JPH07112946A - Production of methanol by partial oxidation of methane - Google Patents
Production of methanol by partial oxidation of methaneInfo
- Publication number
- JPH07112946A JPH07112946A JP28071793A JP28071793A JPH07112946A JP H07112946 A JPH07112946 A JP H07112946A JP 28071793 A JP28071793 A JP 28071793A JP 28071793 A JP28071793 A JP 28071793A JP H07112946 A JPH07112946 A JP H07112946A
- Authority
- JP
- Japan
- Prior art keywords
- methane
- methanol
- temperature region
- oxygen
- gas
- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は，メタンまたはメタンを
主成分とする炭化水素ガスを酸素または含酸素ガスの存
在下で反応させて，メタノールを合成する方法に関す
る。TECHNICAL FIELD The present invention relates to a method for synthesizing methanol by reacting methane or a hydrocarbon gas containing methane as a main component in the presence of oxygen or an oxygen-containing gas.
【０００２】[0002]
【従来の技術】メタノールはそれ自体で燃料，溶剤およ
びホルマリン等の化学製品の原料として有用である。ま
た，重合することでガソリン等の液体燃料にすることも
できるので，石油に依存しないエネルギー資源として極
めて重要である。メタンは，天然ガスの主成分として世
界に豊富に存在する資源であるが，その反応性の低さの
ため，そのほとんどが燃料として消費されており，化学
工業原料としての利用は限られていた。しかし，石油資
源の枯渇が叫ばれて以来，メタンの有効利用が重要な課
題となっている。Methanol is useful by itself as a raw material for fuels, solvents and chemical products such as formalin. In addition, it can be made into a liquid fuel such as gasoline by polymerizing it, which is extremely important as an energy resource that does not depend on petroleum. Methane is an abundant resource that exists abundantly in the world as the main component of natural gas, but due to its low reactivity, most of it is consumed as fuel, and its use as a raw material for chemical industry was limited. . However, effective use of methane has become an important issue since the depletion of petroleum resources was called for.
【０００３】従来のメタンを原料としたメタノールの商
業生産は，水蒸気改質法によって合成ガスを得て，この
合成ガスからCr/Zn系触媒を用いてメタノールを合成す
る方法で行なわれている。しかし，メタンの水蒸気改質
法は大きな吸熱反応のため，高温と多大なエネルギーを
必要とし，また，プロセスも複雑であるため，メタンか
ら合成ガスを経由しないメタノールの製造法の開発が期
待されている。そこで，メタンからメタノールを一段で
合成する方法として，メタンの部分酸化による方法が提
案されている。例えば，英国特許第２，１９６，３３５
号には３００〜５００℃，１０〜１００気圧の条件下，
メタンの酸素による部分酸化でメタノールを合成する方
法が開示されている。Conventionally, commercial production of methanol using methane as a raw material is carried out by a method in which synthesis gas is obtained by a steam reforming method and methanol is synthesized from this synthesis gas using a Cr / Zn-based catalyst. However, since the steam reforming method of methane requires a high temperature and a large amount of energy due to a large endothermic reaction, and the process is complicated, it is expected to develop a method for producing methanol without passing synthesis gas from methane. There is. Therefore, a method based on partial oxidation of methane has been proposed as a method for synthesizing methanol from methane in one step. For example, British Patent No. 2,196,335
No. 300-500 ° C, 10-100 atm pressure,
A method for synthesizing methanol by partial oxidation of methane with oxygen is disclosed.
【０００４】[0004]
【発明が解決しようとする課題】しかし，上記特許では
スケールアップすると高選択率が得られないという問題
があり，より安価な製造方法の開発が期待されている。
一方，上記特許の方法を用いて５００℃以上の高温で反
応した場合では，高温ほどメチルラジカルの発生は有利
となるが，高温ほど生成したメタノールは不安定で一酸
化炭素や二酸化炭素に分解しやすいという二律相反があ
る。本発明は従来の問題点を解決し，メタンからより安
価にメタノールを製造することを目的とするものであ
る。However, in the above patent, there is a problem that a high selectivity cannot be obtained when scaled up, and development of a cheaper manufacturing method is expected.
On the other hand, when the method of the above patent is used and the reaction is carried out at a high temperature of 500 ° C. or higher, the higher the temperature, the more advantageous the generation of methyl radicals, but the higher the temperature, the more stable the generated methanol is and is decomposed into carbon monoxide and carbon dioxide. There is a trade-off that it is easy. The present invention aims to solve the conventional problems and to produce methanol from methane more inexpensively.
