JPH02116604A - Method for reforming methanol - Google Patents
Method for reforming methanolInfo
- Publication number
- JPH02116604A JPH02116604A JP26938588A JP26938588A JPH02116604A JP H02116604 A JPH02116604 A JP H02116604A JP 26938588 A JP26938588 A JP 26938588A JP 26938588 A JP26938588 A JP 26938588A JP H02116604 A JPH02116604 A JP H02116604A
- Authority
- JP
- Japan
- Prior art keywords
- methanol
- reactor
- catalyzed
- reaction
- plates
- 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims description 20
- 238000002407 reforming Methods 0.000 title claims description 10
- 239000007789 gas Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 238000006057 reforming reaction Methods 0.000 abstract description 3
- 239000000567 combustion gas Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01B—BOILING; BOILING APPARATUS ; EVAPORATION; EVAPORATION APPARATUS
- B01B1/00—Boiling; Boiling apparatus for physical or chemical purposes ; Evaporation in general
- B01B1/005—Evaporation for physical or chemical purposes; Evaporation apparatus therefor, e.g. evaporation of liquids for gas phase reactions
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はメタノールを改質し水素含有ガスを製造する方
法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing hydrogen-containing gas by reforming methanol.
従来のメタノールを改質し水素含有ガスを製造する方法
の一態様を第４図によって説明する。An embodiment of a conventional method for producing hydrogen-containing gas by reforming methanol will be explained with reference to FIG.
仁の態様を実施する装置は、メタノール、純水を供給す
る原料ポンプ１、原料を気化させて反応温度まで昇温す
る原料予熱器２及び過熱器５、触媒を充填した反応管を
有する反応器４、未反応原料等ｔ−凝縮する冷却器５及
び凝縮ｇ、金気液分離する気液分離器８、反応に必要な
熱を供給する熱媒加熱器７と熱媒循環ポンプ６、製品と
してガスを精製する梢製器９よシ構成される。The apparatus for carrying out this embodiment includes a raw material pump 1 that supplies methanol and pure water, a raw material preheater 2 and a superheater 5 that vaporize the raw material and raise the temperature to the reaction temperature, and a reactor having a reaction tube filled with a catalyst. 4. Unreacted raw materials etc. t - Cooler 5 to condense and condensate g, Gas-liquid separator 8 to separate gold gas and liquid, Heat medium heater 7 and heat medium circulation pump 6 that supply the heat necessary for reaction, as a product It is also composed of a canopy refiner 9 for purifying gas.
ｍ科ポンプ１で加圧供給された原料は原料予熱器２およ
び過熱器、５で所定の温度まで昇温され、触媒を充填し
た反応器４でメタノールと水の混合蒸気は水素含有ガス
に改質される。The raw material supplied under pressure by the pump 1 is heated to a predetermined temperature in the raw material preheater 2 and the superheater 5, and the mixed vapor of methanol and water is converted into hydrogen-containing gas in the reactor 4 filled with a catalyst. questioned.
ここで云う水素含有ガスとは水素を５０ ｍｏｂ★（乾
ペース）以上含有するガスのことを指し、水素以外のガ
スの主成分は、炭酸ガス（Ｃｏｘ ）、−酸化炭素（Ｃ
Ｏ）でアシ、次の三つの反応の比率によシそのガス濃度
は決定される。The hydrogen-containing gas referred to here refers to a gas containing 50 mob★ (dry pace) or more of hydrogen, and the main components of the gas other than hydrogen are carbon dioxide (Cox), -carbon oxide (C
The gas concentration is determined by the ratio of the following three reactions:
ＣＨ３０Ｈ→ ２Ｈ２＋ ＣＯ
ＣＨ３０Ｈ＋ ｎＨ２Ｏ→（′２＋ｎ）Ｈ２＋ （＋−
ｎ）Ｃｏ ＋ｎｃＯ２（０＜ｎ＜Ｉ）
ＣＨ３０Ｈ＋ Ｈ，Ｏ→ ５Ｈ，＋ ｃｏ。CH30H→ 2H2+ CO CH30H+ nH2O→('2+n)H2+ (+-
n) Co + ncO2 (0<n<I) CH30H+ H,O→ 5H,+co.
これらの反応は吸熱反応であるため、熱媒加熱器７で加
熱された熱媒で熱を補給している。Since these reactions are endothermic reactions, heat is supplied by the heat medium heated by the heat medium heater 7.
冷却器３で凝縮した未反応原料は気液分離器８で回収し
、原料ラインへ戻され循環使用される。The unreacted raw material condensed in the cooler 3 is recovered in the gas-liquid separator 8, returned to the raw material line, and recycled.
