JP2006169095A - Method for immobilizing co2 using microwave - Google Patents
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Abstract
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本発明は、発電所、製鉄分野、石油化学産業分野、一般化学工業分野等において利用できる二酸化炭素（ＣＯ２）の固定化方法に関する。 TECHNICAL FIELD The present invention relates to a method for immobilizing carbon dioxide (CO 2 ) that can be used in a power plant, steelmaking field, petrochemical industry field, general chemical industry field, and the like.
発電所、工場、自動車等の人間の社会的活動に伴って大気中に排出される二酸化炭素は地球温暖化の主たる原因であることが知られており、近年、この二酸化炭素の排出量を削減することが地球環境の保護の大きな課題となっている。これに対し、従来より、発電所等の排煙や大気中の二酸化炭素を固定化し除去するためのシステムが種々提案されている。 It is known that carbon dioxide emitted into the atmosphere due to human social activities such as power plants, factories and automobiles is the main cause of global warming. In recent years, this carbon dioxide emission has been reduced. Doing so has become a major issue in protecting the global environment. In contrast, various systems for fixing and removing flue gas from a power plant or the like and carbon dioxide in the atmosphere have been proposed.
二酸化炭素の固定化方法は、概ね生物的方法、物理的方法、化学的方法の３種類に分けられる。光合成を利用する生物的方法はかなりの量のＣＯ２の固定が期待でき、しかも熱帯林の保護や砂漠化防止にも役立つので、現在広範な植樹と微細藻類の多量かつ連続的な培養、増殖を行う研究開発が行われている。しかし、微細藻類による固定化反応は、微細藻類の表面で進行するため、微細藻類でＣＯ２を固定化するためには広大な面積の微細藻類が必要となる問題がある。 Carbon dioxide immobilization methods are roughly divided into three types: biological methods, physical methods, and chemical methods. Biological methods using photosynthesis can be expected to fix a considerable amount of CO 2 , and also help to protect tropical forests and prevent desertification. Research and development is underway. However, since the immobilization reaction by the microalgae proceeds on the surface of the microalgae, there is a problem that a large area of microalgae is required to immobilize CO 2 with the microalgae.
物理的方法は、ＣＯ２の特殊な媒体への溶解、吸着を利用する分離・濃縮法であり、例えば、ＣＯ２をアルカリ溶液に溶解、反応後、炭酸塩として分離する方法、或いは、ＣＯ２をゼオライト媒体等に吸着させた後、脱着、濃縮する方法などが開発研究されている。しかし、吸着法ではＣＯ２の吸脱着に膨大なエネルギーを要する問題点がある。吸収法では大掛かりな装置が必要である。 The physical method is a separation / concentration method using dissolution and adsorption of CO 2 in a special medium. For example, a method in which CO 2 is dissolved in an alkaline solution and reacted and then separated as a carbonate, or CO 2 Development and research have been conducted on the method of desorption and concentration after adsorbing to a zeolite medium. However, there is a problem that requires enormous energy to adsorption and desorption of CO 2 in the adsorption method. The absorption method requires a large device.
３番目の化学的方法は、電気化学法（電気化学的還元、電気化学的固定）、触媒反応を利用する方法、光反応を利用する方法に分けられる。電気化学法によるＣＯ２の還元としては、特殊な電極を使用して電解溶液中のＣＯ２を分解し、ギ酸、メタン等を常温で生成する方法等が知られているが、大規模な反応槽が必要であり、反応を促進させるためには大量の電気エネルギーを供給する必要がある。 The third chemical method is divided into an electrochemical method (electrochemical reduction, electrochemical fixation), a method using a catalytic reaction, and a method using a photoreaction. As a method for reducing CO 2 by an electrochemical method, there is known a method in which a special electrode is used to decompose CO 2 in an electrolytic solution to produce formic acid, methane, etc. at room temperature. A tank is required and a large amount of electrical energy needs to be supplied to promote the reaction.
