JPH10291801A - Production method of hydrogen and device therefor - Google Patents
Production method of hydrogen and device thereforInfo
- Publication number
- JPH10291801A JPH10291801A JP10049897A JP10049897A JPH10291801A JP H10291801 A JPH10291801 A JP H10291801A JP 10049897 A JP10049897 A JP 10049897A JP 10049897 A JP10049897 A JP 10049897A JP H10291801 A JPH10291801 A JP H10291801A
- Authority
- JP
- Japan
- Prior art keywords
- partial oxidation
- raw material
- steam reforming
- hydrogen
- section
- 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
Links
- 239000001257 hydrogen Substances 0.000 title claims abstract description 76
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 76
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 76
- 239000007789 gas Substances 0.000 claims abstract description 75
- 238000000629 steam reforming Methods 0.000 claims abstract description 74
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 65
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 65
- 239000002994 raw material Substances 0.000 claims abstract description 65
- 230000003647 oxidation Effects 0.000 claims abstract description 64
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 57
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 45
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 230000015572 biosynthetic process Effects 0.000 claims description 39
- 238000003786 synthesis reaction Methods 0.000 claims description 39
- 239000003570 air Substances 0.000 claims description 17
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 4
- 238000002407 reforming Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 22
- 239000000446 fuel Substances 0.000 abstract description 8
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 29
- 238000000034 method Methods 0.000 description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 238000002485 combustion reaction Methods 0.000 description 8
- 239000000567 combustion gas Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000002303 thermal reforming Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- WVYYHSKIGBEZCQ-UHFFFAOYSA-N [O-2].[O-2].[Cr+3].[Fe+2] Chemical compound [O-2].[O-2].[Cr+3].[Fe+2] WVYYHSKIGBEZCQ-UHFFFAOYSA-N 0.000 description 1
- GFCDJPPBUCXJSC-UHFFFAOYSA-N [O-2].[Zn+2].[Cu]=O Chemical compound [O-2].[Zn+2].[Cu]=O GFCDJPPBUCXJSC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229960004424 carbon dioxide Drugs 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Landscapes
- Hydrogen, Water And Hydrids (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、水蒸気改質法と部
分酸化法を組み合わせることにより、両方法の欠点を改
善するようにした水素製造方法およびそれに用いる装置
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 producing hydrogen and an apparatus used therefor, in which a steam reforming method and a partial oxidation method are combined to improve the disadvantages of both methods.
【０００２】[0002]
【従来の技術】従来から、水素の製造方法としては、Ｌ
ＰＧ等を原料とした水蒸気改質法、重質油等を原料とし
た部分酸化法、水の電気分解法、メタノール分解法等が
広く用いられている。これらの方法のうち、炭化水素か
ら水素を製造する方法として、水蒸気改質法と部分酸化
法がある。水蒸気改質法は、ＬＰＧ，ＬＮＧ，ナフサ等
を原料として用い、これらを８００〜９００℃の高温
下、Ｎｉ（ニッケル）触媒上でスチームと反応させ、水
素，一酸化炭素等を含有する合成ガスを発生させるもの
である。その反応は、理論的には、下記の式（１）（原
料はブタン）で示される。2. Description of the Related Art Conventionally, as a method for producing hydrogen, L
A steam reforming method using PG or the like as a raw material, a partial oxidation method using heavy oil or the like as a raw material, a water electrolysis method, a methanol decomposition method, and the like are widely used. Among these methods, methods for producing hydrogen from hydrocarbons include a steam reforming method and a partial oxidation method. The steam reforming method uses LPG, LNG, naphtha and the like as raw materials, and reacts them with steam over a Ni (nickel) catalyst at a high temperature of 800 to 900 ° C. to produce a synthesis gas containing hydrogen, carbon monoxide and the like. Is generated. The reaction is theoretically represented by the following formula (1) (the starting material is butane).
【０００３】[0003]
【化１】 Ｃ4 Ｈ10＋４Ｈ2 Ｏ＝４ＣＯ＋９Ｈ2 ……（１）Embedded image C 4 H 10 + 4H 2 O = 4CO + 9H 2 (1)
【０００４】この場合、理論的には原料１モルから９モ
ルの水素が発生する。この反応は強い吸熱反応であり、
その熱量を補うために炭化水素消費量の３０％前後が燃
料として空気と混合され、Ｎｉ触媒塔の外部で燃焼され
る。また、この燃焼によりＮＯX が発生するため、ＮＯ
X 除去塔が設置されている。このような水蒸気改質法で
は、Ｓ／Ｃ比（スチーム／炭素モル比）は、理論的に
１．０であるが、一般的には炭化水素のコークス化を避
けるために３．０〜３．５で運転される。In this case, 9 moles of hydrogen are theoretically generated from 1 mole of the raw material. This reaction is a strong endothermic reaction,
To compensate for the heat, about 30% of the hydrocarbon consumption is mixed with air as fuel and burned outside the Ni catalyst tower. Further, since NO X is generated by this combustion, NO X
X removal tower is installed. In such a steam reforming method, the S / C ratio (steam / carbon molar ratio) is theoretically 1.0, but is generally 3.0 to 3 in order to avoid coking of hydrocarbons. .5.
【０００５】一方、部分酸化法は、重質油等を原料とし
て用い、炭化水素の完全燃焼に必要な酸素量の３０〜４
０％に相当する量の純酸素または空気で原料を燃焼さ
せ、水素，一酸化炭素等を含む合成ガスを発生させるも
のである。その反応は、理論的には、下記の式（２）
（原料はブタン）で示される。On the other hand, in the partial oxidation method, heavy oil or the like is used as a raw material, and the amount of oxygen required for complete combustion of hydrocarbons is 30 to 4%.
The raw material is burned with pure oxygen or air in an amount corresponding to 0% to generate a synthesis gas containing hydrogen, carbon monoxide and the like. The reaction is theoretically represented by the following formula (2)
(The raw material is butane).
