JPH10194715A - Production of carbon monoxide - Google Patents
Production of carbon monoxideInfo
- Publication number
- JPH10194715A JPH10194715A JP9001533A JP153397A JPH10194715A JP H10194715 A JPH10194715 A JP H10194715A JP 9001533 A JP9001533 A JP 9001533A JP 153397 A JP153397 A JP 153397A JP H10194715 A JPH10194715 A JP H10194715A
- Authority
- JP
- Japan
- Prior art keywords
- methyl formate
- carbon monoxide
- zinc oxide
- catalyst
- reaction
- 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
Classifications
-
- 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
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ギ酸メチルから一
酸化炭素を製造する方法に関するものである。一酸化炭
素はＣ１化学の主原料として、またカルボニル化反応の
原料として重要な物質である。TECHNICAL FIELD The present invention relates to a method for producing carbon monoxide from methyl formate. Carbon monoxide is an important substance as a main raw material for C1 chemistry and as a raw material for the carbonylation reaction.
【０００２】[0002]
【従来の技術】ギ酸メチルを分解して一酸化炭素を得る
方法は、Ｃ１化学の主原料としてメタノールからギ酸メ
チルが安価に得られるようになり、ギ酸メチルが液体で
輸送できることから、高価な設備を用いることなしに、
低温で容易に一酸化炭素を得る方法として注目されてい
る。このようなギ酸メチルを分解して一酸化炭素を得る
方法としては、（１）担持されたアルカリ土類金属酸化
物からなる固体触媒を用いて２００〜５００℃の温度で
で気相熱分解する方法（米国特許第３８１２２１０
号）、（２）活性炭を触媒とし２００〜５５０℃の温度
で気相熱分解する方法（特開昭５２−３６６０９号）、
（３）メタノールと共存するギ酸メチルをナトリウムメ
チラートを触媒として１７．２ＭＰａ以下の圧力および
３５〜２００℃の温度で液相下熱分解する方法（米国特
許第３７１６６１９号）等が知られている。2. Description of the Related Art In a method of decomposing methyl formate to obtain carbon monoxide, methyl formate can be obtained from methanol as a main raw material of C1 chemistry at low cost, and methyl formate can be transported in a liquid form, so that expensive equipment is required. Without using
It is attracting attention as a method for easily obtaining carbon monoxide at low temperatures. As a method for obtaining carbon monoxide by decomposing such methyl formate, (1) gas phase thermal decomposition is performed at a temperature of 200 to 500 ° C. using a solid catalyst comprising a supported alkaline earth metal oxide. Method (US Pat. No. 3,812,210)
(2) a method of performing a gas phase pyrolysis at a temperature of 200 to 550 ° C. using activated carbon as a catalyst (JP-A-52-36609);
(3) A method in which methyl formate coexisting with methanol is pyrolyzed in the liquid phase at a pressure of 17.2 MPa or less and a temperature of 35 to 200 ° C. using sodium methylate as a catalyst (US Pat. No. 3,716,619) is known. .
【０００３】[0003]
【発明が解決しようとする課題】従来技術に記載した上
記の方法において、（１）および（２）の方法は気相で
２５０℃以上の温度で行い蒸発潜熱を必要とするためた
め熱エネルギー的に不利であるだけでなく不純物の副生
が多く、一酸化炭素選択率は低い。（３）の方法は液相
下の反応で条件が温和な点で優れているが、ナトリウム
メチラートが強塩基性であることによる欠点を有する。
すなわち反応時には水分により水酸化ナトリウムさらに
はギ酸ナトリウム等の不純物を副生し触媒損失するだけ
でなく反応系に不溶性の塩類が析出し、装置の運転に支
障を来すことさえある。また取り扱う際、二酸化炭素や
水に触れるなどして失活すると再生は容易でない。さら
に皮膚への刺激が非常に強いためそのとり扱いには細心
の注意を要する。本発明の目的はギ酸メチルを分解して
一酸化炭素を得る方法において、低温で高活性を有する
触媒を開発し、一酸化炭素を工業的に有利に製造する方
法を提供することである。In the above methods described in the prior art, the methods (1) and (2) are performed at a temperature of 250 ° C. or more in the gas phase and require latent heat of evaporation. Not only is it disadvantageous, but also there are many by-products of impurities, and the carbon monoxide selectivity is low. The method (3) is excellent in that the reaction is carried out in a liquid phase and the conditions are mild, but has a drawback due to the strong basicity of sodium methylate.