触媒反応を利用するＣＯ２の還元は、ＣＯ２を一酸化炭素、メタノール等に転化してそれを利用するという手段等が知られており、このような化学的方法は、生物的方法や物理的方法に比べて、エネルギーの低減が図れる可能性があるが、基礎研究の段階である。 The reduction of CO 2 using a catalytic reaction is known as a means of converting CO 2 into carbon monoxide, methanol, etc. and using it, and such chemical methods include biological methods and physical methods. There is a possibility that energy can be reduced compared with the conventional method, but it is in the basic research stage.
例えば、特許文献１には、二酸化炭素と水素の混合物を熱反応器に供給し、該熱反応器中で加圧しながら温度を２２０〜２５０℃に維持し、かつＣｕ系触媒の存在下にメタノールに変換する際に、前記水素をマイクロ波を用いる硫化水素の分解によって取得する方法が提案されている。
ＣＯ２ ＋ ３Ｈ２ → ＣＨ３ＯＨ ＋ Ｈ２Ｏ
CO 2 + 3H 2 → CH 3 OH + H 2 O
しかしながら、特許文献１記載の二酸化炭素の固定化方法は、二酸化炭素を燃料として利用可能なメタノールに変換するために、低温・低圧力で実施可能で、かつ高いメタノール収量を実現するメタノール製造法を得ることを課題とするものであり、水素の産出にマイクロ波を利用しているが、二酸化炭素の固定化反応自体にマイクロ波を利用することにより低エネルギー化を図ったものではない。
However, the method for immobilizing carbon dioxide described in
一方、触媒化学的な方法は反応速度が遅く、気相で還元する方法を用いれば火力発電所の煙道等から排出される大量の二酸化炭素を短時間で処理することができると考えられているが、メタノール等の液状炭化水素に直接転化するためには、高圧下での反応が必要であるため、短時間の処理が難しくなるという問題点があった。 On the other hand, the catalytic chemical method has a slow reaction rate, and it is considered that a large amount of carbon dioxide discharged from the flue of a thermal power plant can be processed in a short time by using a method of reducing in the gas phase. However, in order to directly convert to liquid hydrocarbons such as methanol, a reaction under high pressure is required, so that there has been a problem that it is difficult to process in a short time.
二酸化炭素を水素を用いて気相で還元する方法としては、常圧下で反応が促進する反応として、下記の反応が知られている。
ＣＯ２ ＋ Ｈ２ → ＣＯ＋ Ｈ２Ｏ
As a method of reducing carbon dioxide in the gas phase using hydrogen, the following reactions are known as reactions that promote the reaction under normal pressure.
CO 2 + H 2 → CO + H 2 O
この反応は吸熱反応であるため、一般には高温になればなるほど平衡が右側にシフトして、二酸化炭素が一酸化炭素に転化する比率が増加する。しかし、高温を維持するためにはエネルギーを投入する必要があり、このエネルギー源として化石燃料を使用すれば、二酸化炭素の排出量を低減したことにはならなくなる。 Since this reaction is an endothermic reaction, in general, the higher the temperature, the more the equilibrium shifts to the right, and the rate at which carbon dioxide is converted to carbon monoxide increases. However, in order to maintain a high temperature, it is necessary to input energy. If fossil fuel is used as this energy source, the amount of carbon dioxide emission cannot be reduced.
従って、できるだけ低エネルギーで、化学平衡状態の転化率に近い転化特性を得られるかが、二酸化炭素排出量削減対策として実用化できるかを決定する重要な要素であるといえる。 Therefore, it can be said that it is an important factor to determine whether the conversion characteristic close to the conversion rate in the chemical equilibrium state can be obtained with the lowest possible energy as a measure for reducing carbon dioxide emissions.
これまで検討されてきた二酸化炭素の触媒水素化反応では、触媒活性を研究することにより二酸化炭素の固定化効率の向上を検討してきたものであり、熱エネルギーの低減という観点から検討された例は殆どない。 In the catalytic hydrogenation reaction of carbon dioxide that has been studied so far, the improvement of carbon dioxide immobilization efficiency has been studied by studying the catalytic activity, and examples examined from the viewpoint of reducing thermal energy include Almost no.