又生成ガスはＭ製器９で精製され製品ガスとして回収さ
れる。Also, the produced gas is purified in the M-former 9 and recovered as a product gas.
前記の通り反応は吸熱反応であり、反応器４はシェル・
アンド・チューブの熱交換器型式となっており、チュー
ブ１ｉｌ１１に触媒を充填し、この触媒層に供給された
原料は触媒との接触反応により水素含有ガスに改質され
る。この反応熱はシェル側の熱媒から供給される。触媒
上での上記反応は、比較的速いため、反応管内での水素
生成速度は伝熱律速となっており、伝熱をよくするため
反応器は２０φ闘〜４０φ籠、−船釣には５０φ載と細
ｂ０従って反応管数が非常に多くなシ触媒充填作業に大
きな労力を必要とする。なお多管式のため構造上シェル
側容積が犬きぐなシ設備が大型となる。一方熱媒側伝熱
係数向上のために仕切板を設ける等複雑な構造を必要と
する。As mentioned above, the reaction is an endothermic reaction, and the reactor 4 is a shell
It is an and-tube heat exchanger type, and the tubes 1il11 are filled with a catalyst, and the raw material supplied to this catalyst bed is reformed into a hydrogen-containing gas through a catalytic reaction with the catalyst. This reaction heat is supplied from the heat medium on the shell side. Since the above reaction on the catalyst is relatively fast, the rate of hydrogen production in the reaction tube is determined by heat transfer.In order to improve heat transfer, the reactor is made of a 20φ to 40φ cage, and a 50φ for boat fishing. Therefore, the number of reaction tubes is very large, and the catalyst filling operation requires a great deal of labor. Since it is a multi-tube type, the volume on the shell side is structurally large, making the equipment large. On the other hand, it requires a complicated structure such as providing a partition plate to improve the heat transfer coefficient on the heat medium side.
又反応熱補充のため熱媒ユニットが必要であり、これら
が製品ガスのコストアップとなっている。Furthermore, a heating medium unit is required to replenish the reaction heat, which increases the cost of the product gas.
本発明は上記した従来法の欠点を解決し、コンパクトで
しかも安価にメタノールを改質する方法を提供しようと
するものである。The present invention aims to solve the above-mentioned drawbacks of the conventional methods and provide a compact and inexpensive method for reforming methanol.
本発明はメタノールを水素含有ガスに改質する方法にお
いて、プレート式熱交換器型反応器のプレートの片面を
触媒化し、該触媒化したプレート面側にメタノールと水
の混合蒸気を通し、プレートの他方面側に加熱媒体を通
すことを特徴とするメタノールの改質方法である。The present invention is a method for reforming methanol into a hydrogen-containing gas, in which one side of a plate of a plate heat exchanger type reactor is catalyzed, and a mixed vapor of methanol and water is passed through the catalyzed plate side. This is a methanol reforming method characterized by passing a heating medium through the other side.
本発明に云うプレートの片面が融媒機能を有するプレー
ト式熱交換器型反応器とは、多回流路型、真交流型、向
硫型があるが、これらのプレートの片面に触媒成分をメ
ツ牛、溶射、蒸着、塗布その他の方法で処理し、プレー
トそのものを触媒化したものである。この触媒化の方法
には種々な方法がある。例えば、触媒成分をイオン化し
プレートにメツキする方法、触媒取分をプレートに溶射
又は蒸着する方法、触媒成分をバインダーと混合しプレ
ートに塗布する方法、触媒成分を粉末冶金法で、プレー
ト上に担持する方法その他多くの方法がある。The plate heat exchanger type reactor in which one side of the plate has a melting medium function as used in the present invention includes a multi-channel type, a cross-flow type, and a sulfur-directing type. The plate itself is catalyzed by treatment using thermal spraying, vapor deposition, coating, or other methods. There are various methods for this catalyzation. For example, methods include ionizing the catalyst component and plating it on the plate, spraying or vapor depositing a catalyst fraction onto the plate, mixing the catalyst component with a binder and applying it to the plate, and supporting the catalyst component on the plate using powder metallurgy. There are many other ways to do this.
これらの方法で触媒化した伝熱プレートは、伝熱面その
ものが反応熱を伴う触媒面で口＃）熱移動が大きく、小
型で、か一つ高性能な反応器である。Heat transfer plates catalyzed by these methods have large heat transfer as the heat transfer surface itself is a catalytic surface that carries reaction heat, and is a small, high-performance reactor.
以下本発明の一態様を図面にそって詳細説明する。One embodiment of the present invention will be described in detail below with reference to the drawings.