【０００６】[0006]
【化２】 Ｃ4 Ｈ10＋２Ｏ2 ＝４ＣＯ＋５Ｈ2 ……（２）Embedded image C 4 H 10 + 2O 2 = 4CO + 5H 2 (2)
【０００７】この場合、理論的には原料１モルから５モ
ルの水素が発生する。この反応は強い発熱反応であり、
反応炉内が１３００〜１５００℃の高温に達するため、
温度調節用にスチームを用いる場合がある。In this case, theoretically, 1 to 5 moles of hydrogen are generated from the raw material. This reaction is a strongly exothermic reaction,
Because the inside of the reactor reaches a high temperature of 1300-1500 ° C,
Steam may be used for temperature control.
【０００８】水素製造を目的とする場合には、上述した
反応により得られた合成ガスを一酸化炭素転化反応器に
導入することが行われる。この反応器には、高温（３２
０〜５１０℃）で行う高温転化反応器と、低温（１８０
〜２９０℃）で行う低温転化反応器がある。高温反応に
は、一般に酸化鉄−酸化クロム系触媒が用いられ、硫黄
の被毒に強いが、低温では活性が低いという特徴があ
る。この高温反応では、一酸化炭素含有量を約３〜４％
まで低減することができる。一方、低温反応には酸化銅
−酸化亜鉛系触媒が用いられ、耐被毒性、耐熱性に劣る
が、低温で強い活性を示すという特徴がある。この低温
反応では、一酸化炭素含有量を０．２％程度まで低減す
ることができる。工業的には、両方の反応が組み合わせ
て使用されている。For the purpose of producing hydrogen, the synthesis gas obtained by the above-mentioned reaction is introduced into a carbon monoxide conversion reactor. The reactor contains high temperature (32
0-510 ° C.) and a low temperature (180 ° C.).
290 ° C.). The high-temperature reaction generally uses an iron oxide-chromium oxide catalyst, and is resistant to sulfur poisoning, but is characterized by low activity at low temperatures. In this high temperature reaction, the carbon monoxide content is reduced to about 3-4%.
Can be reduced. On the other hand, a copper oxide-zinc oxide-based catalyst is used for the low-temperature reaction, and although it is inferior to poisoning resistance and heat resistance, it is characterized by showing strong activity at low temperatures. In this low-temperature reaction, the carbon monoxide content can be reduced to about 0.2%. Industrially, both reactions are used in combination.
【０００９】上記のような水蒸気改質法に用いる装置の
概略を、図２に示す。図において、２１は原料導入パイ
プであり、炭化水素原料と水を熱交換器２２に導入し、
この熱交換器２２（を通る後述の燃焼ガス）で炭化水素
原料を所定温度に昇温させるとともに水をスチームに変
え、その状態で反応器２３の２つのＮｉ触媒塔２４に供
給する。このＮｉ触媒塔２４で、炭化水素原料とスチー
ムが反応して水素，一酸化炭素を含む合成ガスを発生さ
せる。２５は燃料供給パイプであり、炭化水素燃料と空
気を反応器２３の周壁に設けたバーナー２６に導入して
燃焼させ、この燃焼熱で両Ｎｉ触媒塔２４を外部から加
熱する。２７は燃焼ガス流出パイプであり、反応器２３
内の燃焼ガスを上記熱交換器２２に導入したのち、ＮＯ
X 除去塔２８に送り、このＮＯX 除去塔２８で燃焼ガス
中のＮＯX を除去する。２９はガス導出パイプであり、
Ｎｉ触媒塔２４を経て得られた合成ガスを熱交換器３０
に導入し、この熱交換器３０（を通る冷却水）で所定温
度に降温させたのち、一酸化炭素転化反応器３１に送
り、この一酸化炭素転化反応器３１に充填した一酸化炭
素転化触媒で一酸化炭素をシフト転化させる。３２は一
酸化炭素転化反応器３１で得られた製品水素を取り出す
製品水素取出しパイプである。FIG. 2 schematically shows an apparatus used in the above-described steam reforming method. In the figure, 21 is a raw material introduction pipe, which introduces a hydrocarbon raw material and water into a heat exchanger 22,
The hydrocarbon feed is heated to a predetermined temperature by the heat exchanger 22 (combustion gas to be described later) and water is changed to steam, and is supplied to the two Ni catalyst towers 24 of the reactor 23 in that state. In the Ni catalyst tower 24, the hydrocarbon raw material reacts with steam to generate a synthesis gas containing hydrogen and carbon monoxide. Reference numeral 25 denotes a fuel supply pipe, which introduces hydrocarbon fuel and air into a burner 26 provided on a peripheral wall of the reactor 23 and burns the fuel, and heats both the Ni catalyst towers 24 from the outside with the combustion heat. Reference numeral 27 denotes a combustion gas outflow pipe,
After the combustion gas in the inside is introduced into the heat exchanger 22, NO
Feeding the X removal column 28, to remove the NO X in the combustion gases in the NO X removal column 28. 29 is a gas outlet pipe,
The synthesis gas obtained through the Ni catalyst tower 24 is passed through the heat exchanger 30
After being cooled to a predetermined temperature by the heat exchanger 30 (cooling water passing therethrough), the mixture is sent to a carbon monoxide conversion reactor 31, and the carbon monoxide conversion catalyst filled in the carbon monoxide conversion reactor 31 Shift-converts carbon monoxide. Reference numeral 32 denotes a product hydrogen extraction pipe for extracting product hydrogen obtained in the carbon monoxide conversion reactor 31.
【００１０】ところが、上記の水蒸気改質法では、水素
源である炭化水素の一部を燃料として消費する必要があ
り、また、その燃焼により生じるＮＯX を除去するため
にＮＯX 除去塔２８を設置しなければならない。しか
も、Ｎｉ触媒を用いているため、数年ごとにＮｉ触媒を
取り替える必要がある。一方、部分酸化法では、水蒸気
改質法と比較して、理論的に水素発生量が少なく、低効
率である。[0010] However, in the steam reforming process described above, it is necessary to consume a portion of the hydrocarbon is a hydrogen source as a fuel, also the NO X removal column 28 to remove the NO X produced by the combustion Must be installed. Moreover, since the Ni catalyst is used, it is necessary to replace the Ni catalyst every few years. On the other hand, the partial oxidation method theoretically generates a smaller amount of hydrogen and has lower efficiency than the steam reforming method.