【０００５】[0005]
【課題を解決するための手段】本発明者らはメタンの部
分酸化反応時に，反応器中に８００℃以上の高温領域と
４００℃以下の低温領域を部分的につくることができる
反応装置を用いることによって，メタンから高選択的に
メタノールを製造し得ることを見出し，この知見に基づ
き，本発明を完成するに至った。The present inventors use a reactor capable of partially forming a high temperature region of 800 ° C. or higher and a low temperature region of 400 ° C. or lower in the reactor during the partial oxidation reaction of methane. As a result, they have found that methanol can be produced from methane with high selectivity, and have completed the present invention based on this finding.
【０００６】すなわち本発明の方法は，上記の反応装置
を用いて，メタンまたはメタンを主成分とする炭化水素
ガスを酸素または含酸素ガスの存在下で反応させてメタ
ノールを合成するに際し，８００℃以上の高温領域で発
生したメチルラジカルなどのメタン活性化物をすみやか
に４００℃以下の低温領域に移動させ、それを該低温領
域で酸素と反応させることによって，生成したメタノー
ルの分解を抑制して効率よくメタノール合成することを
特徴とするものである。また、上記全原料ガス中に３０
Ｖｏｌ％以下の水素を共存させてもよい。水素を共存さ
せるとメタノール収率がさらに向上する。しかしながら
３０Ｖｏｌ％を超えると、水素の酸化反応が促進されて
メタノール合成反応に必要な酸素が消費されてしまうた
め、および全原料ガス中のメタンと酸素の割合が相対的
に減少しすぎて、反応効率が低下するため好ましくな
い。That is, according to the method of the present invention, when methane or a hydrocarbon gas containing methane as a main component is reacted in the presence of oxygen or an oxygen-containing gas to synthesize methanol by using the above-mentioned reactor, 800 ° C. Methane activated compounds such as methyl radicals generated in the above high temperature region are promptly moved to a low temperature region of 400 ° C. or lower and reacted with oxygen in the low temperature region to suppress decomposition of generated methanol and improve efficiency. It is characterized in that methanol is often synthesized. In addition, it is 30
Vol% or less of hydrogen may coexist. The coexistence of hydrogen further improves the yield of methanol. However, if it exceeds 30 Vol%, the oxidation reaction of hydrogen is promoted and oxygen necessary for the methanol synthesis reaction is consumed, and the ratio of methane and oxygen in the total raw material gas is relatively decreased, and the reaction It is not preferable because the efficiency is lowered.
【０００７】本発明のメタノール合成反応は以下の様に
行なわれる。すなわち，メタンと酸素は，メタン／酸素
（モル比）＝５以上，好ましくは１０以上，さらに好ま
しくは２０以上で混合して用いる。モル比が５未満では
好ましくない二酸化炭素の生成が多くなる。このとき，
希釈剤として窒素，ヘリウムまたはアルゴン等の不活性
ガスを共存させることや希釈剤と酸化剤を兼ねて空気を
用いることは差し支えない。水素を共存させる場合の添
加量は，全原料ガス中における添加率として３０vol％
以下，好ましくは０.５〜１０vol％，さらに好ましくは
１〜７vol％である。The methanol synthesis reaction of the present invention is carried out as follows. That is, methane and oxygen are used in a mixture of methane / oxygen (molar ratio) = 5 or more, preferably 10 or more, more preferably 20 or more. When the molar ratio is less than 5, undesired carbon dioxide is produced in a large amount. At this time,
It does not matter that an inert gas such as nitrogen, helium, or argon coexists as the diluent, or that air serves as both the diluent and the oxidizer. When hydrogen coexists, the amount of addition is 30 vol% as an addition rate in all raw material gases.
Below, it is preferably 0.5 to 10 vol%, more preferably 1 to 7 vol%.
【０００８】これらの混合ガスを，通常８００℃以上の
高温領域と４００℃以下の低温領域，好ましくは１００
０℃以上の高温領域と３００℃以下の低温領域を部分的
につくることができる反応装置に供給して反応を行な
う。高温領域が８００℃未満であるとメチルラジカルな
どのメタン活性化物が発生しにくく，低温領域が４００
℃を超えると二酸化炭素の生成が多くなる。These mixed gases are generally used in a high temperature region of 800 ° C. or higher and a low temperature region of 400 ° C. or lower, preferably 100 ° C.
The reaction is carried out by supplying it to a reactor capable of partially forming a high temperature region of 0 ° C. or higher and a low temperature region of 300 ° C. or lower. If the high temperature range is less than 800 ° C, methane activated compounds such as methyl radicals are less likely to be generated, and the low temperature range is 400
If it exceeds ℃, carbon dioxide will increase.
