Recently, the ethylene polyphase hydroformylation and hydrogenation technology to produce n-propanol industrialization plant was successfully put into operation in Ningbo Juhua New Materials Co., LTD. The core technology of the device by the Chinese Academy of Sciences Dalian Institute of Chemical Physics Ding Yunjie researcher, Yan Li researcher team independent research and development, creative use of single atom catalyzed olefin polyphase hydroformylation technology. The quality of propanaldehyde and n-propanol have reached the international standard of excellence, and the aldehydes produced can be further converted into alcohols, acids and esters and other chemicals.

The concept of single atom catalysis was put forward by Chinese scientist Zhang Tao, academician of Dalian Institute of Chemical Compounds, in 2011, and has become a frontier research hotspot in the field of catalysis in recent years. The core catalyst of the ethylene hydroformyl chemical industrial unit put into production uses a single atom catalyst, so that the concept in a laboratory has realized the practical application of industrial production in a short period of 9 years. The successful operation of the device not only provides an example for the wide industrial application of single atom catalyst, but also further enriches the theory of single atom catalysis. At the same time, the polyphase hydroformylation technology can be extended to the process of hydroformylation of other olefins to produce aldehydes.

There are some problems in the hydroformylation of

olefin, such as difficult separation of catalyst and product, loss of precious metal and ligand, large amount of low grade reaction heat can not be effectively utilized, and large amount of solvent is used. Although many academic articles have reported that the use of its research and development of heterogeneous catalysts can achieve olefin hydroformylation process, but so far, olefin hydroformylation industrial production can only use homogeneous catalytic process to achieve.

The research team of Ding Yunjie and Yan Li has been committed to the research of hydroformylation homogeneous catalytic heterogeneous technology for many years, and has successfully developed a heterogeneous catalytic technology that produces homogeneous catalytic active sites in situ by modifying organic ligands on the supported metal nanocrystals, but the technology has the problem of low utilization rate of precious metals. In 2012, the team designed and synthesized vinyl functionalized organic ligand monomers containing phosphorus or nitrogen atoms at the molecular level, and prepared organic polymer materials with highly exposed phosphorus or nitrogen atom skeleton as the structural unit, with large specific surface area and multistage pore structure. Such polymer materials have the dual functions of carrier and ligand. To form a single atom catalyst with multiple coordination structures and high stability with hydroformylated active metal components. In 2017, ethylene polyphase hydroformylation to propanal/n-propanol pilot test technology passed the technical appraisal organized by China Petroleum and Chemical Industry Federation. At the end of 2018, the construction of 50,000 tons/year ethylene hydroformylation to prepare propanal/n-propanol industrial plant began, and was successfully put into operation recently.

The device uses heterogeneous catalysis technology to solve the problems such as the loss of ligands and active metal components that have not been solved in homogeneous catalytic heterogeneous for more than 80 years. The device adopts the radial fixed bed reaction process for hydroformylation reaction, which not only realizes solvo-free industrial production, but also realizes the organic integration of the core technology of the catalyst and the key technology of the process, and solves the problem of effectively utilizing a large number of low-grade reaction heat.

Olefin hydroformylation reaction is the reaction that converts olefin, hydrogen and carbon monoxide into aldehydes. The utilization rate of raw materials in this process is close to 100%, which is of great significance in optimizing the utilization of resources. At present, the total production capacity of aldehydes and alcohols produced by olefins hydroformylation and hydrogenation technology in the world has reached about 24 million tons per year, of which the output of propylene hydroformylation to produce butanoctyl alcohol has reached about 16 million tons, of which China's consumption is 5 million tons.

At present has been industrialized ethylene hydroformylation technology, mainly by DP(Davy Power) and Dow Chemical (Dow) and JM (Johnson Matthey) three companies jointly developed, the catalyst for oil-soluble rhodium-phosphine ligand complex, The homogenous catalytic process is used. The production of ethylene polyphase hydroformylation and hydrogenation of n-propanol industrial plant is provided by Dalian Chemical Institute core technology, designed by Shanghai Huanqiu Engineering Co., LTD., and invested by Ningbo Juhua New Materials Co., LTD., with complete independent intellectual property rights of the heterogeneous catalytic process, can meet China's demand for independent production of aldehyde products.

Compared with the existing olefin hydroformylation technology outside China, the olefin polyphase hydroformylation technology uses a new catalyst, the utilization rate of precious metals on the catalyst is close to 100%, that is, all precious metals on the catalyst have played a catalytic role, and the loss of active components of the catalyst can be negligible. The technology also has a good economy, the catalyst and the reaction system do not need to be separated, greatly reducing the reaction cost; Through the clever energy-saving design in the engineering process, a large number of low-grade heat in the hydroformylation reaction and hydrogenation reaction can be efficiently used, and the reuse rate of reaction heat can reach more than 90%. In addition, the reaction system adopts a solvation-free green environmental protection process, without adding additional solvents, so it is more environmentally friendly.