【００１１】そこで、炭化水素原料の一部を燃料として
消費する必要がなく、しかも、ＮＯ X の除去設備を必要
としない方法が提案されている。この方法は、水蒸気改
質法と部分酸化法を１段の反応器で行う内熱式改質法と
呼ばれるものである。この内熱式改質法では、図３に示
すように、反応原料となる炭化水素，酸素（あるいは空
気）およびスチームが予熱されたのち、反応器３５の頂
部のバーナー３６を通して部分酸化部３７に導入され
る。この部分酸化部３７では、炭化水素と酸素が発熱反
応である部分酸化反応を起こし、１１００〜１２００℃
の高温下、水素，一酸化炭素を含む合成ガスを発生す
る。この合成ガスには、上記反応で未反応の炭化水素も
含まれており、これらがスチームとともに部分酸化部３
７の下部の水蒸気改質部（Ｎｉ触媒層）３８に導入さ
れ、この水蒸気改質部３８でスチームと水蒸気改質反応
を起こし、さらに水素，一酸化炭素を発生する。吸熱反
応である水蒸気改質反応に必要な熱量は、部分酸化反応
での発熱量によりまかなわれる。こうして発生される水
素，一酸化炭素を含む合成ガスは、水素製造を目的とす
る場合には、一酸化炭素転化反応器に送られる。Therefore, part of the hydrocarbon feedstock is used as fuel.
No need to consume and NO XNeed removal equipment
And no method has been proposed. This method is
Reforming method in which the quality method and partial oxidation method are performed in a single-stage reactor.
What is called. In this internal thermal reforming method, as shown in FIG.
As described above, hydrocarbons, oxygen (or
Q) and after the steam has been preheated,
Into the partial oxidation section 37 through the burner 36 of the section
You. In the partial oxidation section 37, hydrocarbons and oxygen generate heat.
Causes a partial oxidation reaction,
Generates synthesis gas containing hydrogen and carbon monoxide at high temperatures
You. This synthesis gas contains hydrocarbons that have not been reacted in the above reaction.
And these are partly oxidized with steam 3
7 into the steam reforming section (Ni catalyst layer) 38 below.
In the steam reforming section 38, steam and steam reforming reaction
To generate hydrogen and carbon monoxide. Heat absorption
The amount of heat required for the steam reforming reaction is
It is covered by the calorific value at Water generated in this way
Synthesis gas containing carbon and carbon monoxide is intended for hydrogen production
, It is sent to a carbon monoxide conversion reactor.
【００１２】[0012]
【発明が解決しようとする課題】しかしながら、上記の
内熱式改質法では、水素源となる全ての炭化水素原料を
反応器３５の頂部から導入するため、部分酸化部３７で
はある程度の炭化水素を未反応のまま残存させておき、
この残存炭化水素を水蒸気改質部３８へ導入する必要が
ある。このことから、部分酸化部３７においては、Ｏ2
に対して炭化水素の割合がかなり高くなり、最適な燃焼
状態であるとはいえない。つまり、部分酸化反応の発熱
量で水蒸気改質反応の吸熱量をまかなうためにはかなり
の割合の炭化水素が理論的に効率の悪い部分酸化部３７
で反応しなければならず、水素発生効率が悪い。However, in the above-mentioned internal thermal reforming method, all hydrocarbon raw materials serving as a hydrogen source are introduced from the top of the reactor 35. Is left unreacted,
It is necessary to introduce this residual hydrocarbon into the steam reforming section 38. From this, in the partial oxidation part 37, O 2
However, the ratio of hydrocarbons is considerably high, and it cannot be said that the combustion state is optimal. In other words, in order to cover the endothermic amount of the steam reforming reaction with the amount of heat generated by the partial oxidation reaction, a considerable proportion of hydrocarbons is required to have a theoretically inefficient partial oxidation unit 37.
And the efficiency of hydrogen generation is poor.
【００１３】本発明は、このような事情に鑑みなされた
もので、炭化水素原料の一部を燃料として消費すること
がなく、しかも、ＮＯX を除去するための設備を設置す
る必要がなく、水蒸気改質用触媒の取り替えピッチを長
くすることができ、水素発生効率が高い水素製造方法お
よびそれに用いる装置の提供をその目的とする。[0013] The present invention has been made in view of such circumstances, without consuming a portion of the hydrocarbon feedstock as a fuel, moreover, it is not necessary to install a facility for removing NO X, It is an object of the present invention to provide a hydrogen production method and a device used therefor that can increase the replacement pitch of a steam reforming catalyst and have high hydrogen generation efficiency.
