An Introduction of CO2 Conversion by Dry Reforming with Methane and New Route of Low-Temperature Methanol Synthesis
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- 作者：Lei Shi ; Guohui Yang ; Kai Tao ; Yoshiharu Yoneyama ; Yisheng Tan ; Noritatsu Tsubaki
- 刊名：Accounts of Chemical Research
- 出版年：2013
- 出版时间：August 20, 2013
- 年：2013
- 卷：46
- 期：8
- 页码：1838-1847
- 全文大小：484K
- 年卷期：v.46,no.8(August 20, 2013)
- ISSN：1520-4898
文摘
Carbon dioxide is one of the highest contributors to the greenhouse effect, as well as a cheap and nontoxic building block for single carbon source chemistry. As such, CO2 conversion is one of most important research areas in energy and environment sciences, as well as in catalysis technology. For chemical conversion of CO2, natural gas (mainly CH4) is a promising counterpart molecule to the CO2-related reaction, due to its high availability and low price. More importantly, being able to convert CH4 to useful fuels and molecules is advantageous, because it is also a kind of 鈥済reenhouse effect鈥?gas, and can be an energy alternative to petroleum oil. In this Account, we discuss our development of efficient catalysts with precisely designed nanostructure for CO2 reforming of CH4 to produce syngas (mixture of CO and H2), which can then be converted to many chemicals and energy products. This new production flow can establish a GTL (gas-to-liquid) industry, being currently pushed by the shale gas revolution.
From the viewpoint of GTL industry, developing a catalyst for CO2 reforming of CH4 is a challenge, because they need a very high production rate to make the huge GTL methane reformer as small as possible. In addition, since both CO2 and CH4 give off carbon deposits that deactivate non-precious metallic catalysts very quickly, the total design of catalyst support and supported metallic nanoparticles is necessary. We present a simple but useful method to prepare bimodal catalyst support, where small pores are formed inside large ones during the self-organization of nanoparticles from solution. Large pores enhance the mass transfer rate, while small pores provide large surface areas to disperse active metallic nanoparticles. More importantly, building materials for small pores can also be used as promoters or cocatalysts to further enhance the total activity and stability.
Produced syngas from methane reforming is generally catalytically converted in situ via one of two main routes. The first is to use Fischer鈥揟ropsch synthesis (FTS), a process that catalytically converts syngas to hydrocarbons of varying molecular weights. The second is methanol synthesis. The latter has better atomic economy, since the oxygen atom in CO is included in the product and CO2 can be blended into syngas as a reactant. However, production of methanol is very inefficient in this reaction: only 10鈥?5% one-pass conversion typically at 5.0鈥?0.0 MPa and 523鈥?73 K, due to the severe thermodynamic limitations of this exothermal reaction (CO + 2H2 = CH3OH). In this Account, we propose and develop a new route of low-temperature methanol synthesis from CO2-containing syngas only by adding alcohols, including methanol itself. These alcohols act as homogeneous cocatalysts and the solvent, realizing 70鈥?00% one-pass conversion at only 5.0 MPa and 443 K. The key step is the reaction of the adsorbed formate species with alcohols to yield ester species at low temperatures, followed by the hydrogenation of ester by hydrogen atoms on metallic Cu. This changes the normal reaction path of conventional, high-temperature methanol synthesis from formate via methoxy to methanol.
From the viewpoint of GTL industry, developing a catalyst for CO2 reforming of CH4 is a challenge, because they need a very high production rate to make the huge GTL methane reformer as small as possible. In addition, since both CO2 and CH4 give off carbon deposits that deactivate non-precious metallic catalysts very quickly, the total design of catalyst support and supported metallic nanoparticles is necessary. We present a simple but useful method to prepare bimodal catalyst support, where small pores are formed inside large ones during the self-organization of nanoparticles from solution. Large pores enhance the mass transfer rate, while small pores provide large surface areas to disperse active metallic nanoparticles. More importantly, building materials for small pores can also be used as promoters or cocatalysts to further enhance the total activity and stability.
Produced syngas from methane reforming is generally catalytically converted in situ via one of two main routes. The first is to use Fischer鈥揟ropsch synthesis (FTS), a process that catalytically converts syngas to hydrocarbons of varying molecular weights. The second is methanol synthesis. The latter has better atomic economy, since the oxygen atom in CO is included in the product and CO2 can be blended into syngas as a reactant. However, production of methanol is very inefficient in this reaction: only 10鈥?5% one-pass conversion typically at 5.0鈥?0.0 MPa and 523鈥?73 K, due to the severe thermodynamic limitations of this exothermal reaction (CO + 2H2 = CH3OH). In this Account, we propose and develop a new route of low-temperature methanol synthesis from CO2-containing syngas only by adding alcohols, including methanol itself. These alcohols act as homogeneous cocatalysts and the solvent, realizing 70鈥?00% one-pass conversion at only 5.0 MPa and 443 K. The key step is the reaction of the adsorbed formate species with alcohols to yield ester species at low temperatures, followed by the hydrogenation of ester by hydrogen atoms on metallic Cu. This changes the normal reaction path of conventional, high-temperature methanol synthesis from formate via methoxy to methanol.