本発明は、上記課題に鑑み、低エネルギーで二酸化炭素の固定化反応を加速できる新規な二酸化炭素の固定化方法を提供することを目的とする。 An object of this invention is to provide the novel fixing method of a carbon dioxide which can accelerate the fixing reaction of a carbon dioxide with low energy in view of the said subject.
前記課題を解決するため、本発明者らは鋭意検討した結果、化学的固定化方法における触媒反応をマイクロ波による加熱状態で行わせることにより、より少ないエネルギーで二酸化炭素の固定化反応を加速できることを見出し、本発明に到達した。 In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, by performing the catalytic reaction in the chemical immobilization method in a heated state by microwaves, the carbon dioxide immobilization reaction can be accelerated with less energy. And reached the present invention.
すなわち、本発明は、二酸化炭素と水素との混合物に、触媒存在下でマイクロ波を照射することを特徴とする二酸化炭素の固定化方法を提供する。 That is, the present invention provides a method for immobilizing carbon dioxide, which comprises irradiating a mixture of carbon dioxide and hydrogen with microwaves in the presence of a catalyst.
また、本発明は、二酸化炭素と水素との混合物に、触媒存在下でマイクロ波を照射することにより、二酸化炭素を一酸化炭素及びメタノールに転化することを特徴とする二酸化炭素の固定化方法を提供する。 Further, the present invention provides a method for immobilizing carbon dioxide, characterized in that carbon dioxide is converted into carbon monoxide and methanol by irradiating a mixture of carbon dioxide and hydrogen with microwaves in the presence of a catalyst. provide.
また、本発明は、二酸化炭素と水素との混合物に、触媒存在下でマイクロ波を照射することにより、二酸化炭素を一酸化炭素、メタン及びメタノールに転化することを特徴とする二酸化炭素の固定化方法を提供する。 In addition, the present invention is a carbon dioxide immobilization characterized by converting carbon dioxide into carbon monoxide, methane and methanol by irradiating a mixture of carbon dioxide and hydrogen with microwaves in the presence of a catalyst. Provide a method.
上記本発明の二酸化炭素固定化方法においては、触媒は、Ｃｕ、Ｚｎ、Ｃｒ、Ａｌ、Ａｕ、Ｚｒのいずれかの元素を１種類以上含むものであることが好ましい。 In the carbon dioxide fixing method of the present invention, the catalyst preferably contains one or more elements of any one of Cu, Zn, Cr, Al, Au, and Zr.
上記本発明の二酸化炭素固定化方法においては、二酸化炭素及び水素を含む触媒充填層へマイクロ波を照射することが好ましい。 In the carbon dioxide fixing method of the present invention, it is preferable to irradiate the catalyst packed bed containing carbon dioxide and hydrogen with microwaves.
本発明の二酸化炭素固定化方法によれば、二酸化炭素と水素との混合物に触媒存在下でマイクロ波を照射し、触媒反応をマイクロ波による加熱状態で行わせることにより、マイクロ波と触媒との相乗効果によって、より少ないエネルギーで二酸化炭素の固定化反応を加速できる。 According to the carbon dioxide immobilization method of the present invention, a mixture of carbon dioxide and hydrogen is irradiated with microwaves in the presence of a catalyst, and the catalytic reaction is performed in a heated state by microwaves. The synergistic effect can accelerate the carbon dioxide fixation reaction with less energy.
本発明の二酸化炭素固定化方法によれば、二酸化炭素と水素との混合物に触媒存在下でマイクロ波を照射することにより、より少ないエネルギーで二酸化炭素からメタノールを製造することができる。 According to the carbon dioxide fixing method of the present invention, methanol can be produced from carbon dioxide with less energy by irradiating a mixture of carbon dioxide and hydrogen with microwaves in the presence of a catalyst.
本発明の二酸化炭素固定化方法によれば、二酸化炭素と水素との混合物に触媒存在下でマイクロ波を照射することにより、より少ないエネルギーで二酸化炭素からメタン及びメタノールを製造することができる。 According to the carbon dioxide immobilization method of the present invention, methane and methanol can be produced from carbon dioxide with less energy by irradiating a mixture of carbon dioxide and hydrogen with microwaves in the presence of a catalyst.