【００１４】[0014]
【課題を解決するための手段】上記の目的を達成するた
め、本発明は、炭化水素原料と、酸素または空気と、水
蒸気を反応器の部分酸化部に導入し、この部分酸化部に
おける部分酸化により水素と一酸化炭素との合成ガスを
生成させ、この生成した合成ガスを水蒸気とともに部分
酸化部から取り出したのち上記合成ガスに炭化水素原料
を供給して反応器の水蒸気改質部に導入し、上記部分酸
化による発熱を利用して上記水蒸気改質部における水蒸
気改質を行い、上記水蒸気改質部で生成した合成ガスを
製品ガスとして取り出すようにした水素製造方法を第１
の要旨とし、炭化水素原料と、酸素または空気を反応器
の部分酸化部に導入し、この部分酸化部における部分酸
化により水素と一酸化炭素との合成ガスを生成させ、こ
の生成した合成ガスを上記部分酸化部から取り出したの
ち上記合成ガスに炭化水素原料と水蒸気を供給して反応
器の水蒸気改質部に導入し、上記部分酸化による発熱を
利用して上記水蒸気改質部における水蒸気改質を行い、
上記水蒸気改質部で生成した合成ガスを製品ガスとして
取り出すようにした水素製造方法を第２の要旨とし、内
部に燃焼器付き部分酸化部と水蒸気改質部を直列に配設
した反応器と、炭化水素原料と、酸素または空気と、水
蒸気を上記部分酸化部の燃焼器に導入する第１の原料導
入路と、上記部分酸化部と水蒸気改質部を連結する連結
路と、この連結路に炭化水素原料を導入する第２の原料
導入路と、上記水蒸気改質部で生成した水素と一酸化炭
素の合成ガスを製品ガスとして取り出す製品ガス取出し
路とを設けた水素製造装置を第３の要旨とし、内部に燃
焼器付き部分酸化部と水蒸気改質部を直列に配設した反
応器と、炭化水素原料と、酸素または空気を上記部分酸
化部の燃焼器に導入する第１の原料導入路と、上記部分
酸化部と水蒸気改質部を連結する連結路と、この連結路
に炭化水素原料と水蒸気を導入する第２の原料導入路
と、上記水蒸気改質部で生成した水素と一酸化炭素の合
成ガスを製品ガスとして取り出す製品ガス取出し路とを
設けた水素製造装置を第４の要旨とする。In order to achieve the above object, the present invention provides a method for introducing a hydrocarbon feedstock, oxygen or air, and steam into a partial oxidation section of a reactor. To generate a synthesis gas of hydrogen and carbon monoxide.Then, the generated synthesis gas is taken out from the partial oxidation section together with the steam, and then a hydrocarbon raw material is supplied to the synthesis gas and introduced into the steam reforming section of the reactor. The first method for producing hydrogen is that steam reforming is performed in the steam reforming section using heat generated by the partial oxidation, and the synthesis gas generated in the steam reforming section is taken out as a product gas.
The hydrocarbon feedstock and oxygen or air are introduced into the partial oxidation section of the reactor, and the partial oxidation in the partial oxidation section generates a synthesis gas of hydrogen and carbon monoxide. After being taken out from the partial oxidation section, a hydrocarbon raw material and steam are supplied to the synthesis gas and introduced into the steam reforming section of the reactor, and the steam reforming section in the steam reforming section utilizes heat generated by the partial oxidation. Do
A second aspect of the present invention is a hydrogen production method in which the synthesis gas generated in the steam reforming section is taken out as a product gas, and a reactor in which a partial oxidation section with a combustor and a steam reforming section are arranged in series. A first raw material introduction path for introducing a hydrocarbon raw material, oxygen or air, and steam into the combustor of the partial oxidation unit; a connection path for connecting the partial oxidation unit and the steam reforming unit; A hydrogen feeder for introducing a hydrocarbon feedstock into the reactor and a product gas takeout passage for taking out a synthesis gas of hydrogen and carbon monoxide generated in the steam reforming section as a product gas. A reactor in which a partial oxidation section with a combustor and a steam reforming section are arranged in series, a hydrocarbon raw material, and a first raw material for introducing oxygen or air into the combustor of the partial oxidation section The introduction path, the partial oxidation section and steam A second raw material introduction path for introducing a hydrocarbon raw material and steam into the connection path, and a product for extracting a synthesis gas of hydrogen and carbon monoxide generated in the steam reforming section as a product gas. A fourth aspect is a hydrogen production apparatus provided with a gas extraction path.
【００１５】すなわち、本発明の第１の水素製造方法
は、まず、水素源となる炭化水素原料の一部と、酸素ま
たは空気と、スチームを反応器の部分酸化部に導入し、
この部分酸化部で水素と一酸化炭素を含む合成ガスを発
生させ、つぎに、この合成ガスに、水素源となる炭化水
素原料の残部を供給し、そののち、これらを反応器の水
蒸気改質部に導入する。上記部分酸化室での部分酸化は
発熱反応であるため、この発熱量を利用し、部分酸化と
水蒸気改質部における水蒸気改質を同時に行い、水素と
一酸化炭素を含む合成ガスを水蒸気改質部で発生させ
る。このように、本発明では、部分酸化反応用の炭化水
素原料と水蒸気改質反応用の炭化水素原料を分割して反
応器に導入する点に、特徴がある。これにより、部分酸
化部での反応と水蒸気改質部での反応を最適な条件で行
わせることができ、効率よく水素および一酸化炭素を発
生することが可能となる。しかも、部分酸化反応と水蒸
気改質反応それぞれ最適な条件下で行うことができ、制
御も簡単である。さらに、従来例と同様に、簡単な構造
である。さらに、部分酸化反応では、ＮＯX が発生しな
いため、従来例のようなＮＯX 除去塔２８が不要にな
る。さらに、水蒸気改質部に導入する炭化水素原料の量
が大幅に減少するため、水蒸気改質用触媒の消費量が大
幅に減少し、触媒の取り替えピッチを大幅に長くするこ
とができる。また、本発明の第２の水素製造方法では、
炭化水素原料と、酸素または空気を反応器の部分酸化部
に供給し、この部分酸化部で生成させた合成ガスに炭化
水素原料と水蒸気を供給している。この方法でも、上記
の第１の水素製造方法と同様の作用・効果を奏する。一
方、本発明の水素製造装置によれば、本発明の方法を容
易に達成することができる。なお、本発明では、部分酸
化反応は水蒸気改質反応の吸熱量とのバランス，生成物
の組成等を考慮して，酸素量，スチーム量を調節して最
適な条件で行われる。また、水蒸気改質反応用の炭化水
素原料の量は水蒸気改質反応の条件が最適となるように
調整される。That is, in the first hydrogen production method of the present invention, first, a part of a hydrocarbon source material serving as a hydrogen source, oxygen or air, and steam are introduced into a partial oxidation section of a reactor.
