JP3035038B2 - Hydrogen production method - Google Patents
Hydrogen production methodInfo
- Publication number
- JP3035038B2 JP3035038B2 JP3309265A JP30926591A JP3035038B2 JP 3035038 B2 JP3035038 B2 JP 3035038B2 JP 3309265 A JP3309265 A JP 3309265A JP 30926591 A JP30926591 A JP 30926591A JP 3035038 B2 JP3035038 B2 JP 3035038B2
- Authority
- JP
- Japan
- Prior art keywords
- gas
- hydrogen
- reformer
- combustion
- raw material
- 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.)
- Expired - Lifetime
Links
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 51
- 239000001257 hydrogen Substances 0.000 title claims description 51
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 40
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000007789 gas Substances 0.000 claims description 68
- 238000002485 combustion reaction Methods 0.000 claims description 27
- 239000011261 inert gas Substances 0.000 claims description 25
- 239000002994 raw material Substances 0.000 claims description 22
- 150000002431 hydrogen Chemical class 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 8
- 238000002407 reforming Methods 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000000567 combustion gas Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 4
- 238000000629 steam reforming Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 239000000498 cooling water Substances 0.000 description 10
- 239000000446 fuel Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910001252 Pd alloy Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- -1 steam Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0405—Purification by membrane separation
- C01B2203/041—In-situ membrane purification during hydrogen production
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Hydrogen, Water And Hydrids (AREA)
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【産業上の利用分野】本発明は水素製造方法に関し、特
に水素分離型リフォーマを用いて水素を製造する方法に
関する。The present invention relates to a method for producing hydrogen, and more particularly to a method for producing hydrogen using a hydrogen separation type reformer.
【０００２】[0002]
【従来の技術】水素分離型リフォーマを用いた水素製造
装置ではメタンやメタノール等の炭化水素や含酸素炭化
水素からなる原料ガスを、水蒸気改質反応とＣＯシフト
反応によって主に水素と二酸化炭素に分解し、発生した
水素をリフォーマに内蔵された水素分離膜を通して選択
的に分離するようにしている。水素分離は該分離膜の透
過側に不活性ガスを流すか、あるいは減圧にすることに
より実施されている。該水素分離膜として、例えばパラ
ジウム合金からなるものが利用される。2. Description of the Related Art In a hydrogen production apparatus using a hydrogen separation type reformer, a raw material gas composed of a hydrocarbon such as methane or methanol or an oxygen-containing hydrocarbon is mainly converted into hydrogen and carbon dioxide by a steam reforming reaction and a CO shift reaction. The hydrogen generated by the decomposition is selectively separated through a hydrogen separation membrane built in the reformer. Hydrogen separation is performed by flowing an inert gas to the permeate side of the separation membrane or reducing the pressure. As the hydrogen separation membrane, for example, a membrane made of a palladium alloy is used.