本発明の二酸化炭素固定化方法においては、二酸化炭素は少なくとも二酸化炭素を含むガス等であればよい。二酸化炭素ガスは勿論のこと、石炭、石油、ＬＮＧ、プラスチックの燃焼により生じた燃焼排ガスや、熱風炉排ガス、高炉排ガス、転炉排ガス、燃焼排ガス等の製鉄所副生ガスのように、二酸化炭素を１〜４０容量％含有する排ガス処理を行う場合、或いは、自動車のエンジンの排気ガス処理を行う場合でも本発明は適用できる。 In the carbon dioxide fixing method of the present invention, the carbon dioxide may be a gas containing at least carbon dioxide. Carbon dioxide gas, as well as combustion exhaust gas generated by combustion of coal, petroleum, LNG, plastics, and by-product gas of steelworks such as hot blast furnace exhaust gas, blast furnace exhaust gas, converter exhaust gas, combustion exhaust gas, etc. The present invention can be applied even when exhaust gas treatment containing 1 to 40% by volume is performed, or when exhaust gas treatment of an automobile engine is performed.
二酸化炭素と水素の比率は、５０／５０〜５／９５（モル比）、好ましくは３０／７０〜８／９２（モル比）、より好ましくは２０／８０〜１０／９０（モル比）とするのがよい。二酸化炭素に対する水素の混合比が高いほど、メタノール生成量が多くなるが、二酸化炭素の固定化効率を考慮すると上記範囲が好ましい。 The ratio of carbon dioxide to hydrogen is 50/50 to 5/95 (molar ratio), preferably 30/70 to 8/92 (molar ratio), more preferably 20/80 to 10/90 (molar ratio). It is good. The higher the mixing ratio of hydrogen to carbon dioxide, the larger the amount of methanol produced, but the above range is preferable in view of the fixation efficiency of carbon dioxide.
本発明の固定化方法では、触媒存在下において上記の二酸化炭素と水素との混合物にマイクロ波を照射することが重要であり、触媒が存在しない状態で該混合物にマイクロ波を照射しても、反応系の温度上昇が期待できず、また、反応速度は著しく遅くなる。二酸化炭素、水素及び触媒が十分接触するように、触媒充填層を形成した触媒充填装置内に二酸化炭素及び水素を導入し、二酸化炭素及び水素を含む触媒充填層へマイクロ波を照射する方法が、エネルギー効率的に好ましい。この方法によれば、ヒーター等の加熱手段と異なり、マイクロ波が触媒に当ることによって触媒表面が優先的に活性化されるので、エネルギー利用効率を著しく高めることが可能となる。 In the immobilization method of the present invention, it is important to irradiate the above mixture of carbon dioxide and hydrogen with microwaves in the presence of a catalyst, and even if the mixture is irradiated with microwaves in the absence of a catalyst, The temperature rise of the reaction system cannot be expected, and the reaction rate becomes extremely slow. A method in which carbon dioxide and hydrogen are introduced into a catalyst filling device in which a catalyst packed bed is formed so that carbon dioxide, hydrogen and the catalyst are in sufficient contact, and the catalyst packed bed containing carbon dioxide and hydrogen is irradiated with microwaves. Energy efficient. According to this method, unlike the heating means such as a heater, the catalyst surface is preferentially activated by the microwaves striking the catalyst, so that the energy utilization efficiency can be remarkably increased.
触媒としては、Ｃｕ、Ｚｎ、Ｃｒ、Ａｌ、Ａｕ、Ｚｒのいずれかの元素を１種類以上含む触媒を使用することが好ましく、該触媒と酸化チタンなどを担体とするパラジウム触媒等を併用してもよい。メタノール製造用触媒としては、例えばＣｕＯ−ＺｎＯ等が挙げられ、又、メタン及びメタノール製造用触媒としては、例えばＣｕＯ−ＺｎＯ−Ｃｒ２Ｏ３等が挙げられる。これらの触媒をＳｉＯ２、Ａｌ２Ｏ３、ＭｇＯなどの担体に担持したものでも良い。 As the catalyst, it is preferable to use a catalyst containing one or more elements of any one of Cu, Zn, Cr, Al, Au, and Zr. The catalyst is used in combination with a palladium catalyst using titanium oxide or the like as a carrier. Also good. Examples of the catalyst for methanol production include CuO-ZnO, and examples of the catalyst for methane and methanol production include CuO-ZnO-Cr 2 O 3 . These catalysts may be supported on a carrier such as SiO 2 , Al 2 O 3 , or MgO.
