詳細を示す構成説明図である。FIG. 3 is a configuration explanatory view showing details of a hydrogen purification facility (PSA unit) according to a second embodiment of the present invention.

【符号の説明】[Explanation of symbols]

１０ 深冷空気分離設備 １２、４２ 天然ガス改質器 １４、４８ ＣＯシフト反応器（一酸化炭素変成器） １６、４６ 水素精製設備 １８ ＣＯ2液化設備 ２０ 除湿器 ２２、７２、７４ 予冷却器 ２４、７６ 冷却器 ２６ 加熱炉 ２８、３０、５０ 予熱器 ３２ スチーム発生器（廃熱ボイラ） ３４ 純水製造設備 ３６ ボイラ用薬注設備 ３８ 脱気器 ４０ 蒸気ドラム ４４ バーナ ５２ 凝縮器 ５４、８６ 水冷の冷却器 ５６ ＰＳＡの吸着塔 ５８ 精製水素・中間タンク ６０ ＰＳＡオフガスタンク ６２ 水素ガスホルダー ６４、７０、９２ 圧縮機 ６６ 充填設備 ６８ 水素液化機 ７８ 膨張タービン ８０ 低温吸着器 ８２ リサイクル圧縮機 ８４ ボイルオフガス圧縮機 ８８ 低温天然ガスによる冷却器 ９０ 除湿塔 ９４ ＣＯ2液化器 ９６ 液化ＣＯ2タンク10 Chilled air separation facility 12, 42 Natural gas reformer 14, 48 CO shift reactor (carbon monoxide shifter) 16, 46 Hydrogen purification facility 18 CO 2 liquefaction facility 20 Dehumidifier 22, 72, 74 Precooler 24, 76 Cooler 26 Heating furnaces 28, 30, 50 Preheater 32 Steam generator (waste heat boiler) 34 Pure water production equipment 36 Chemical injection equipment for boiler 38 Deaerator 40 Steam drum 44 Burner 52 Condenser 54, 86 Water-cooled cooler 56 PSA adsorption tower 58 Purified hydrogen / intermediate tank 60 PSA off-gas tank 62 Hydrogen gas holders 64, 70, 92 Compressor 66 Filling equipment 68 Hydrogen liquefier 78 Expansion turbine 80 Low-temperature adsorber 82 Recycle compressor 84 Boil-off Gas compressor 88 Low-temperature natural gas cooler 90 Dehumidification tower 94 CO 2 liquefier 96 Liquefied CO 2 tank

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｆ２５Ｊ 3/04 Ｆ２５Ｊ 3/04 Ｂ １０１ １０１ (72)発明者 中西 誠一 神戸市中央区東川崎町３丁目１番１号 川 崎重工業株式会社神戸工場内 (72)発明者 川越 英司 千葉県野田市二ツ塚118番地 川崎重工業 株式会社野田工場内 (72)発明者 原口 憲次郎 千葉県野田市二ツ塚118番地 川崎重工業 株式会社野田工場内 (72)発明者 神谷 祥二 兵庫県明石市川崎町１番１号 川崎重工業 株式会社明石工場内 (72)発明者 小川 賢 大阪市北区中之島３丁目３番22号 関西電 力株式会社内 (72)発明者 本田 宏 大阪市北区中之島３丁目３番22号 関西電 力株式会社内 Ｆターム(参考） 4D047 AA02 AA08 AB01 AB02 CA04 CA07 DA03 4D052 AA00 CD00 HA03 4G040 EA03 EA06 EB31 EB44 4G046 JB08 JB21 4G066 AA61B CA43 DA02 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) F25J 3/04 F25J 3/04 B 101 101 (72) Inventor Seiichi Nakanishi 3-chome, Higashikawasaki-cho, Chuo-ku, Kobe-shi No. 1 Kawasaki Heavy Industries, Ltd. Kobe Factory (72) Inventor Eiji Kawagoe 118 Futtsuka, Noda, Chiba Prefecture Kawasaki Heavy Industries Ltd. Noda Factory (72) Inventor Kenjiro Haraguchi 118, Futtsuka, Noda, Chiba Kawasaki Heavy Industries Ltd. Company Noda Factory (72) Inventor Shoji Kamiya 1-1 Kawasaki-cho Akashi-shi, Hyogo Prefecture Kawasaki Heavy Industries Ltd. Akashi Factory (72) Inventor Ken Ogawa 3-3-22 Nakanoshima, Kita-ku, Osaka Kansai Electric Power Co., Inc. In-house (72) Inventor Hiroshi Honda 3-22-2 Nakanoshima, Kita-ku, Osaka Kansai Electric Power Co., Inc. F-term (reference) 4D047 AA02 A A08 AB01 AB02 CA04 CA07 DA03 4D052 AA00 CD00 HA03 4G040 EA03 EA06 EB31 EB44 4G046 JB08 JB21 4G066 AA61B CA43 DA02

