When it comes to carbon dioxide (CO2), it is generally regarded as waste wood, not only of little use, but also one of the culprits that destroys the climate and causes global warming. So far, researchers have thought of many ways to deal with it, imprisoning it (solidifying and sealing), driving it into a water cell (drilling into the seabed), etc. However, in the eyes of Zhang Xiangping, a researcher at the Institute of Process Engineering of the Chinese Academy of Sciences, CO2 is a good raw material, which is cheap and readily available. For more than a decade, her ionic liquid team, led by Academician Zhang Suojiang, has been thinking about how to efficiently convert and use CO2 and turn it into waste.
To deal with stubborn guys, send activists as "lobbies"
CO2 utilization is a major global strategic issue. The European Union launched a plan in June 2016 to take CO2 utilization as a major research direction; Japan has formulated a CO2 utilization planning roadmap; China ’s National Development and Reform Commission and the Energy Bureau listed it as a key research task in the Action Plan. However, due to the CO2 molecule's difficulty in activation, complex reaction path, and low product selectivity, its activation conversion has become one of the internationally recognized scientific problems.
"CO2 is a common compound in the air, and it is not easy to convert it. We know that CO2 molecules are made up of two oxygen atoms and one carbon atom connected by a solid double bond. If you want to" knock "them all at once The tightly linked carbon-oxygen double bond is very laborious to reduce it to oxygen and carbon. "Zhang Xiangping said in an interview with the Science and Technology Daily reporter.
Zhang Xiangping further explained that CO2 directly activates bond breaking, which needs to be carried out under high temperature and high pressure, but if other active molecules can be found to be "lobbies", such as epoxy compounds, CO2 activation can be induced to make it Conversion is easier. In addition, a "medium", that is, a suitable catalyst, is needed to promote the efficient conversion of CO2.
Over the past ten years, after not knowing how many experiments, the research team has gradually found a competent "competent" who does not disgrace the mission-an ionic liquid catalyst with multiple active sites synergistically, which not only activates the CO2 double bond, but also allows it to react with it The ethylene oxide (EO) becomes active and easier to open the ring, so that CO2 and EO together can react to synthesize important chemical raw materials such as ethylene carbonate.
Zhang Xiangping pointed out that through further chemical bond chain loading, the team successfully prepared a solid-supported ionic liquid catalyst, which avoids the difficulties of easy loss and deactivation of the homogeneous catalyst, difficulty in catalyst recovery and high energy consumption, and impact on product quality.
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Not only have high-efficiency catalysts been developed, but also reactors matching them are needed to provide suitable sites for reactions.
Zhang Xiangping said: "Following the law of reaction-flow-transfer coupling, the team optimized the internal components of the reactor to achieve uniform distribution of the flow field / temperature field, and innovatively developed a 10,000-ton solid-loaded ionic liquid gas-liquid-solid three-phase tubular reaction. Reactor, and the heat quickly released during the reaction can be discharged from the system as soon as possible, so that the reactor does not overheat and realize safe operation. "
On this basis, the research team adopted the alcoholysis reaction-pressure swing azeotropic distillation coupling process intensification technology to realize the optimization integration of the entire system thermal network, which greatly reduced energy consumption, significantly improved economy, and reduced equipment investment.
"In the process, we also need to design a whole process to connect the entire reaction and separation process to get the final qualified product from the raw materials." Zhang Xiangping told reporters, "We optimize the integration of materials and energy for the entire process, in energy consumption , Efficiency, economy, product quality and other aspects have been greatly improved to meet the needs of enterprises and markets. "
According to reports, under the special support of the national key research and development plan "clean and efficient use of coal and new energy-saving technologies", since May 2018, the "New Technology of CO2 Efficient Synthesis of Important Chemicals" project, led by the Institute of Process Engineering of the Chinese Academy of Sciences, In the CO2 carbonylation reaction, a functional ionic liquid catalyst with multiple active sites was designed and synthesized to achieve efficient conversion of CO2 under mild conditions. At the same time, a carbonylation catalyst that meets Industrial needs was prepared, and a continuous reaction device was built; for ethylene carbonate Ester alcoholysis reaction, the development of high-activity, low-cost catalysts, built a 10-ton / year alcoholysis continuous device, and established a 10,000-ton industrial test device.
Open up new ways to synthesize multiple important chemicals
CO2 capture, utilization and storage (CCUS) technology is one of the main ways for China's coal to achieve low carbon emissions, and the high value utilization of collected CO2 can not only reduce carbon emissions, alleviate the greenhouse effect, but also produce Significant socio-economic value.
After years of unremitting efforts, through the original innovation of the catalyst, the optimization of the reactor structure and the integrated innovation of the system, the ionic liquid team of the Institute of Process Engineering of the Chinese Academy of Sciences has developed CO2 and high-energy substance ethylene oxide as raw materials to synthesize ethylene carbonate A new route for the high-value utilization of co-production of ethylene glycol with the production of dimethyl carbonate has been formed, and a new technology of all-atom utilization for the gentle conversion of CO2 has been formed.
Just like turning a stone into gold, the products produced by CO2 can be described as high-value "babies", with a wide range of application fields and considerable market prospects, and facing the problems of poor economic benefits after being used before.
Zhang Xiangping said that in the diversified products, dimethyl carbonate is mainly used for the synthesis of important organic chemical intermediates, known as the "new cornerstone" of green chemistry in the 21st century, and can be widely used for carbonylation, methylation, Methoxylation, carbonyl methylation, polycarbon and other organic synthesis reactions. In recent years, with the rapid development of related industries such as power lithium batteries and polycarbon, the demand for dimethyl carbonate continues to grow rapidly. China is expected to 2020 The demand is 4 million tons, and it will exceed 10 million tons in 2030. Ethylene glycol is the raw material for synthetic polyester fibers and resins. China ’s annual demand is greater than 14 million tons, and its external dependence is greater than 60%.
The industry believes that this technology has obvious advantages compared with the reaction route of CO2 direct conversion to synthetic chemicals, such as mild reaction conditions, good atom economy, and broad industrialization prospects. The implementation of the project will help China seize the international commanding heights of CO2 utilization technology, solve and break through the bottleneck problem of clean and efficient utilization of coal in China, and open up a new path for the high-value utilization of CO2, which has important strategic significance. (Reporter Hua Ling)
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