In the partial oxidation section, a synthesis gas containing hydrogen and carbon monoxide is generated. Next, the remainder of the hydrocarbon raw material serving as a hydrogen source is supplied to the synthesis gas, which is then subjected to steam reforming in a reactor. Introduction to the department. Since the partial oxidation in the partial oxidation chamber is an exothermic reaction, the calorific value is used to perform the partial oxidation and the steam reforming in the steam reforming unit at the same time to steam reform the synthesis gas containing hydrogen and carbon monoxide. Generated in the part. As described above, the present invention is characterized in that the hydrocarbon raw material for the partial oxidation reaction and the hydrocarbon raw material for the steam reforming reaction are divided and introduced into the reactor. Thus, the reaction in the partial oxidation section and the reaction in the steam reforming section can be performed under optimal conditions, and hydrogen and carbon monoxide can be generated efficiently. In addition, the partial oxidation reaction and the steam reforming reaction can be performed under optimum conditions, respectively, and the control is simple. Furthermore, the structure is simple as in the conventional example. Further, since NO X is not generated in the partial oxidation reaction, the NO X removing tower 28 as in the conventional example becomes unnecessary. Further, since the amount of the hydrocarbon feedstock introduced into the steam reforming section is greatly reduced, the consumption of the steam reforming catalyst is greatly reduced, and the catalyst replacement pitch can be greatly lengthened. In the second hydrogen production method of the present invention,
A hydrocarbon raw material and oxygen or air are supplied to a partial oxidation part of the reactor, and the hydrocarbon raw material and steam are supplied to the synthesis gas generated in the partial oxidation part. Also in this method, the same operation and effect as those of the first hydrogen production method are obtained. On the other hand, according to the hydrogen production apparatus of the present invention, the method of the present invention can be easily achieved. In the present invention, the partial oxidation reaction is performed under optimal conditions by adjusting the amount of oxygen and the amount of steam in consideration of the balance with the endothermic amount of the steam reforming reaction, the composition of the product, and the like. Further, the amount of the hydrocarbon raw material for the steam reforming reaction is adjusted so that the conditions of the steam reforming reaction are optimized.
【００１６】本発明において、製品ガス（水素と一酸化
炭素を含む合成ガス）中の一酸化炭素を水素に転化する
ことにより水素を富化するようにした場合には、高純度
水素を主成分とした製品ガスが得られる。一方、製品ガ
ス中に含まれる多量の一酸化炭素を主製品とする場合
は、そのまま精製装置へ送ることが行われる。In the present invention, when hydrogen is enriched by converting carbon monoxide in a product gas (synthesis gas containing hydrogen and carbon monoxide) into hydrogen, high-purity hydrogen is mainly contained. Product gas is obtained. On the other hand, when the main product is a large amount of carbon monoxide contained in the product gas, the product gas is directly sent to a purification device.
【００１７】[0017]
【発明の実施の形態】つぎに、本発明の実施の形態を図
面にもとづいて詳しく説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, embodiments of the present invention will be described in detail with reference to the drawings.
【００１８】図１は本発明の水素製造装置の一実施の形
態を示している。図において、１は反応器であり、２は
上記反応器１の上部に設けた部分酸化部である。この部
分酸化部２は、その上壁にバーナー３（燃焼器）を取り
付けた部分酸化反応室４で構成されている。上記バーナ
ー３には、そのガス入口（図示せず）に、炭化水素原料
（水素源となる炭化水素原料の一部）と酸素（または空
気）とスチームが供給される。このような炭化水素原
料，酸素およびスチームの供給は、図１に示すように、
それぞれ別々に、３本の第１原料導入パイプ１０〜１２
を用いて行ってもよいし、２本もしくは１本の第１原料
導入パイプを用いて行ってもよい。５は部分酸化部２の
下壁２ａとの間に所定の隙間をあけて設けられた水蒸気
改質部であり、Ｎｉ触媒が充填されたＮｉ触媒塔で構成
されている。このような水蒸気改質部５は、部分酸化部
２が１３００〜１５００℃である時に８００〜９００℃
となるように設計されている。６は部分酸化部２に設け
たガス出口（図示せず）と水蒸気改質部５の上端部に設
けたガス入口（図示せず）とを連結する連結パイプであ
り、部分酸化部２で生成された合成ガスを水蒸気改質部
５に導入する。１３は連結パイプ６に炭化水素原料（水
素源となる炭化水素原料の残部）を供給する第２原料導
入パイプである。１４は製品ガス取出しパイプであり、
水蒸気改質部５で生成された合成ガスを取り出し、一酸
化炭素転化反応器（図示せず）に送る。FIG. 1 shows an embodiment of the hydrogen production apparatus of the present invention. In the figure, reference numeral 1 denotes a reactor, and reference numeral 2 denotes a partial oxidation unit provided on the upper part of the reactor 1. The partial oxidation section 2 is composed of a partial oxidation reaction chamber 4 having a burner 3 (combustor) attached to its upper wall. The gas inlet (not shown) of the burner 3 is supplied with a hydrocarbon raw material (part of the hydrocarbon raw material serving as a hydrogen source), oxygen (or air), and steam. The supply of such hydrocarbon raw material, oxygen and steam is as shown in FIG.
Each of the three first raw material introduction pipes 10 to 12
May be used, or two or one first raw material introduction pipe may be used. Reference numeral 5 denotes a steam reforming unit provided with a predetermined gap between the partial oxidizing unit 2 and the lower wall 2a, and is constituted by a Ni catalyst tower filled with a Ni catalyst. Such a steam reforming section 5 has a temperature of 800 to 900 ° C. when the partial oxidation section 2 has a temperature of 1300 to 1500 ° C.
It is designed to be. Reference numeral 6 denotes a connection pipe connecting a gas outlet (not shown) provided in the partial oxidation unit 2 and a gas inlet (not shown) provided at the upper end of the steam reforming unit 5. The synthesis gas thus obtained is introduced into the steam reforming section 5. Reference numeral 13 denotes a second raw material introduction pipe for supplying a hydrocarbon raw material (remaining hydrocarbon raw material serving as a hydrogen source) to the connecting pipe 6. 14 is a product gas extraction pipe,
The synthesis gas generated in the steam reforming section 5 is taken out and sent to a carbon monoxide conversion reactor (not shown).