照射するマイクロ波の出力や周波数、照射方法は、特に限定されるものではなく、反応温度が所定の範囲に保持できるよう電気的に制御すればよい。出力が低すぎる場合は固定化反応の進行が遅くとなり、出力が高すぎる場合はマイクロ波の利用率が悪くなる。マイクロ波の周波数は、通常、１ＧＨｚ〜３００ＧＨｚである。１ＧＨｚ未満又は３００ＧＨｚを超える周波数範囲では、反応促進効果が不十分となる。 The output, frequency, and irradiation method of the microwave to be irradiated are not particularly limited, and may be electrically controlled so that the reaction temperature can be maintained within a predetermined range. When the output is too low, the progress of the immobilization reaction is slow, and when the output is too high, the utilization rate of the microwave is deteriorated. The frequency of the microwave is usually 1 GHz to 300 GHz. In the frequency range below 1 GHz or above 300 GHz, the reaction promoting effect is insufficient.
マイクロ波の照射は連続照射、間欠照射のいずれの方法であってもよい。照射時間及び照射停止時間は、反応に供する二酸化炭素の濃度、又は反応触媒の種類等に応じて適宜に決定することができる。 Microwave irradiation may be either continuous irradiation or intermittent irradiation. The irradiation time and the irradiation stop time can be appropriately determined according to the concentration of carbon dioxide to be subjected to the reaction, the type of reaction catalyst, or the like.
固定化反応における反応温度は使用する触媒の種類によっても異なるが、反応温度１２０〜３００℃、好ましくは１５０〜２５０℃、より好ましくは１７０〜２２０℃で行うのがよい。 The reaction temperature in the immobilization reaction varies depending on the type of catalyst used, but the reaction temperature is 120 to 300 ° C, preferably 150 to 250 ° C, more preferably 170 to 220 ° C.
固定化反応における反応圧力は、常圧、加圧の何れでもかまわないが、通常、０．１ＭＰａ（常圧）〜３０ＭＰａ、好ましくは０．１ＭＰａ（常圧）〜２０ＭＰａ、より好ましくは常圧である。 The reaction pressure in the immobilization reaction may be either normal pressure or pressurized, but is usually 0.1 MPa (normal pressure) to 30 MPa, preferably 0.1 MPa (normal pressure) to 20 MPa, more preferably normal pressure. is there.
固定化反応における反応時間は、触媒量と反応温度に左右されて一定しないが、通常は反応進行状況を見ながら適宜に決定すればよい。 The reaction time in the immobilization reaction depends on the amount of catalyst and the reaction temperature and is not constant, but it is usually determined appropriately while observing the progress of the reaction.
以下、本発明の実施例について図面を参照して説明するが、本発明は以下の実施例にのみ限定されるものではない。なお、以下において示す％はことわりのない限り容量％である。 Hereinafter, examples of the present invention will be described with reference to the drawings. However, the present invention is not limited to the following examples. In addition,% shown below is a capacity% unless there is particular notice.
（実施例１）
図１は本発明の固定化反応で用いるマイクロ波反応装置全体を示す概略構成図である。図１において、１０はマイクロ波反応装置全体のフロー、１は反応装置、２はＣＯ２ガスとＨ２ガスの混合ガスを収容するテドラーパック、３はガス配管、４は循環ポンプ、５は排気ガスの排気口、６はインピンジャー、７はＮ２ボンベ、８は生成ガスを随時サンプリングして分析するためのパージサンプリングパックである。反応装置には、ガス流量計、圧力計、及び調整弁が設けてある。
Example 1
FIG. 1 is a schematic configuration diagram showing the entire microwave reactor used in the immobilization reaction of the present invention. In FIG. 1, 10 is a flow of the whole microwave reactor, 1 is a reactor, 2 is a Tedlar pack that contains a mixed gas of CO 2 gas and H 2 gas, 3 is a gas pipe, 4 is a circulation pump, and 5 is an exhaust gas. , 6 is an impinger, 7 is an N 2 cylinder, and 8 is a purge sampling pack for sampling and analyzing the generated gas as needed. The reaction apparatus is provided with a gas flow meter, a pressure gauge, and a regulating valve.