【０００３】従来例を図３を用いて更に詳しく説明す
る。１は水素分離型リフォーマであり、改質触媒層３内
に水素分離膜４を有する。例えばメタン等の炭化水素か
らなる原料ガス８はガス中のイオウ分を脱硫器３６で除
去後、脱硫原料ガス９は該リフォーマ１の燃焼器７での
燃焼用原料ガス１０と前記触媒層３へ供給する原料ガス
１１とに分割後、スチーム２５と混合し混合ガス１２と
する。該混合ガス１２を熱交換器１８で反応温度まで加
熱して高温反応ガス１３とし、前記触媒層３に導入す
る。触媒層３では下記反応で原料ガス８が水素、一酸化
炭素及び二酸化炭素に分解される。 Ｃn Ｈm ＋ nＨ2 Ｏ ＝ nＣＯ ＋ (n+m/2)Ｈ2 （１） Ｃn Ｈm ＋ 2nＨ2 Ｏ ＝ nＣＯ2 ＋(2n+m/2)Ｈ2 （２） Ｃn Ｈm ＋ nＣＯ2 ＝ 2nＣＯ ＋ m/2Ｈ2 （３）A conventional example will be described in more detail with reference to FIG. Reference numeral 1 denotes a hydrogen separation type reformer having a hydrogen separation film 4 in the reforming catalyst layer 3. For example, the raw material gas 8 composed of a hydrocarbon such as methane removes the sulfur content in the gas by a desulfurizer 36, and the desulfurized raw material gas 9 is transferred to the raw material gas 10 for combustion in the combustor 7 of the reformer 1 and to the catalyst layer 3. After being divided into the raw material gas 11 to be supplied, it is mixed with the steam 25 to form a mixed gas 12. The mixed gas 12 is heated to a reaction temperature by a heat exchanger 18 to form a high-temperature reaction gas 13 and introduced into the catalyst layer 3. In the catalyst layer 3, the source gas 8 is decomposed into hydrogen, carbon monoxide and carbon dioxide by the following reaction. Cn Hm + nH 2 O = nCO + (n + m / 2) H 2 (1) Cn Hm + 2nH 2 O = nCO 2 + (2n + m / 2) H 2 (2) Cn Hm + nCO 2 = 2nCO + M / 2H 2 (3)
【０００４】これら分解ガスのうち水素だけが例えばパ
ラジウム合金からなる水素分離膜４を通して透過部５に
分離される。主に二酸化炭素からなる未反応ガス１４は
熱交換器１５において冷却水３５によって冷却後低温未
反応ガス６となり、前記燃料用原料ガス１０と混合後、
ストリーム１６としてリフォーマ１の燃焼器７に導入さ
れ燃焼用の燃料にされる。燃焼器７からの燃焼ガスは燃
焼側２を通過し改質触媒層３へ反応熱を供給後、燃焼排
ガス１７としてリフォーマ１から排出される。燃焼排ガ
ス１７は熱交換器１９で冷却されストリーム２０となり
ベントへ送られる。[0004] Of these decomposition gases, only hydrogen is separated into a permeation section 5 through a hydrogen separation membrane 4 made of, for example, a palladium alloy. The unreacted gas 14 mainly composed of carbon dioxide becomes low-temperature unreacted gas 6 after being cooled by the cooling water 35 in the heat exchanger 15, and after being mixed with the fuel raw material gas 10,
The stream 16 is introduced into the combustor 7 of the reformer 1 and is used as fuel for combustion. The combustion gas from the combustor 7 passes through the combustion side 2 and supplies reaction heat to the reforming catalyst layer 3, and then is discharged from the reformer 1 as combustion exhaust gas 17. The flue gas 17 is cooled by the heat exchanger 19 to become a stream 20 and sent to the vent.
【０００５】透過部５には不活性ガス２４が熱交換器２
６で加熱後、高温不活性ガス２７として供給される。リ
フォーマで分離された水素は該不活性ガス２７によって
払い出される。水素ガスと不活性ガスとの混合ガス２８
は熱交換器２９において冷却水３４によって冷却され水
素ガスと不活性ガスの混合ガス３２として取り出され
る。In the permeation section 5, an inert gas 24 is supplied with heat exchanger 2.
After heating at 6, it is supplied as a high temperature inert gas 27. Hydrogen separated by the reformer is discharged by the inert gas 27. Mixed gas 28 of hydrogen gas and inert gas
Is cooled by a cooling water 34 in a heat exchanger 29 and is taken out as a mixed gas 32 of a hydrogen gas and an inert gas.
【０００６】燃焼用の空気２１は空気予熱器２３で加熱
後、高温空気２２となり燃焼器７へ送られる。[0006] After the combustion air 21 is heated by the air preheater 23, it becomes high-temperature air 22 and is sent to the combustor 7.