第１図は直交流型プレート式熱交換器型反応器の要部を
示したもので、反応部（触媒化した面でグロセスガス流
路ンと加熱部（熱媒体流路）は１層ごとのサンドイッチ
型となっている。反応部と加熱部の伝熱プレート自身が
触媒化機能を有しているため、反応部に粉粒体の触媒を
充填する必要がなく、伝熱プレート内の隙間は構造上最
小にすることができるため、小型で高性能な反応器であ
る。Figure 1 shows the main parts of a cross-flow plate heat exchanger type reactor. It is a sandwich type.Since the heat transfer plates in the reaction section and heating section themselves have a catalytic function, there is no need to fill the reaction section with powder catalyst, and the gaps in the heat transfer plates are It is a small and high-performance reactor because it can be minimized in terms of structure.
第２図は触媒機能を有するプレート式熱交換器型反応器
を用い、熱源として燃焼排ガスを用いたプロセスフロー
である。第２図のプロセスフローの構成機器はメタノー
ル、純水を供給する原料ポンプ１、ｙＡ８Ｆ＋全８Ｆ＋
スで予熱する原料予熱器２及び原料ｔ−蒸発する蒸発器
１０、原料を反応温度まで加熱する過熱器５、プレート
に触媒機能をもたせたプレート式熱交換器型反応器４、
製品ガスを冷却する冷却器３、製品ガス中の凝縮成分を
分離する気液分離器８、凝縮成分を分離した製品ガスを
精製する精製器９及び反応に必要な熱を供給する燃焼ガ
ス発生器１１より構成されている。FIG. 2 is a process flow using a plate heat exchanger type reactor having a catalytic function and using combustion exhaust gas as a heat source. The components of the process flow in Figure 2 are raw material pump 1 that supplies methanol and pure water, yA8F + total 8F +
A raw material preheater 2 for preheating the raw material and an evaporator 10 for evaporating the raw material, a superheater 5 for heating the raw material to the reaction temperature, a plate heat exchanger type reactor 4 in which the plates have a catalytic function,
A cooler 3 that cools the product gas, a gas-liquid separator 8 that separates condensed components from the product gas, a purifier 9 that refines the product gas from which the condensed components have been separated, and a combustion gas generator that supplies the heat necessary for the reaction. It is composed of 11.
第３図は、原料蒸発器１０、原料過熱器５、反応器４゛
をそれぞれ燃焼排ガスの温度レベルに応じて順次配列し
た・プレート式熱交換器型反応器を用いたプロセス７０
−を示すものであり、より小型でかつ高性能なメタノー
ル改質方法である。FIG. 3 shows a process 70 using a plate heat exchanger type reactor in which a raw material evaporator 10, a raw material superheater 5, and a reactor 4 are arranged in sequence according to the temperature level of the combustion exhaust gas.
-, it is a smaller and higher performance methanol reforming method.
〔実施例１〕
第５図に示したプレート式熱交換型反応器にメタノール
を工２ｋｇ／ｈ、純水を２．７ｋｐ／ｈ供給し、８００
℃の燃焼排ガスを１０ Ｎｍ３／ｈ供給し、メタノール
改質反応を実施した。[Example 1] Methanol was supplied at 2 kg/h and pure water at 2.7 kp/h into the plate heat exchange reactor shown in Fig. 5.
C. combustion exhaust gas was supplied at 10 Nm3/h to carry out a methanol reforming reaction.
プレート式熱交換型反応器の高温側（燃焼排ガス入口側
）のプレートには、原料蒸気の通る面にアルミナを溶射
したものを所定の濃度の塩化白金酸水溶液に含浸し乾燥
、焼成後、水素還元して白金を担持させたプレートを、
また低温側（燃焼排ガス出口側）のプレートには、原料
蒸気の通る面に融メツキ法により鋼、亜鉛をメツキした
プレートを配置したプレート式熱交換型反応器を用いて
メタノールの改質反応を行ったところ、表１に示す結果
が得られた。The plate on the high temperature side (combustion exhaust gas inlet side) of the plate heat exchange reactor is sprayed with alumina on the surface through which the raw material vapor passes, impregnated with a chloroplatinic acid aqueous solution of a predetermined concentration, dried, fired, and heated with hydrogen. A plate that has been reduced to support platinum,
In addition, on the low temperature side (combustion exhaust gas outlet side), a plate type heat exchange reactor is used, in which a plate plated with steel and zinc using the hot-dip plating method is placed on the surface through which the raw material vapor passes, to carry out the methanol reforming reaction. As a result, the results shown in Table 1 were obtained.