【００１９】上記装置を用い、水素を製造する場合に
は、まず、第１原料導入パイプ１０〜１２により炭化水
素原料と酸素とスチームをバーナー３に導入し、導入し
た炭化水素原料の一部と酸素を燃焼させる。この燃焼熱
により残存炭化水素原料を部分酸化反応室４で部分酸化
させ、水素と一酸化炭素を含む合成ガスを生成させる。
この生成させた合成ガスをスチームとともにガス出口か
ら送り出して連結パイプ６に導入したのち、第２原料導
入パイプ１３により供給される炭化水素原料と合流さ
せ、水蒸気改質部５に導入する。この水蒸気改質部５で
はＮｉ触媒の作用により炭化水素原料をスチームと水蒸
気改質させ、水素と一酸化炭素を含む合成ガスを生成さ
せる。この水蒸気改質を部分酸化による燃焼熱を利用し
て、部分酸化と同時に行う。このようにして生成させた
合成ガスを製品ガス取出しパイプ１４により取り出した
のち、一酸化炭素転化反応器に送り、この一酸化炭素転
化反応器で一酸化炭素を水素にシフト転化し、高純度水
素を得る。In the case of producing hydrogen using the above-mentioned apparatus, first, a hydrocarbon raw material, oxygen and steam are introduced into the burner 3 through the first raw material introduction pipes 10 to 12, and a part of the introduced hydrocarbon raw material is introduced. Burns oxygen. The residual heat of the hydrocarbon is partially oxidized by the heat of combustion in the partial oxidation reaction chamber 4 to generate a synthesis gas containing hydrogen and carbon monoxide.
After the generated synthesis gas is sent out from the gas outlet together with the steam and introduced into the connection pipe 6, it is combined with the hydrocarbon raw material supplied by the second raw material introduction pipe 13 and introduced into the steam reforming section 5. In the steam reforming section 5, the hydrocarbon raw material is steam-reformed with steam by the action of the Ni catalyst to generate a synthesis gas containing hydrogen and carbon monoxide. This steam reforming is performed simultaneously with the partial oxidation by utilizing the heat of combustion by the partial oxidation. After the synthesis gas thus generated is taken out through the product gas take-out pipe 14, it is sent to a carbon monoxide conversion reactor, where carbon monoxide is shifted and converted into hydrogen by the carbon monoxide conversion reactor to obtain high-purity hydrogen. Get.
【００２０】上記のように、この実施の形態では、部分
酸化における燃焼熱を利用して水蒸気改質を行うため、
炭化水素原料をすべて水素源として有効に利用すること
ができる。しかも、部分酸化部２での反応と水蒸気改質
部５での反応を最適な条件で行わせることができ、高効
率に水素および一酸化炭素を発生することができる。さ
らに、部分酸化反応では、ＮＯX が発生しないため、Ｎ
ＯX 除去用の設備が不要になる。さらに、水蒸気改質部
５のＮｉ触媒の消費量が大幅に減少する。As described above, in this embodiment, since the steam reforming is performed using the heat of combustion in the partial oxidation,
All hydrocarbon raw materials can be effectively used as a hydrogen source. Moreover, the reaction in the partial oxidation section 2 and the reaction in the steam reforming section 5 can be performed under optimal conditions, and hydrogen and carbon monoxide can be generated with high efficiency. Furthermore, the partial oxidation reaction, since the NO X does not occur, N
Equipment for O X removal is not required. Further, the consumption of the Ni catalyst in the steam reforming section 5 is greatly reduced.
【００２１】なお、上記実施の形態では、部分酸化部２
に酸素を導入しているが、これに限定するものではな
く、酸素に代えて空気を導入してもよい。また、部分酸
化部２に炭化水素原料と酸素とスチームを導入し、連結
パイプ６に炭化水素原料を導入しているが、これに限定
するものではなく、部分酸化部２に炭化水素原料と酸素
を導入し、連結パイプ６に炭化水素原料とスチームを導
入してもよい。In the above embodiment, the partial oxidation unit 2
Although oxygen is introduced into the air, the present invention is not limited to this, and air may be introduced instead of oxygen. In addition, a hydrocarbon raw material, oxygen and steam are introduced into the partial oxidation section 2 and a hydrocarbon raw material is introduced into the connecting pipe 6, but the present invention is not limited to this. May be introduced, and a hydrocarbon raw material and steam may be introduced into the connection pipe 6.
【００２２】図１に示す装置において、炭化水素原料と
してブタンを用いた場合を例に挙げて、理論的算出によ
り、その有効性を確認した。その結果を下記の表１に示
す。下記の表１から明らかなように、本発明の方が従来
例に比較して、高効率で水素を発生できることがわか
る。The effectiveness of the apparatus shown in FIG. 1 was confirmed by theoretical calculation, taking as an example the case where butane was used as the hydrocarbon raw material. The results are shown in Table 1 below. As is clear from Table 1 below, it can be seen that the present invention can generate hydrogen with higher efficiency than the conventional example.