【０００７】このように従来の装置では原料ガス、不活
性ガス及び燃焼用空気を独立の熱交換器かあるいは水素
製造装置内の適当な温度レベルにあるストリームによっ
て加熱していた。また、残ガスや分離水素ガスの冷却に
主に冷却水を利用していた。As described above, in the conventional apparatus, the raw material gas, the inert gas and the combustion air are heated by an independent heat exchanger or a stream at an appropriate temperature level in the hydrogen production apparatus. In addition, cooling water is mainly used for cooling the residual gas and the separated hydrogen gas.
【０００８】[0008]
（１）水素製造装置への供給ガス、すなわち、原料ガ
ス、スチーム、不活性ガス及び燃焼用空気の予熱用に独
立した熱交換器を用いていたために装置の熱効率が悪く
必要以上の原料ガスを燃焼させる必要があった。 （２）リフォーマから流出する高温のストリームによっ
て前記供給ガスを加熱する場合でも温度レベルから考え
た効率的な熱交換がなされていないために熱効率が悪い
例が多く、また、場合によっては分離水素のストリーム
を燃焼用空気で冷却するなど安全上問題となることもあ
った。 （３）リフォーマから流出する高温のストリームを主に
水で冷却する場合には必要水量が多くなり経済的でなか
った。(1) The supply gas to the hydrogen production apparatus, that is, the raw material gas, steam, inert gas, and the use of an independent heat exchanger for preheating the combustion air, resulting in poor thermal efficiency of the apparatus and unnecessary raw material gas. It needed to be burned. (2) Even when the supply gas is heated by the high-temperature stream flowing out of the reformer, there are many cases where heat efficiency is poor because efficient heat exchange is not performed in consideration of the temperature level. There were also safety issues such as cooling the stream with combustion air. (3) When the high-temperature stream flowing out of the reformer is mainly cooled by water, the required amount of water is increased, which is not economical.
【０００９】[0009]
【課題を解決するための手段】本発明は改質触媒を充填
した反応管内に水素分離膜で区切られた水素透過部を有
し、かつ該反応管の外側に燃焼ガス通路を有するリフォ
ーマによって、炭化水素又は含酸素炭化水素を原料とし
て水蒸気改質反応を行わせて水素を製造する方法におい
て、前記燃焼ガス通路より排出される燃焼排ガスによ
り、先ずリフォーマに供給される炭化水素又は含酸素炭
化水素と水蒸気よりなる原料ガスを予熱し、次いでリフ
ォーマの燃焼器に供給される空気を予熱すると共に、前
記水素透過部に透過した水素を払い出すための不活性ガ
ス又は水蒸気を該透過部から払い出された高温の水素及
び不活性ガス又は水蒸気の混合ガスにより予熱するよう
にすることを特徴とする水素製造方法である。According to the present invention, there is provided a reformer having a hydrogen permeable portion separated by a hydrogen separation membrane in a reaction tube filled with a reforming catalyst, and having a combustion gas passage outside the reaction tube. In a method for producing hydrogen by performing a steam reforming reaction using a hydrocarbon or an oxygen-containing hydrocarbon as a raw material, a hydrocarbon or an oxygen-containing hydrocarbon first supplied to a reformer by a combustion exhaust gas discharged from the combustion gas passage. Preheats a raw material gas comprising water and steam, then preheats air supplied to a combustor of the reformer, and discharges an inert gas or water vapor for discharging hydrogen permeated to the hydrogen permeable portion from the permeable portion. This is a method for producing hydrogen by preheating with a mixed gas of high-temperature hydrogen and an inert gas or water vapor.