That is, at the time of the reaction, impurities such as sodium hydroxide and sodium formate are produced as by-products due to moisture, and not only catalyst loss, but also insoluble salts precipitate in the reaction system, which may even hinder the operation of the apparatus. Also, when handling, if it is deactivated by touching carbon dioxide or water, regeneration is not easy. Furthermore, since the skin is very irritating, careful handling is required. An object of the present invention is to develop a catalyst having a high activity at a low temperature in a method for decomposing methyl formate to obtain carbon monoxide, and to provide a method for industrially advantageously producing carbon monoxide.
【０００４】[0004]
【課題を解決するための手段】発明者等は上記の如き課
題を有するギ酸メチルを分解して一酸化炭素を得る方法
について鋭意研究した結果、フッ化アルカリと酸化亜鉛
を組み合わせた新規な触媒が、液相でのギ酸メチル分解
反応による一酸化炭素の製造において高活性、高選択率
を発現し、またフッ化アルカリおよび酸化亜鉛は強塩基
でないことから取扱が容易で工業的に有利に一酸化炭素
を製造できることを見い出し、本発明に到達した。すな
わち本発明は、フッ化アルカリ及び酸化亜鉛の存在下、
ギ酸メチルを液相下で分解することを特徴とする一酸化
炭素の製造方法である。The inventors of the present invention have conducted intensive studies on a method for obtaining carbon monoxide by decomposing methyl formate, which has the above-mentioned problems, and as a result, a novel catalyst combining alkali fluoride and zinc oxide has been found. High activity and high selectivity in the production of carbon monoxide by decomposition of methyl formate in the liquid phase. Also, alkali fluoride and zinc oxide are not strong bases, so they are easy to handle and industrially advantageous. The inventors have found that carbon can be produced, and have reached the present invention. That is, the present invention, in the presence of alkali fluoride and zinc oxide,
A method for producing carbon monoxide, comprising decomposing methyl formate in a liquid phase.
【０００５】[0005]
【発明の実施の形態】本発明の方法では触媒としてフッ
化アルカリと酸化亜鉛を併用する。フッ化アルカリと酸
化亜鉛は単独で用いても活性は極めて低いが、両者を併
用することにより、驚くべきことに活性が著しく増大す
る。またフッ化アルカリおよび酸化亜鉛は、ナトリウム
メチラートほど皮膚への刺激が強くないので、工業的に
も取扱いが容易である。フッ化アルカリは周期律表Ｉａ
族元素のフッ化物であって、フッ化ナトリウム、フッ化
カリウム、フッ化セシウムなどが挙げられる。フッ化ア
ルカリはＣＯ2と反応しないため空気中のＣＯ2 によっ
て失活することもなく、吸湿しても１００℃以上で乾燥
して使用すればよく、空気中での取り扱いが可能であ
る。BEST MODE FOR CARRYING OUT THE INVENTION In the method of the present invention, an alkali fluoride and zinc oxide are used in combination as a catalyst. Although the activities of alkali fluoride and zinc oxide are extremely low when used alone, surprisingly, the activity is significantly increased by using both together. In addition, alkali fluoride and zinc oxide are not so irritating to the skin as sodium methylate, and therefore are easy to handle industrially. Alkali fluoride is in the periodic table Ia
It is a fluoride of a group element, such as sodium fluoride, potassium fluoride, and cesium fluoride. Since alkali fluoride does not react with CO 2 , it does not deactivate due to CO 2 in the air. Even if it absorbs moisture, it may be dried at 100 ° C. or more and used, and can be handled in the air.