図２は、図１に示す反応装置１を拡大した断面図である。１１は触媒を充填するための触媒仕切り板、１２はボールフィルター、１３は触媒、１４は光ファイバー温度計、２１は反応装置へ導入される入口ガス、２２は反応装置から排出される出口ガスである。図２に示すように、反応装置１の上部よりガス２１を反応装置内に送り込む。導入されたガスは、反応装置１の下部に設けられたボールフィルター１２の微細孔を通じてフィルター内部から外部へ流れ出し、流れ出たガスが反応装置１内を上昇する間に触媒付近で反応が起きるようになっている。反応生成ガス２２は、反応装置１の上部に設けられたガス出口から排出される。
FIG. 2 is an enlarged cross-sectional view of the
反応装置内にＣｕＯ−ＺｎＯ系触媒（日揮化学社製 Ｎ２１１）７１ｇを加え、図１に示すマイクロ波反応装置内に設置した。窒素ボンベより装置内に窒素を供給し、装置内を窒素雰囲気にした。ＣＯ２／Ｈ２＝３０／７０（モル比）の混合ガスを充填した容量１０リットルのテドラーパックを、反応装置の配管内に設置した。循環ポンプを起動させ、テドラーパック内のガスを流しながら排気口に排気を行った。テドラーパック内のガスが全て排気された後、排気、循環ポンプを停止させた。 71 g of CuO—ZnO-based catalyst (N2C manufactured by JGC Chemical Co., Ltd.) was added to the reaction apparatus and installed in the microwave reaction apparatus shown in FIG. Nitrogen was supplied into the apparatus from a nitrogen cylinder, and the inside of the apparatus was put into a nitrogen atmosphere. A 10 liter Tedlar pack filled with a mixed gas of CO 2 / H 2 = 30/70 (molar ratio) was installed in the piping of the reactor. The circulation pump was activated, and the exhaust gas was exhausted while flowing the gas in the Tedlar pack. After all the gas in the Tedlar pack was exhausted, the exhaust and circulation pumps were stopped.
再度、ＣＯ２／Ｈ２＝３０／７０（モル比）の混合ガスを充填した容量１０リットルのテドラーパックを、反応装置の配管内に設置し、循環ポンプを起動させ１．０Ｌ／ｍｉｎの流速でガスを流しながら、周波数２．４５ＧＨｚのマイクロ波を反応装置に照射して２５０℃まで昇温させた後、常圧、温度２５０℃で６０分間加熱を行いＣＯ２の固定化反応を行った。反応中のマイクロ波の平均照射出力は２７２．３Ｗであった。 Again, a 10 liter Tedlar pack filled with a mixed gas of CO 2 / H 2 = 30/70 (molar ratio) was installed in the reactor piping, the circulation pump was started, and the flow rate was 1.0 L / min. While flowing the gas, the reactor was irradiated with microwaves having a frequency of 2.45 GHz to raise the temperature to 250 ° C., and then heated at normal pressure and a temperature of 250 ° C. for 60 minutes to perform CO 2 fixation reaction. The average irradiation power of microwaves during the reaction was 272.3 W.
反応後、配管中のガス及びインピンジャー内の液体をガスクロマトグラフィーを用いてそれぞれ分析し、同定・定量した。その結果、ガス中にＣＯが１７％、ＣＨ４が１０６ｐｐｍ、液層中にメタノールが１．１６ｍｇ生成した。 After the reaction, the gas in the pipe and the liquid in the impinger were analyzed and identified and quantified using gas chromatography. As a result, CO was 17% in the gas, CH 4 was 106 ppm, and methanol was 1.16 mg in the liquid layer.