【００１０】[0010]
（１）水素製造装置へ供給するガス、すなわち原料ガ
ス、スチーム、不活性ガス及び燃焼用空気の予熱のため
にリフォーマから流出するストリーム、すなわち、分離
水素ガスと不活性ガスとの混合ガス、燃焼排ガスの排熱
を用いる。 （２）熱交換には各ストリームの温度レベルとストリー
ムの組成を考慮し燃焼排ガスによってまず、原料ガスと
スチームの混合ガスを加熱し、次に燃焼用の低温空気を
加熱する。さらに、リフォーマからの分離水素と不活性
ガスとの混合ガスによって分離水素払出しのための不活
性ガスを加熱する。また、リフォーマからの未反応ガス
によっても不活性ガスを加熱してもよい。 （３）高温ガスをさらに冷却するためには冷却水を用い
る。(1) Gases to be supplied to the hydrogen production apparatus, that is, a stream flowing out of the reformer for preheating the raw material gas, steam, inert gas, and combustion air, that is, a mixed gas of separated hydrogen gas and inert gas, combustion The exhaust heat of the exhaust gas is used. (2) In the heat exchange, the mixed gas of the raw material gas and the steam is first heated by the combustion exhaust gas in consideration of the temperature level of each stream and the composition of the stream, and then the low-temperature air for combustion is heated. Further, the inert gas for discharging the separated hydrogen is heated by the mixed gas of the separated hydrogen and the inert gas from the reformer. Further, the inert gas may be heated by the unreacted gas from the reformer. (3) Cooling water is used to further cool the high-temperature gas.
【００１１】[0011]
【実施例】図１によって、本発明の一実施例を説明す
る。メタン等の炭化水素からなる原料ガス８はガス中の
イオウ分を脱硫器３６で除去後、脱硫原料ガス９はリフ
ォーマ１の燃焼器７へ供給するガス１０と改質触媒層側
３へ供給するガス１１とに分割後、ガス１１はスチーム
２５と混合する。該混合ガス１２を混合ガス予熱器１８
で反応温度まで加熱して高温反応ガス１３とし、触媒層
３へ導入する。触媒層３では前記反応（１）〜（３）に
よって原料ガス８が水素、一酸化炭素及び二酸化炭素に
分解される。FIG. 1 shows an embodiment of the present invention. The raw material gas 8 composed of a hydrocarbon such as methane removes the sulfur content in the gas by a desulfurizer 36, and the desulfurized raw material gas 9 is supplied to the gas 10 to be supplied to the combustor 7 of the reformer 1 and to the reforming catalyst layer 3 side. After being divided into the gas 11, the gas 11 is mixed with the steam 25. The mixed gas 12 is supplied to a mixed gas preheater 18.
Then, the mixture is heated to a reaction temperature to form a high-temperature reaction gas 13 and introduced into the catalyst layer 3. In the catalyst layer 3, the raw material gas 8 is decomposed into hydrogen, carbon monoxide and carbon dioxide by the reactions (1) to (3).
【００１２】これら分解ガスのうち水素だけが例えばパ
ラジウム合金からなる水素分離膜４を通して透過部５に
分離される。主に二酸化炭素からなる未反応ガス１４は
冷却器１５において冷却水３５によって冷却後、低温未
反応ガス６となり、前記燃料用原料ガス１０と混合後、
ストリーム１６としてリフォーマ１の燃焼器７に導入さ
れ燃焼用の燃料とされる。燃焼器７からの燃焼ガスは燃
焼側２を通過し改質触媒層３へ反応熱を供給後、燃焼排
ガス１７としてリフォーマ１から排出される。燃焼排ガ
ス１７はまず混合ガス予熱器１８で熱交換し、次に空気
予熱器１９で空気を加熱後、ストリーム２０となりベン
トから排出される。[0012] Of these decomposition gases, only hydrogen is separated into a permeation section 5 through a hydrogen separation membrane 4 made of, for example, a palladium alloy. After the unreacted gas 14 mainly composed of carbon dioxide is cooled by the cooling water 35 in the cooler 15, the unreacted gas 14 becomes the low-temperature unreacted gas 6, and after mixing with the fuel raw material gas 10,
The stream 16 is introduced into the combustor 7 of the reformer 1 and is used as fuel for combustion. The combustion gas from the combustor 7 passes through the combustion side 2 and supplies reaction heat to the reforming catalyst layer 3, and then is discharged from the reformer 1 as combustion exhaust gas 17. The flue gas 17 is first heat-exchanged by a mixed gas preheater 18, then heated by an air preheater 19, becomes a stream 20, and is discharged from a vent.