【０００６】酸化亜鉛はそのまま市販品を用いるか、ま
たはアルミナ、シリカその他の担体に担持したもの、あ
るいは共沈法その他の方法により担体成分を加えて調製
したものが用いられる。酸化亜鉛は取り扱いに際してＣ
Ｏ2 と接触しないことが望ましく、２００〜８００℃で
前処理することにより容易に最高の活性を発現する。フ
ッ化アルカリと酸化亜鉛のモル比は０．０５〜５０であ
り、好ましくは０．１〜１０である。As the zinc oxide, a commercially available product may be used as it is, a product supported on alumina, silica or another carrier, or a product prepared by adding a carrier component by a coprecipitation method or another method. When handling zinc oxide, C
It is desirable not to come into contact with O 2, and the highest activity is easily exhibited by pretreatment at 200 to 800 ° C. The molar ratio of alkali fluoride to zinc oxide is 0.05 to 50, preferably 0.1 to 10.
【０００７】本発明における原料ギ酸メチルは工業用グ
レードをそのまま使用することができるが、使用に先だ
って乾燥剤を用いるなどして、水分を極力少なくするこ
とが好ましい。ギ酸メチルと触媒のモル比は特に制限さ
れないが、５０：１〜５００：１が好ましい。ギ酸メチ
ル分解の反応温度は１００℃からギ酸メチルの臨界温度
未満、好ましくは１２０℃から２００℃である。反応圧
力は、反応器内で安定に液相を保つ必要から反応温度に
おけるギ酸メチルの蒸気圧以上の反応圧力を用いること
が望ましい。反応圧力とギ酸メチル蒸気分圧との差は窒
素、アルゴン、ヘリウムなどの不活性ガス及び分解ガス
で補われる。本発明に従う反応方式は、原料と触媒が接
触する方法なら特に制限はなく、回分方式、流通方式の
いずれも可能である。As the raw material methyl formate in the present invention, an industrial grade can be used as it is, but it is preferable to reduce the water content as much as possible by using a desiccant prior to use. The molar ratio between methyl formate and the catalyst is not particularly limited, but is preferably from 50: 1 to 500: 1. The reaction temperature for methyl formate decomposition is from 100 ° C. to below the critical temperature of methyl formate, preferably from 120 ° C. to 200 ° C. As the reaction pressure, it is desirable to use a reaction pressure equal to or higher than the vapor pressure of methyl formate at the reaction temperature because it is necessary to maintain a stable liquid phase in the reactor. The difference between the reaction pressure and the methyl formate vapor partial pressure is compensated by an inert gas such as nitrogen, argon, and helium and a decomposition gas. The reaction system according to the present invention is not particularly limited as long as the raw material and the catalyst are in contact with each other, and may be any of a batch system and a distribution system.
【０００８】[0008]
【実施例】以下に実施例により本発明をさらに具体的に
説明するが、本発明がこれらの実施例で制限されるもの
でない。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
【０００９】実施例１ 内容積１００ｍｌのステンレス製オートクレーブにフッ
化カリウム０．３２ｇ、酸化亜鉛０．３０ｇ、ギ酸メチ
ル１７６ｍｍｏｌを充填した。オートクレーブの内部を
窒素ガスで充分に置換した後、振盪しながら１８０℃に
加熱し、２時間振盪反応の後、オートクレーブを水中で
冷却した。オートクレーブの内部ガスを徐々にパージ
し、ガス量を計量するとともに組成を分析した。オート
クレーブ圧力が大気圧になったら内容物を取り出し、秤
量したのち分析した。その結果、一酸化炭素の収率は３
０．１％であり、生成ガス中のＣＯ／Ｈ2 のモル比は９
９．７５／０．２５であった。Example 1 A stainless steel autoclave having an inner volume of 100 ml was charged with 0.32 g of potassium fluoride, 0.30 g of zinc oxide and 176 mmol of methyl formate. After sufficiently replacing the inside of the autoclave with nitrogen gas, the autoclave was heated to 180 ° C. with shaking, and after a shaking reaction for 2 hours, the autoclave was cooled in water. The gas inside the autoclave was gradually purged, the amount of gas was measured, and the composition was analyzed. When the autoclave pressure reached atmospheric pressure, the contents were taken out, weighed and analyzed. As a result, the yield of carbon monoxide was 3
0.1%, and the molar ratio of CO / H 2 in the product gas is 9%.