（実施例２）
触媒をＣｕＯ−ＺｎＯ−Ｃｒ２Ｏ３系触媒（日揮化学社製 Ｎ２１１Ｂ）５８ｇとＰｄ−ＴｉＯ２触媒１ｇを用い、反応温度を１５０℃、ガスの循環流量を１．５Ｌ／ｍｉｎにした以外は、実施例１と同様な方法によりＣＯ２の固定化反応を行った。反応中のマイクロ波の平均照射出力：１０４Ｗ。反応後、実施例１同様、生成ガスと液体を分析し、同定・定量した。その結果、ガス中にＣＯが０．８７％、液層中にメタノールが１．１６ｍｇ生成した。
(Example 2)
Except for using 58 g of a CuO—ZnO—Cr 2 O 3 catalyst (N211B manufactured by JGC Chemical Co., Ltd.) and 1 g of Pd—TiO 2 catalyst as the catalyst, the reaction temperature was 150 ° C., and the gas circulation flow rate was 1.5 L / min Then, the CO 2 immobilization reaction was carried out in the same manner as in Example 1. Average irradiation power of microwave during reaction: 104W. After the reaction, the product gas and liquid were analyzed, identified and quantified as in Example 1. As a result, CO was 0.87% in the gas and 1.16 mg of methanol was produced in the liquid layer.
（実施例３）
反応温度を２００℃にした以外は、実施例２と同様な方法によりＣＯ２の固定化反応を行った。反応中のマイクロ波の平均照射出力：１２１Ｗ。その結果、ガス中にＣＯが７．６％、液層中にメタノールが３．７７ｍｇ生成した。
(Example 3)
A CO 2 immobilization reaction was carried out in the same manner as in Example 2 except that the reaction temperature was 200 ° C. Average irradiation power of microwave during reaction: 121 W. As a result, CO was 7.6% in the gas, and 3.77 mg of methanol was produced in the liquid layer.
（実施例４）
反応温度を２５０℃にした以外は、実施例２と同様な方法によりＣＯ２の固定化反応を行った。反応中のマイクロ波の平均照射出力：１５５Ｗ。その結果、ガス中にＣＯが１４．４％、液層中にメタノールが２．５６ｍｇ生成した。
Example 4
A CO 2 immobilization reaction was carried out in the same manner as in Example 2 except that the reaction temperature was 250 ° C. Average irradiation power of microwave during reaction: 155 W. As a result, 14.4% CO was generated in the gas, and 2.56 mg of methanol was generated in the liquid layer.
（実施例５）
原料ガスの組成をＣＯ２／Ｈ２＝１０／９０（モル比）にした以外は、実施例３と同様な方法によりＣＯ２の固定化反応を行った。反応中のマイクロ波の平均照射出力：１３６Ｗ。その結果、ガス中にＣＯが４．６％、液層中にメタノールが３．４０ｍｇ生成した。
(Example 5)
A CO 2 immobilization reaction was performed in the same manner as in Example 3 except that the composition of the source gas was changed to CO 2 / H 2 = 10/90 (molar ratio). Average irradiation power of microwave during reaction: 136W. As a result, 4.6% of CO was produced in the gas and 3.40 mg of methanol was produced in the liquid layer.
（実施例６）
原料ガスの組成をＣＯ２／Ｈ２＝２０／８０（モル比）にした以外は、実施例３と同様な方法によりＣＯ２の固定化反応を行った。反応中のマイクロ波の平均照射出力：１２８Ｗ。その結果、ガス中にＣＯが７．４％、液層中にメタノールが４．０８ｍｇ生成した。
(Example 6)
A CO 2 immobilization reaction was carried out in the same manner as in Example 3 except that the composition of the source gas was changed to CO 2 / H 2 = 20/80 (molar ratio). Average irradiation power of microwave during reaction: 128W. As a result, 7.4% of CO was produced in the gas, and 4.08 mg of methanol was produced in the liquid layer.
（実施例７）
ガスの循環流量を０．５Ｌ／ｍｉｎにした以外は、実施例３と同様な方法によりＣＯ２の固定化反応を行った。その結果、ガス中にＣＯが４．５％、液層中にメタノールが２．７３ｍｇ生成した。
(Example 7)
A CO 2 immobilization reaction was carried out in the same manner as in Example 3 except that the gas circulation flow rate was changed to 0.5 L / min. As a result, 4.5% of CO was produced in the gas and 2.73 mg of methanol was produced in the liquid layer.