【００２３】[0023]
【表１】 [Table 1]
【００２４】[0024]
【発明の効果】以上のように、本発明は、部分酸化反応
用の炭化水素原料と水蒸気改質反応用の炭化水素原料を
分割して反応器に導入する点に、特徴があり、これによ
り、部分酸化部での反応と水蒸気改質部での反応を最適
な条件で行わせることができ、効率よく水素および一酸
化炭素を発生することが可能となる。しかも、部分酸化
反応と水蒸気改質反応それぞれ最適な条件下で行うこと
ができ、制御も簡単である。さらに、従来例と同様に、
簡単な構造である。さらに、部分酸化反応では、ＮＯX
が発生しないため、従来例のようなＮＯX 除去塔２８が
不要になる。さらに、水蒸気改質部に導入する炭化水素
原料の量が大幅に減少するため、水蒸気改質用触媒の消
費量が大幅に減少し、触媒の取り替えピッチを大幅に長
くすることができる。また、本発明の第２の水素製造方
法では、炭化水素原料と、酸素または空気を反応器の部
分酸化部に供給し、この部分酸化部で生成させた合成ガ
スに炭化水素原料と水蒸気を供給している。この方法で
も、上記の第１の水素製造方法と同様の作用・効果を奏
する。一方、本発明の水素製造装置によれば、本発明の
方法を容易に達成することができる。As described above, the present invention is characterized in that a hydrocarbon material for a partial oxidation reaction and a hydrocarbon material for a steam reforming reaction are divided and introduced into a reactor. The reaction in the partial oxidation section and the reaction in the steam reforming section can be performed under optimal conditions, and hydrogen and carbon monoxide can be generated efficiently. In addition, the partial oxidation reaction and the steam reforming reaction can be performed under optimum conditions, respectively, and the control is simple. Furthermore, similar to the conventional example,
It has a simple structure. Furthermore, in the partial oxidation reaction, NO X
Because There does not occur, NO X removal column 28 as in the prior art is not required. Further, since the amount of the hydrocarbon feedstock introduced into the steam reforming section is greatly reduced, the consumption of the steam reforming catalyst is greatly reduced, and the catalyst replacement pitch can be greatly lengthened. In the second hydrogen production method of the present invention, the hydrocarbon raw material and oxygen or air are supplied to the partial oxidation part of the reactor, and the hydrocarbon raw material and steam are supplied to the synthesis gas generated in the partial oxidation part. doing. Also in this method, the same operation and effect as those of the first hydrogen production method are obtained. On the other hand, according to the hydrogen production apparatus of the present invention, the method of the present invention can be easily achieved.
【００２５】本発明において、製品ガス（水素と一酸化
炭素を含む合成ガス）中の一酸化炭素を水素に転化する
ことにより水素を富化するようにした場合には、高純度
水素を主成分とした製品ガスが得られる。一方、製品ガ
ス中に含まれる多量の一酸化炭素を主製品とする場合
は、そのまま精製装置へ送ることが行われる。In the present invention, when hydrogen is enriched by converting carbon monoxide in a product gas (synthesis gas containing hydrogen and carbon monoxide) to hydrogen, high-purity hydrogen is the main component. Product gas is obtained. On the other hand, when the main product is a large amount of carbon monoxide contained in the product gas, the product gas is directly sent to a purification device.
【図１】本発明の一実施の形態を示す概略説明図であ
る。FIG. 1 is a schematic explanatory view showing an embodiment of the present invention.
【図２】従来例の概略説明図である。FIG. 2 is a schematic explanatory view of a conventional example.
【図３】他の従来例の概略説明図である。FIG. 3 is a schematic explanatory view of another conventional example.
１ 反応器 ２ 部分酸化部 ５ 水蒸気改質部 ６ 連結パイプ １０〜１２ 第１原料導入パイプ １３ 第２原料導入パイプ DESCRIPTION OF SYMBOLS 1 Reactor 2 Partial oxidation part 5 Steam reforming part 6 Connecting pipe 10-12 First raw material introduction pipe 13 Second raw material introduction pipe
───────────────────────────────────────────────────── フロントページの続き (72)発明者 末長 純也 大阪府堺市築港新町２丁６番地40 大同ほ くさん株式会社堺工場内 (72)発明者 宮本 英樹 大阪府堺市築港新町２丁６番地40 大同ほ くさん株式会社堺工場内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Junya Suenaga 2-6-6 Chikushinmachi, Sakai City, Osaka Inside Daido Hokusan Co., Ltd. Sakai Plant (72) Inventor Hideki Miyamoto 2-6 Chikushinmachi, Sakai City, Osaka Prefecture 40 Daido Hokusan Co., Ltd. Sakai Plant
Claims (6)
蒸気を反応器の部分酸化部に導入し、この部分酸化部に
おける部分酸化により水素と一酸化炭素との合成ガスを
生成させ、この生成した合成ガスを水蒸気とともに部分
酸化部から取り出したのち上記合成ガスに炭化水素原料
を供給して反応器の水蒸気改質部に導入し、上記部分酸
化による発熱を利用して上記水蒸気改質部における水蒸
気改質を行い、上記水蒸気改質部で生成した合成ガスを
製品ガスとして取り出すようにしたことを特徴とする水
素製造方法。1. A hydrocarbon feedstock, oxygen or air, and steam are introduced into a partial oxidation part of a reactor, and a partial oxidation in the partial oxidation part produces a synthesis gas of hydrogen and carbon monoxide. After removing the synthesized gas together with steam from the partial oxidation section, a hydrocarbon raw material is supplied to the synthesis gas and introduced into the steam reforming section of the reactor, and the heat generated by the partial oxidation is used in the steam reforming section. A method for producing hydrogen, comprising performing steam reforming and extracting a synthesis gas generated in the steam reforming section as a product gas.
器の部分酸化部に導入し、この部分酸化部における部分
酸化により水素と一酸化炭素との合成ガスを生成させ、
この生成した合成ガスを上記部分酸化部から取り出した
のち上記合成ガスに炭化水素原料と水蒸気を供給して反
応器の水蒸気改質部に導入し、上記部分酸化による発熱
を利用して上記水蒸気改質部における水蒸気改質を行
い、上記水蒸気改質部で生成した合成ガスを製品ガスと
して取り出すようにしたことを特徴とする水素製造方
法。2. A hydrocarbon raw material and oxygen or air are introduced into a partial oxidation section of the reactor, and a partial oxidation in the partial oxidation section generates a synthesis gas of hydrogen and carbon monoxide,
After taking out the generated synthesis gas from the partial oxidation section, a hydrocarbon raw material and steam are supplied to the synthesis gas and introduced into the steam reforming section of the reactor, and the steam reforming section utilizes the heat generated by the partial oxidation. A method for producing hydrogen, comprising performing steam reforming in a reforming section, and extracting a synthesis gas generated in the steam reforming section as a product gas.
化することにより水素を富化するようにした請求項１ま
たは２記載の水素製造方法。3. The hydrogen production method according to claim 1, wherein carbon monoxide in the product gas is converted into hydrogen to enrich hydrogen.