It was 9.75 / 0.25.
【００１０】実施例２ 内部撹拌装置を有する内容積１００ｍｌのステンレス製
槽型オートクレーブにフッ化カリウム１．２ｇ、酸化亜
鉛１．６ｇ、ギ酸メチル８３３ｍｍｏｌを充填した。内
部を窒素ガスで充分に置換し、窒素ガス圧力４．９ＭＰ
ａとした。内部を撹拌しながら１８０℃に加熱した。反
応の進行とともにガスが生成するので、圧力が４．９Ｍ
Ｐａ一定になるようにガスを抜き出しながら２時間反応
した後、オートクレーブを水中で冷却し、反応を停止し
た。オートクレーブのバルブを開いて内部ガスを徐々に
パージし、ガス量を計量するとともに組成を分析した。
オートクレーブ圧力が大気になったら内容物を取り出
し、秤量したのち分析した。その結果、一酸化炭素の収
率は８８．３％であり、生成ガス中のＣＯ／Ｈ2 のモル
比は９９．９５／０．０５であった。EXAMPLE 2 A stainless steel autoclave having an internal volume of 100 ml and having an internal stirring device was charged with 1.2 g of potassium fluoride, 1.6 g of zinc oxide and 833 mmol of methyl formate. The inside is sufficiently replaced with nitrogen gas, and nitrogen gas pressure is 4.9MP.
a. The inside was heated to 180 ° C. with stirring. Since gas is generated as the reaction proceeds, the pressure is 4.9M
After reacting for 2 hours while extracting gas so that Pa became constant, the autoclave was cooled in water to stop the reaction. The internal gas was gradually purged by opening the autoclave valve, the gas amount was measured, and the composition was analyzed.
When the autoclave pressure became atmospheric, the contents were taken out, weighed and analyzed. As a result, the yield of carbon monoxide was 88.3%, and the molar ratio of CO / H 2 in the produced gas was 99.95 / 0.05.
【００１１】実施例３ フッ化セシウム０．８６ｇ、酸化亜鉛０．３２ｇ、ギ酸
メチル１６７ｍｍｏｌを充填し、実施例１と同様に反応
を行った。その結果、一酸化炭素の収率は９０．９％で
あり、生成ガス中のＣＯ／Ｈ2 のモル比は９８．６／
１．４であった。Example 3 0.86 g of cesium fluoride, 0.32 g of zinc oxide and 167 mmol of methyl formate were charged, and the reaction was carried out in the same manner as in Example 1. As a result, the yield of carbon monoxide was 90.9%, and the molar ratio of CO / H 2 in the product gas was 98.6 /.
1.4.
【００１２】比較例１〜２ 内容積１００ｍｌのステンレス製オートクレーブに、所
定量の触媒とギ酸メチルを充填した。オートクレーブの
内部を窒素ガスで充分に置換した後、振盪しながら１８
０℃に加熱した。２時間振盪しながら反応の後、オート
クレーブを水中で冷却、反応を停止した。オートクレー
ブのバルブを開いて内部ガスを徐々にパージし、ガス量
を計量するとともに組成を分析した。オートクレーブ圧
力が大気になったら蓋を開けて内容物を取り出し、秤量
したのち分析した。反応条件と結果を表１に示す。Comparative Examples 1 and 2 A predetermined amount of a catalyst and methyl formate were charged in a stainless steel autoclave having an internal volume of 100 ml. After sufficiently replacing the inside of the autoclave with nitrogen gas, the autoclave is shaken for 18 hours.
Heated to 0 ° C. After the reaction with shaking for 2 hours, the autoclave was cooled in water to stop the reaction. The internal gas was gradually purged by opening the autoclave valve, the gas amount was measured, and the composition was analyzed. When the autoclave pressure became atmospheric, the lid was opened and the contents were taken out, weighed and analyzed. Table 1 shows the reaction conditions and the results.