（実施例８〜１１）
原料ガスの組成をＣＯ２／Ｈ２＝１０／９０（モル比）とし、触媒としてＣｕＯ−ＺｎＯ−Ａｌ２Ｏ３系触媒２０ｇを用い、反応温度を１２０〜２５０℃、ガスの循環流量を１．１Ｌ／ｍｉｎにした以外は、実施例１と同様な方法によりＣＯ２の固定化反応を行った。反応中のマイクロ波の平均照射出力は１１４Ｗ〜２０５Ｗであった。反応後、実施例１同様、生成ガスと液体を分析し、同定・定量した。その結果、ガス中にＣＯ、液層中にメタノールが生成した。
(Examples 8 to 11)
The composition of the raw material gas is CO 2 / H 2 = 10/90 (molar ratio), 20 g of a CuO—ZnO—Al 2 O 3 catalyst is used as the catalyst, the reaction temperature is 120 to 250 ° C., and the gas circulation flow rate is 1. The CO 2 immobilization reaction was carried out in the same manner as in Example 1 except that the rate was changed to 1 L / min. The average irradiation power of the microwave during the reaction was 114W to 205W. After the reaction, the product gas and liquid were analyzed, identified and quantified as in Example 1. As a result, CO was produced in the gas and methanol was produced in the liquid layer.
（実施例１２）
原料ガスの組成をＣＯ２／Ｈ２＝２０／８０（モル比）にした以外は、実施例９と同様な方法によりＣＯ２の固定化反応を行った。その結果、ガス中にＣＯ、液層中にメタノールが生成した。
(Example 12)
A CO 2 immobilization reaction was performed in the same manner as in Example 9 except that the composition of the source gas was changed to CO 2 / H 2 = 20/80 (molar ratio). As a result, CO was produced in the gas and methanol was produced in the liquid layer.
（実施例１３〜１６）
原料ガスの組成をＣＯ２／Ｈ２＝１０／９０（モル比）とし、触媒としてＣｕＯ−ＺｎＯ−Ｃｒ２Ｏ３系触媒５０ｇを用い、反応温度を１５０〜３００℃、ガスの循環流量を１．５Ｌ／ｍｉｎにした以外は、実施例１と同様な方法によりＣＯ２の固定化反応を行った。反応中のマイクロ波の平均照射出力は１３１Ｗ〜２２２Ｗであった。反応後、実施例１同様、生成ガスと液体を分析し、同定・定量した。その結果、ガス中にＣＯ、液層中にメタノールが生成した。
(Examples 13 to 16)
The composition of the raw material gas is CO 2 / H 2 = 10/90 (molar ratio), a CuO—ZnO—Cr 2 O 3 catalyst 50 g is used as a catalyst, the reaction temperature is 150 to 300 ° C., and the gas circulation flow rate is 1. The CO 2 immobilization reaction was carried out in the same manner as in Example 1 except that the rate was changed to 5 L / min. The average irradiation power of the microwave during the reaction was 131 W to 222 W. After the reaction, the product gas and liquid were analyzed, identified and quantified as in Example 1. As a result, CO was produced in the gas and methanol was produced in the liquid layer.
実施例１〜１６の結果を表１にまとめて示した。なお、表中のメタノール転化率は下記式より求めた値である。
メタノール転化率（％）＝メタノール生成量（ｍｏｌ）／ＣＯ２（ｍｏｌ）×１００
The results of Examples 1 to 16 are summarized in Table 1. In addition, the methanol conversion rate in a table | surface is the value calculated | required from the following formula.
Methanol conversion (%) = methanol production (mol) / CO 2 (mol) × 100
１ 反応装置
２ テドラーパック
３ 配管
４ ポンプ
５ 排気口
６ インピンジャー
７ 窒素ボンベ
８ パージサンプリング
１１ 触媒仕切り板
１２ ボールフィルター
１３ 触媒
１４ 光ファイバー温度計
２１ 入口ガス
２２ 出口ガス
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