【０００９】部分的に高温領域を発生させる方法として
は，電気や燃焼などを利用して８００℃以上の温度にす
ることができれば如何なる方法でもよいが，例えば，電
熱体に電気を流す方法，アーク，グロー放電，プラズマ
等の電気エネルギーを利用する方法，バーナーで可燃性
ガスを燃焼させる方法がある。電熱体としては，Ni-Cr
線やタングステン線が好ましく，場合によっては電熱体
上にメチルラジカルの発生を促進するような金属酸化物
触媒を担持してもよい。反応器は，反応器内の混合気体
の物質移動を促進するため攪拌機等を設置しても良い。
反応器内圧力は，通常１〜１００気圧，好ましくは２５
〜８０気圧である。Any method may be used to partially generate the high temperature region as long as the temperature can be raised to 800 ° C. or higher by using electricity or combustion. For example, a method of passing electricity through an electric heating element, an arc There are methods of using electric energy such as glow discharge and plasma, and methods of burning combustible gas with a burner. As an electric heating element, Ni-Cr
A wire or a tungsten wire is preferable, and in some cases, a metal oxide catalyst that promotes the generation of methyl radicals may be supported on the heating element. The reactor may be equipped with a stirrer or the like in order to promote mass transfer of the mixed gas in the reactor.
The pressure in the reactor is usually 1 to 100 atm, preferably 25
~ 80 atm.
【００１０】前記反応には，通常天然ガスから分離した
メタンを用いるが，石炭その他の物質から製造されたメ
タンを用いても良い。さらに，メタンを含む天然ガスそ
のものを原料として用いることもできる。酸素は，空気
から深冷分離されたものや，ガス分離膜により濃縮され
たものなどを用いることができる。さらに，空気中の酸
素をそのまま用いることも可能である。以下，本発明を
実施例に基づいてさらに詳しく説明するが，本発明はこ
れに限定されるものでない。Although methane separated from natural gas is usually used in the above reaction, methane produced from coal or other substances may be used. Furthermore, natural gas itself containing methane can also be used as a raw material. Oxygen that has been cryogenicly separated from air, or oxygen that has been concentrated by a gas separation membrane can be used. Furthermore, it is possible to use oxygen in the air as it is. Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.
【００１１】[0011]
（実施例１）反応はステンレス製防爆型オートクレーブ
を用いて行なった。オートクレーブの上部にはマックス
ター型攪拌子が，下部には部分高温を発生させるための
Ni-Cr線のフィラメント（７０cm，０.３mm径，単位抵抗
１５オーム）がセットされている。また，オートクレー
ブの外周にはヒーターおよび冷却用の配管が設置されて
いて，気相温度をコントロールできるようになってい
る。上記オートクレーブに，CH4：Air：H2＝７：１：
０.３の混合ガスを充填し，フィラメントに１６０Ｗの
電力をかけて，１分間に７５０ｒｐｍの速度で回転させ
ながら，４０kg/cm2の圧力下，気相温度２２０℃で１５
分間反応させた。反応生成物を分析したところ，メタン
転化率０.５％でメタノール選択率（C-％）９７％の成
績が得られた。(Example 1) The reaction was carried out using a stainless steel explosion-proof autoclave. The upper part of the autoclave has a Maxter-type stirrer, and the lower part is for generating partial high temperature.
Ni-Cr wire filament (70 cm, 0.3 mm diameter, unit resistance 15 ohm) is set. In addition, heaters and cooling pipes are installed on the outer circumference of the autoclave to control the gas phase temperature. CH 4 : Air: H 2 = 7: 1:
It is filled with 0.3 gas mixture, and while applying a power of 160 W to the filament and rotating it at a speed of 750 rpm for 1 minute, under a pressure of 40 kg / cm 2 and a vapor phase temperature of 220 ° C. for 15 minutes.
Let react for minutes. When the reaction product was analyzed, a result of a methane conversion rate of 0.5% and a methanol selectivity (C-%) of 97% was obtained.
【００１２】（実施例２）反応条件のうち，CH4：O2：N
2＝４０：２：１０の混合ガス，５０kg/cm2の圧力下，
気相温度２００℃，反応時間１５０分にした以外は実施
例１と同様にして反応させた。 反応生成物を分析した
ところ，メタン転化率０.１％でメタノール選択率（C-
％）８０％の成績が得られた。Example 2 Of the reaction conditions, CH 4 : O 2 : N
2 = 40: 2: 10 mixed gas, under pressure of 50 kg / cm 2 ,
The reaction was carried out in the same manner as in Example 1 except that the gas phase temperature was 200 ° C. and the reaction time was 150 minutes. Analysis of the reaction product showed that the methane conversion was 0.1% and the methanol selectivity (C-
%) A score of 80% was obtained.