【００１３】[0013]
【表１】比較例 １ 2 触媒（触媒量) ZnO(0.31g) KF(0.32g) ギ酸メチル仕込量(mmol) 172 167 反応温度（℃) 180 180 一酸化炭素収率(mol%) 0.5 0.0 一酸化炭素選択率(%) 100 − Comparative Example 1 2 Catalyst (catalytic amount) ZnO (0.31 g) KF (0.32 g) Methyl formate charge (mmol) 172 167 Reaction temperature (° C) 180 180 Carbon monoxide yield (mol%) 0.5 0.0 Carbon monoxide selectivity (%) 100 −
【００１４】[0014]
【発明の効果】以上の比較例からフッ化カリウムまたは
酸化亜鉛のみではギ酸メチルの分解活性が極めて低い
が、フッ化カリウムおよび酸化亜鉛からなる触媒を用い
る本発明の実施例ではギ酸メチル分解活性が高いことが
分かる。本発明の触媒は強塩基でないので取扱が容易で
あり、液相下ギ酸メチルを分解することにより高選択率
で工業的に有利に一酸化炭素を製造することができるこ
とから、本発明の産業上の意義は大きい。According to the above comparative examples, the decomposition activity of methyl formate is extremely low only with potassium fluoride or zinc oxide. However, in the embodiment of the present invention using a catalyst comprising potassium fluoride and zinc oxide, the decomposition activity of methyl formate is low. It turns out that it is high. Since the catalyst of the present invention is not a strong base, it is easy to handle, and carbon monoxide can be industrially advantageously produced at a high selectivity by decomposing methyl formate in the liquid phase. Is significant.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 江端 秀司 新潟県新潟市太夫浜字新割182番地 三菱 瓦斯化学株式会社新潟研究所内 (72)発明者 中村 賢司 新潟県新潟市太夫浜字新割182番地 三菱 瓦斯化学株式会社新潟研究所内 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Hideji Ebata 182 Niigata-shi Niigata City Niigata Research Institute Niigata Research Institute (72) Inventor Kenji Nakamura Kenji Nakamura Niigata Niigata City Niigata City Niigata 182 Address: Niigata Research Laboratory, Mitsubishi Gas Chemical Co., Ltd.
Claims (1)
酸メチルを液相下で分解することを特徴とする一酸化炭
素の製造方法。1. A method for producing carbon monoxide, comprising decomposing methyl formate in a liquid phase in the presence of alkali fluoride and zinc oxide.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00153397A JP3931928B2 (en) | 1997-01-08 | 1997-01-08 | Carbon monoxide production method |
| DE69706514T DE69706514T2 (en) | 1997-01-08 | 1997-12-31 | Method for the recovery and use of heat by using chemical energy in the synthesis and cleavage of methyl formate |
| EP97123031A EP0853075B1 (en) | 1997-01-08 | 1997-12-31 | Method for heat recovery and utilization by use of chemical energy of synthesis and decomposition of methyl formate |
| US09/004,101 US5965769A (en) | 1997-01-08 | 1998-01-07 | Method for heat recovery and utilization by use of chemical energy of synthesis and decomposition of methyl formate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00153397A JP3931928B2 (en) | 1997-01-08 | 1997-01-08 | Carbon monoxide production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10194715A true JPH10194715A (en) | 1998-07-28 |
| JP3931928B2 JP3931928B2 (en) | 2007-06-20 |
Family
ID=11504167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP00153397A Expired - Fee Related JP3931928B2 (en) | 1997-01-08 | 1997-01-08 | Carbon monoxide production method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3931928B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002114509A (en) * | 2000-09-29 | 2002-04-16 | Mitsubishi Gas Chem Co Inc | Method for producing carbon monoxide |
-
1997
- 1997-01-08 JP JP00153397A patent/JP3931928B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002114509A (en) * | 2000-09-29 | 2002-04-16 | Mitsubishi Gas Chem Co Inc | Method for producing carbon monoxide |
| JP4609613B2 (en) * | 2000-09-29 | 2011-01-12 | 三菱瓦斯化学株式会社 | Carbon monoxide production method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3931928B2 (en) | 2007-06-20 |
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