【００１３】一般に、熱交換の順序は加熱されるガスの
加熱後の温度レベルの順序によって決まり、より高温ま
で加熱されるストリームを初めに加熱した方が熱効率上
有利となる。この装置では原料ガスとスチームの混合ガ
ス１２をほぼ５００度Ｃまで、燃焼用空気２１を１００
〜４００度Ｃまで加熱する必要がある。このため、まず
混合ガス１２を加熱し、次に燃焼用空気２１を加熱して
いる。In general, the order of the heat exchange is determined by the order of the temperature levels of the gas to be heated after heating, and it is advantageous in terms of thermal efficiency to heat the stream to be heated to a higher temperature first. In this apparatus, the mixed gas 12 of the raw material gas and the steam is reduced to approximately 500 ° C., and the combustion air 21 is reduced to 100 ° C.
It is necessary to heat to ~ 400 ° C. For this reason, the mixed gas 12 is heated first, and then the combustion air 21 is heated.
【００１４】透過部５には不活性ガス２４が熱交換器２
６で加熱され、高温不活性ガス２７として供給される。
リフォーマ１で発生する水素は該不活性ガス２７によっ
て払い出される。この分離水素ガスと不活性ガスとの混
合ガス２８は前記のごとく、熱交換器２６において不活
性ガス２４を加熱し、次に、冷却器２９で冷却水３４に
よって冷却され水素ガスと不活性ガスの混合ガス３２と
して取り出される。An inert gas 24 is supplied to the heat exchanger 2 in the permeation section 5.
6, and is supplied as a high-temperature inert gas 27.
Hydrogen generated in the reformer 1 is discharged by the inert gas 27. As described above, the mixed gas 28 of the separated hydrogen gas and the inert gas heats the inert gas 24 in the heat exchanger 26, and is then cooled by the cooling water 34 in the cooler 29, and As a mixed gas 32.
【００１５】ストリーム２８の冷却には燃焼用空気２１
を用いることも考えられるが、ストリーム２８中に水素
を含むことから安全上問題となる。このため、冷却用の
ストリームとしては不活性ガス２４かあるいは冷却水３
４が適切なものとなる。The stream 28 is cooled by the combustion air 21.
Although it is conceivable to use hydrogen, it is a safety problem since hydrogen is contained in the stream 28. For this reason, the cooling stream is either inert gas 24 or cooling water 3.
4 would be appropriate.
【００１６】燃焼用の空気２１は空気予熱器１９で加熱
後、高温空気２２となり燃焼器７へ送られる。After the combustion air 21 is heated by the air preheater 19, it becomes hot air 22 and is sent to the combustor 7.
【００１７】改質触媒層３からの未反応ガス１４は４０
０〜６００度Ｃである。このストリームは一旦冷却後、
燃焼用燃料として利用される。このストリーム中には水
素等の可燃ガスが含まれているために不活性ガスか冷却
水で冷却する必要がある。この実施例では、冷却器１５
において冷却水３５によって冷却し原料ガス１０と混合
後、燃焼用燃料としてリフォーマの燃焼器７へ供給され
る。The unreacted gas 14 from the reforming catalyst layer 3 is 40
0 to 600 degrees C. Once this stream cools,
Used as fuel for combustion. Since this stream contains a flammable gas such as hydrogen, it needs to be cooled with an inert gas or cooling water. In this embodiment, the cooler 15
After being cooled by the cooling water 35 and mixed with the raw material gas 10, it is supplied to the combustor 7 of the reformer as combustion fuel.
【００１８】以上の通り、本発明に係る実施例によれ
ば、燃焼排ガスと分離水素ガスの排熱を効率よくかつ安
全に回収できるため、水素製造装置の熱効率を向上させ
ることができる。As described above, according to the embodiment of the present invention, since the exhaust heat of the combustion exhaust gas and the separated hydrogen gas can be efficiently and safely recovered, the thermal efficiency of the hydrogen production apparatus can be improved.