【００１３】[0013]
【発明の効果】本発明によれば，メタンまたはメタンを
含む天然ガスを酸素または含酸素ガスで部分酸化するに
際し，高温領域で発生させたメチルラジカルなどのメタ
ン活性化物をすみやかに低温領域に移動させるので，生
成したメタノールの分解が抑制されて，合成ガスを経由
せずに一段反応で選択的に効率よくメタノールを合成す
ることができる。According to the present invention, upon partial oxidation of methane or a natural gas containing methane with oxygen or an oxygen-containing gas, a methane activated product such as a methyl radical generated in a high temperature region is promptly moved to a low temperature region. Therefore, the decomposition of the produced methanol is suppressed, and the methanol can be selectively and efficiently synthesized by the one-step reaction without passing through the synthesis gas.
Claims (2)
水素ガスを分子状酸素または含酸素ガスで部分酸化して
メタノールを合成する方法において，反応器の中に８０
０℃以上の高温領域と４００℃以下の低温領域を部分的
につくることができる反応装置を用いて，前記高温領域
でメタン活性化物を生成させ，それを前記低温部分で酸
素と反応させることによりメタノールを選択的に合成す
ることを特徴とするメタノールの製造方法。1. In a method for synthesizing methanol by partially oxidizing methane or a hydrocarbon gas containing methane as a main component with molecular oxygen or an oxygen-containing gas, 80
By using a reactor capable of partially forming a high temperature region of 0 ° C. or higher and a low temperature region of 400 ° C. or lower, a methane activated compound is produced in the high temperature region and reacted with oxygen in the low temperature region. A method for producing methanol, which comprises synthesizing methanol selectively.
共存させる請求項１のメタノールの製造方法。2. The method for producing methanol according to claim 1, wherein 30 vol% or less of hydrogen is allowed to coexist in all raw material gases.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28071793A JP3472606B2 (en) | 1993-10-15 | 1993-10-15 | Method for producing methanol by partial oxidation of methane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28071793A JP3472606B2 (en) | 1993-10-15 | 1993-10-15 | Method for producing methanol by partial oxidation of methane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07112946A true JPH07112946A (en) | 1995-05-02 |
| JP3472606B2 JP3472606B2 (en) | 2003-12-02 |
Family
ID=17628973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28071793A Expired - Fee Related JP3472606B2 (en) | 1993-10-15 | 1993-10-15 | Method for producing methanol by partial oxidation of methane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3472606B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009521529A (en) * | 2005-12-27 | 2009-06-04 | ガス テクノロジーズ エルエルシー | Method and apparatus for producing methanol |
| JP2009521528A (en) * | 2005-12-27 | 2009-06-04 | ガス テクノロジーズ エルエルシー | Methanol production method and apparatus |
| WO2014100813A1 (en) * | 2012-12-22 | 2014-06-26 | Gas Technologies Llc | Method and apparatus for providing oxygenated hydrocarbons |
| RU2641701C1 (en) * | 2016-12-06 | 2018-01-22 | Федеральное государственное бюджетное учреждение науки Институт проблем химической физики Российской академии наук (ИПХФ РАН) | Method of associated and natural gases processing |
-
1993
- 1993-10-15 JP JP28071793A patent/JP3472606B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009521529A (en) * | 2005-12-27 | 2009-06-04 | ガス テクノロジーズ エルエルシー | Method and apparatus for producing methanol |
| JP2009521528A (en) * | 2005-12-27 | 2009-06-04 | ガス テクノロジーズ エルエルシー | Methanol production method and apparatus |
| WO2014100813A1 (en) * | 2012-12-22 | 2014-06-26 | Gas Technologies Llc | Method and apparatus for providing oxygenated hydrocarbons |
| CN104870412A (en) * | 2012-12-22 | 2015-08-26 | 气体技术有限公司 | Method and apparatus for providing oxygenated hydrocarbons |
| RU2641701C1 (en) * | 2016-12-06 | 2018-01-22 | Федеральное государственное бюджетное учреждение науки Институт проблем химической физики Российской академии наук (ИПХФ РАН) | Method of associated and natural gases processing |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3472606B2 (en) | 2003-12-02 |
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