Claims (5)

【特許請求の範囲】[Claims] 【請求項１】 天然ガスを水蒸気改質して水素に富む改
質ガスとし、この改質ガスから水素を分離精製し、水素
の精製工程で分離された可燃物を含むオフガスを主燃料
として改質工程での燃焼加熱に用いる水素製造方法にお
いて、改質工程でのオフガス燃焼のための酸化剤として
純酸素又は高濃度の酸素を導入し、この燃焼で発生する
燃焼排ガス中の炭酸ガスを高濃度にして、燃焼排ガスか
ら炭酸ガスを容易に液体状態で分離・回収することを特
徴とする液化ＣＯ2回収を伴う水素製造方法。1. A natural gas is steam-reformed into a hydrogen-rich reformed gas, hydrogen is separated and refined from the reformed gas, and an off-gas containing a combustible substance separated in the hydrogen refining step is used as a main fuel. In the hydrogen production method used for combustion heating in the quality process, pure oxygen or high-concentration oxygen is introduced as an oxidant for off-gas combustion in the reforming process, and the carbon dioxide gas in the combustion exhaust gas generated in this combustion is increased. A method for producing hydrogen with liquefied CO 2 recovery, wherein carbon dioxide gas is easily separated and recovered in a liquid state from a combustion exhaust gas in a concentration. 【請求項２】 天然ガスの供給形態が液化天然ガスであ
り、その液化冷熱を利用した深冷空気分離により純酸素
又は高濃度の酸素を製造し、この酸素を改質工程でのオ
フガス燃焼のための酸化剤として使用し、深冷空気分離
で得られた液化窒素を精製した水素の液化に利用する請
求項１記載の液化ＣＯ2回収を伴う水素製造方法。2. The supply form of natural gas is liquefied natural gas, and pure oxygen or high-concentration oxygen is produced by cryogenic air separation using the liquefied cold heat, and this oxygen is used for off-gas combustion in a reforming process. The method for producing hydrogen with liquefied CO 2 recovery according to claim 1, wherein the liquefied nitrogen obtained by the cryogenic air separation is used for the liquefaction of purified hydrogen. 【請求項３】 天然ガスの供給形態が液化天然ガスであ
り、その液化冷熱を有効利用して、オフガス燃焼で発生
する燃焼排ガスから炭酸ガスを液体状態で分離・回収す
る請求項１又は２記載の液化ＣＯ2回収を伴う水素製造
方法。3. A method of supplying natural gas in the form of liquefied natural gas, and by effectively utilizing the liquefied cold heat of the liquefied natural gas, carbon dioxide is separated and recovered in a liquid state from combustion exhaust gas generated by off-gas combustion. Method for producing hydrogen with recovery of liquefied CO 2 from 【請求項４】 高濃度の炭酸ガスを含んだ燃焼排ガスか
ら液化ＣＯ2を分離・回収するに際し、前処理として燃
焼排ガス中に含まれる水分を除去した後、炭酸ガスの液
化が可能な圧力に昇圧し、液化天然ガスの冷熱を用いて
冷却することにより液化ＣＯ2を得る請求項３記載の液
化ＣＯ2回収を伴う水素製造方法。4. When separating and recovering liquefied CO 2 from a combustion exhaust gas containing a high concentration of carbon dioxide gas, after removing water contained in the combustion exhaust gas as a pretreatment, the pressure is adjusted to a liquefaction of carbon dioxide gas. boosted, hydrogen production methods involving liquefied CO 2 recovery according to claim 3, wherein obtaining a liquefied CO 2 by cooling with cold energy of the liquefied natural gas. 【請求項５】 水分除去のための前処理として、水分を
選択的に吸着する合成ゼオライト３Ａ型を用いて燃焼排
ガス中に含まれる水分を除去する請求項４記載の液化Ｃ
Ｏ2回収を伴う水素製造方法。5. The liquefied C according to claim 4, wherein as a pretreatment for removing water, the water contained in the combustion exhaust gas is removed using a synthetic zeolite 3A type that selectively adsorbs water.
Hydrogen production method with O 2 recovery.
JP2001268396A 2001-09-05 2001-09-05 Method and apparatus for producing hydrogen with liquefied CO2 recovery Expired - Lifetime JP3670229B2 (en)

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