【００１９】次に、図２によって他の実施例を説明す
る。この実施例では、分離水素払い出し用の不活性ガス
の代わりにスチーム２４を利用するものである。この装
置では冷却器２９でスチームが凝縮し発生した水を水分
離器３１でドレン３３として分離後、水素を回収する。Next, another embodiment will be described with reference to FIG. In this embodiment, steam 24 is used in place of the inert gas for discharging separated hydrogen. In this device, water generated by condensation of steam in the cooler 29 is separated as drain 33 in the water separator 31 and then hydrogen is recovered.
【００２０】前記実施例と同様に燃焼排ガスと分離水素
ガスの排熱を安全に効率よく回収できるため、水素製造
装置の熱効率を向上させることができる。Since the exhaust heat of the combustion exhaust gas and the separated hydrogen gas can be safely and efficiently recovered as in the above embodiment, the thermal efficiency of the hydrogen production apparatus can be improved.
【００２１】[0021]
（１）リフォーマからの燃焼排ガスと分離水素ガスの排
熱を回収し燃焼用空気、原料ガス及びスチームを予熱す
ることによって水素製造装置の熱効率を向上させること
ができる。 （２）水素を含むストリームをスチームや不活性ガスの
ような酸素を含まないストリームと熱交換することによ
って安全性が向上する。 （３）リフォーマからの高温ストリームを冷却するため
に、リフォーマへ供給する低温ストリームの一部を利用
するために冷却水量を低減することができる。(1) The thermal efficiency of the hydrogen production apparatus can be improved by recovering the exhaust heat of the combustion exhaust gas and the separated hydrogen gas from the reformer and preheating the combustion air, raw material gas and steam. (2) Safety is improved by heat exchange of the stream containing hydrogen with a stream that does not contain oxygen, such as steam or an inert gas. (3) In order to cool the high-temperature stream from the reformer, the amount of cooling water can be reduced because a part of the low-temperature stream supplied to the reformer is used.
【図１】本発明の一実施例の説明図。FIG. 1 is an explanatory diagram of one embodiment of the present invention.
【図２】本発明の他の実施例の説明図。FIG. 2 is an explanatory view of another embodiment of the present invention.
【図３】従来の水素製造方法の一実施態様の説明図。FIG. 3 is an explanatory view of one embodiment of a conventional hydrogen production method.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 黒田 健之助 東京都千代田区丸の内二丁目５番１号 三菱重工業株式会社 本社内 (56)参考文献 特開 平２−129001（ＪＰ，Ａ) 特開 昭50−86502（ＪＰ，Ａ) 特開 平２−311301（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C01B 3/32 - 3/48 ──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Kennosuke Kuroda 2-5-1 Marunouchi, Chiyoda-ku, Tokyo Mitsubishi Heavy Industries, Ltd. Headquarters (56) References JP-A-2-129001 (JP, A) JP-A Sho 50-86502 (JP, A) JP-A-2-311301 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C01B 3/32-3/48
Claims (1)
膜で区切られた水素透過部を有し、かつ該反応管の外側
に燃焼ガス通路を有するリフォーマによって、炭化水素
又は含酸素炭化水素を原料として水蒸気改質反応を行わ
せて水素を製造する方法において、前記燃焼ガス通路よ
り排出される燃焼排ガスにより、先ずリフォーマに供給
される炭化水素又は含酸素炭化水素と水蒸気よりなる原
料ガスを予熱し、次いでリフォーマの燃焼器に供給され
る空気を予熱すると共に、前記水素透過部に透過した水
素を払い出すための不活性ガス又は水蒸気を該透過部か
ら払い出された高温の水素及び不活性ガス又は水蒸気の
混合ガスにより予熱するようにすることを特徴とする水
素製造方法。1. A reformer having a hydrogen permeable portion separated by a hydrogen separation membrane in a reaction tube filled with a reforming catalyst and having a combustion gas passage outside the reaction tube, the hydrocarbon or the oxygen-containing hydrocarbon. In the method of producing hydrogen by performing a steam reforming reaction using as a raw material, first, a raw material gas comprising hydrocarbons or oxygen-containing hydrocarbons and water vapor supplied to a reformer by a combustion exhaust gas discharged from the combustion gas passage. Preheating, then preheating the air supplied to the combustor of the reformer, and supplying an inert gas or water vapor for discharging the hydrogen permeated to the hydrogen permeable portion with the high-temperature hydrogen and the non-hydrogen discharged from the permeable portion. A method for producing hydrogen, comprising preheating with a mixed gas of an active gas or steam.