表 １
〔実施例２〕
実施例１における純水の供給をα２ｋｐ／ｈとした以外
は実施例１と同じようにして実施したところ、表２に示
す・結果が得られた。Table 1 [Example 2] The same procedure as in Example 1 was carried out except that the pure water supply in Example 1 was changed to α2kp/h, and the results shown in Table 2 were obtained.
表 ２ 業的価値は極めて筒い。Table 2 The commercial value is extremely significant.
第１図は本発明に使用する触媒機能を有したプレート式
熱交換器反応装置の一例の概略図、第２図及び第３図は
本発明方法の態様を示すプロセスフロー図、第４図は従
来の管型反応器を使用したメタノール改質法のプロセス
フロー図である。
〔発明の効果〕Figure 1 is a schematic diagram of an example of a plate heat exchanger reactor having a catalytic function used in the present invention, Figures 2 and 3 are process flow diagrams showing aspects of the method of the present invention, and Figure 4 is a 1 is a process flow diagram of a methanol reforming method using a conventional tubular reactor. 〔Effect of the invention〕
Claims (1)
レート式熱交換器型反応器のプレートの片面を触媒化し
、該触媒化したプレート面側にメタノールと水の混合蒸
気を通し、プレートの他方面側に加熱媒体を通すことを
特徴とするメタノールの改質方法。In a method for reforming methanol into hydrogen-containing gas, one side of the plate of a plate heat exchanger type reactor is catalyzed, a mixed vapor of methanol and water is passed through the catalyzed plate side, and the other side of the plate is catalyzed. A method for reforming methanol, which comprises passing a heating medium through.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63269385A JP2607644B2 (en) | 1988-10-27 | 1988-10-27 | Methanol reforming method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63269385A JP2607644B2 (en) | 1988-10-27 | 1988-10-27 | Methanol reforming method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02116604A true JPH02116604A (en) | 1990-05-01 |
| JP2607644B2 JP2607644B2 (en) | 1997-05-07 |
Family
ID=17471672
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63269385A Expired - Fee Related JP2607644B2 (en) | 1988-10-27 | 1988-10-27 | Methanol reforming method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2607644B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0369503A (en) * | 1989-08-10 | 1991-03-25 | Fuji Electric Co Ltd | Fuel reformer |
| EP0578218A2 (en) * | 1992-07-08 | 1994-01-12 | Air Products And Chemicals, Inc. | Reformation in a plate-fin heat exchanger |
| JPH10297904A (en) * | 1997-01-22 | 1998-11-10 | Haldor Topsoee As | Production of synthesis gas by steam reforming using material having catalytic action |
| JP2001064001A (en) * | 1999-07-15 | 2001-03-13 | Haldor Topsoe As | Catalytic steam reforming method of hydrocarbon supply material |
| JP2004044905A (en) * | 2002-07-11 | 2004-02-12 | Honda Motor Co Ltd | Evaporator |
| US7490580B2 (en) | 2002-07-11 | 2009-02-17 | Honda Motor Co., Ltd. | Vaporizer that vaporizes a liquid to generate vapor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0230601A (en) * | 1988-07-19 | 1990-02-01 | Agency Of Ind Science & Technol | Apparatus for reforming methanol |
-
1988
- 1988-10-27 JP JP63269385A patent/JP2607644B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0230601A (en) * | 1988-07-19 | 1990-02-01 | Agency Of Ind Science & Technol | Apparatus for reforming methanol |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0369503A (en) * | 1989-08-10 | 1991-03-25 | Fuji Electric Co Ltd | Fuel reformer |
| EP0578218A2 (en) * | 1992-07-08 | 1994-01-12 | Air Products And Chemicals, Inc. | Reformation in a plate-fin heat exchanger |
| EP0578218A3 (en) * | 1992-07-08 | 1994-10-26 | Air Prod & Chem | Reformation in a plate-fin heat exchanger. |
| JPH10297904A (en) * | 1997-01-22 | 1998-11-10 | Haldor Topsoee As | Production of synthesis gas by steam reforming using material having catalytic action |
| JP4521735B2 (en) * | 1997-01-22 | 2010-08-11 | ハルドール・トプサー・アクチエゼルスカベット | Method for producing synthesis gas by steam reforming using catalytic equipment |
| JP2001064001A (en) * | 1999-07-15 | 2001-03-13 | Haldor Topsoe As | Catalytic steam reforming method of hydrocarbon supply material |
| JP2004044905A (en) * | 2002-07-11 | 2004-02-12 | Honda Motor Co Ltd | Evaporator |
| US7490580B2 (en) | 2002-07-11 | 2009-02-17 | Honda Motor Co., Ltd. | Vaporizer that vaporizes a liquid to generate vapor |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2607644B2 (en) | 1997-05-07 |
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