質部を直列に配設した反応器と、炭化水素原料と、酸素
または空気と、水蒸気を上記部分酸化部の燃焼器に導入
する第１の原料導入路と、上記部分酸化部と水蒸気改質
部を連結する連結路と、この連結路に炭化水素原料を導
入する第２の原料導入路と、上記水蒸気改質部で生成し
た水素と一酸化炭素の合成ガスを製品ガスとして取り出
す製品ガス取出し路とを設けたことを特徴とする水素製
造装置。4. A reactor in which a partial oxidation section with a combustor and a steam reforming section are arranged in series, a hydrocarbon raw material, oxygen or air, and steam are introduced into the combustor of the partial oxidation section. A first raw material introduction path, a connection path connecting the partial oxidation section and the steam reforming section, a second raw material introduction path for introducing a hydrocarbon raw material into the connection path, and a gas generated by the steam reforming section. A hydrogen production apparatus, comprising: a product gas extraction passage for extracting a synthesis gas of hydrogen and carbon monoxide as a product gas.
質部を直列に配設した反応器と、炭化水素原料と、酸素
または空気を上記部分酸化部の燃焼器に導入する第１の
原料導入路と、上記部分酸化部と水蒸気改質部を連結す
る連結路と、この連結路に炭化水素原料と水蒸気を導入
する第２の原料導入路と、上記水蒸気改質部で生成した
水素と一酸化炭素の合成ガスを製品ガスとして取り出す
製品ガス取出し路とを設けたことを特徴とする水素製造
装置。5. A first reactor in which a partial oxidation unit with a combustor and a steam reforming unit are arranged in series, a hydrocarbon raw material and oxygen or air are introduced into the combustor of the partial oxidation unit. A raw material introduction path, a connection path for connecting the partial oxidation section and the steam reforming section, a second raw material introduction path for introducing a hydrocarbon raw material and steam into the connection path, and hydrogen generated in the steam reforming section. And a product gas take-out path for taking out a synthesis gas of carbon monoxide as a product gas.
手段を設け、この一酸化炭素転化手段により製品ガス中
の一酸化炭素を水素に転化するようにした請求項４また
は５記載の水素製造装置。6. The hydrogen production according to claim 4, wherein a carbon monoxide converting means is provided in the product gas take-out path, and carbon monoxide in the product gas is converted into hydrogen by the carbon monoxide converting means. apparatus.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10049897A JP3947266B2 (en) | 1997-04-17 | 1997-04-17 | Hydrogen production method and apparatus used therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10049897A JP3947266B2 (en) | 1997-04-17 | 1997-04-17 | Hydrogen production method and apparatus used therefor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10291801A true JPH10291801A (en) | 1998-11-04 |
| JP3947266B2 JP3947266B2 (en) | 2007-07-18 |
Family
ID=14275606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10049897A Expired - Fee Related JP3947266B2 (en) | 1997-04-17 | 1997-04-17 | Hydrogen production method and apparatus used therefor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3947266B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101472767B1 (en) * | 2007-05-24 | 2014-12-24 | 에어 워터 가부시키가이샤 | Apparatus and method for producing carbon monoxide gas |
| CN106006553A (en) * | 2016-05-09 | 2016-10-12 | 大连理工大学 | Methanol oxidation and steam reforming staged combined on-line hydrogen production method and equipment |
-
1997
- 1997-04-17 JP JP10049897A patent/JP3947266B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101472767B1 (en) * | 2007-05-24 | 2014-12-24 | 에어 워터 가부시키가이샤 | Apparatus and method for producing carbon monoxide gas |
| CN106006553A (en) * | 2016-05-09 | 2016-10-12 | 大连理工大学 | Methanol oxidation and steam reforming staged combined on-line hydrogen production method and equipment |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3947266B2 (en) | 2007-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US12172896B2 (en) | ATR-based hydrogen process and plant | |
| KR20210151778A (en) | chemical synthesis plant | |
| AU2004221826B2 (en) | Autothermal reformer-reforming exchanger arrangement for hydrogen production | |
| CA3185308C (en) | Low carbon hydrogen fuel | |
| WO2006027175A1 (en) | Process for production of hydrogen and/or carbon monoxide | |
| KR20240028346A (en) | Method and device for producing hydrogen from ammonia | |
| KR20210151776A (en) | chemical synthesis plant | |
| US20240253984A1 (en) | Heat exchange reactor for co2 shift | |
| CA2330302A1 (en) | Method and apparatus for the production of synthesis gas | |
| US20230339747A1 (en) | Syngas stage for chemical synthesis plant | |
| EP4347479A1 (en) | Heat exchange reactor with reduced metal dusting | |
| KR20250008953A (en) | Process of producing power from a gas turbine | |
| US20240101417A1 (en) | Method for preparing a synthesis gas | |
| JP3947266B2 (en) | Hydrogen production method and apparatus used therefor | |
| JPH10291802A (en) | Production method of hydrogen and device therefor | |
| EP4382476A1 (en) | System and process for producing synthetic fuels | |
| WO2024094818A1 (en) | Conversion of unsaturated hydrocarbon containing off-gases for more efficient hydrocarbon production plant | |
| DK202100198A1 (en) | Process for synthesis gas generation | |
| KR960003232B1 (en) | Self heating steam reforming method | |
| EA046288B1 (en) | LOW CARBON HYDROGEN FUEL | |
| JPS608274B2 (en) | Method for producing high calorific value gas from coke oven gas | |
| JPS58194707A (en) | Gasification of hydrocarbon |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Effective date: 20040412 Free format text: JAPANESE INTERMEDIATE CODE: A621 |
|
| A977 | Report on retrieval |
Effective date: 20061101 Free format text: JAPANESE INTERMEDIATE CODE: A971007 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20070116 |
|
| A521 | Written amendment |
Effective date: 20070306 Free format text: JAPANESE INTERMEDIATE CODE: A523 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20070403 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20070413 |
|
| R150 | Certificate of patent (=grant) or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 4 Free format text: PAYMENT UNTIL: 20110420 |
|
| LAPS | Cancellation because of no payment of annual fees |