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3309265A JP3035038B2 (en) | 1991-11-25 | 1991-11-25 | Hydrogen production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3309265A JP3035038B2 (en) | 1991-11-25 | 1991-11-25 | Hydrogen production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05147902A JPH05147902A (en) | 1993-06-15 |
| JP3035038B2 true JP3035038B2 (en) | 2000-04-17 |
Family
ID=17990920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3309265A Expired - Lifetime JP3035038B2 (en) | 1991-11-25 | 1991-11-25 | Hydrogen production method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3035038B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9061909B2 (en) | 2009-09-10 | 2015-06-23 | The University Of Tokyo | Method for simultaneously producing carbon nanotubes and hydrogen, and device for simultaneously producing carbon nanotubes and hydrogen |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07315801A (en) * | 1994-05-23 | 1995-12-05 | Ngk Insulators Ltd | System for producing high-purity hydrogen, production of high-purity hydrogen and fuel cell system |
| JP4519225B2 (en) * | 1999-10-19 | 2010-08-04 | 日本碍子株式会社 | Fuel cell system and control method thereof |
| JP2002033113A (en) | 1999-11-18 | 2002-01-31 | Toyota Motor Corp | Fuel gas generator for fuel cell and composite material for hydrogen separation |
| US6656617B2 (en) | 2000-01-24 | 2003-12-02 | Toyota Jidosha Kabushiki Kaisha | Fuel gas production system for fuel cells |
| EP1167283B1 (en) * | 2000-06-27 | 2005-09-28 | Nisshin Steel Co., Ltd. | A gas reformer for recovery of hydrogen |
| NO317382B1 (en) | 2001-02-16 | 2004-10-18 | Norsk Hydro As | Method for carrying out a catalytic or non-catalytic process |
| US7341609B2 (en) * | 2002-10-03 | 2008-03-11 | Genesis Fueltech, Inc. | Reforming and hydrogen purification system |
| WO2005075344A1 (en) * | 2004-02-09 | 2005-08-18 | Ngk Insulators, Ltd. | Process for reforming hydrocarbons with carbon dioxide by the use of a selectively permeable membrane reactor |
| WO2009091791A1 (en) * | 2008-01-16 | 2009-07-23 | Shell Oil Company | A system and process for making hydrogen from a hydrocarbon stream |
| JP5333722B2 (en) * | 2008-07-16 | 2013-11-06 | 日産自動車株式会社 | Hydrogen generator |
| TWI471262B (en) * | 2011-12-27 | 2015-02-01 | Ind Tech Res Inst | Filtration-enhanced hydrogen generator |
| TWI464110B (en) * | 2011-12-29 | 2014-12-11 | Ind Tech Res Inst | Membrane-based reforming hydrogen generator for hydrocarbons |
-
1991
- 1991-11-25 JP JP3309265A patent/JP3035038B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9061909B2 (en) | 2009-09-10 | 2015-06-23 | The University Of Tokyo | Method for simultaneously producing carbon nanotubes and hydrogen, and device for simultaneously producing carbon nanotubes and hydrogen |
| US10633249B2 (en) * | 2009-09-10 | 2020-04-28 | The University Of Tokyo | Device for simultaneously producing carbon nanotubes and hydrogen |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05147902A (en) | 1993-06-15 |
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