【Ten Years of Great Progress in Chemical Technology】The world’s first plant for producing n-propanol using single-atom catalysts came online from 191 to 2020
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The chemical industry has seen significant development over the past decade; let’s praise the prosperity and strength of modern China. By sharing our insights, we can encourage more people to participate and make the discussions more lively. HaiChuan becomes even better with your involvement – we welcome everyone to join in the forum discussions. It’s hot in July, so be careful to prevent fires. ------------------------------------------- n-Propyl alcohol is a widely used chemical product that is currently applied in coatings, paints, adhesives, cosmetics, plastics, and fungicides. It also serves as an important raw material in various fields such as food additives, feed additives, synthetic fragrances, cleaners, preservatives, and brake fluids. Furthermore, n-propanol also has very important applications in the field of pharmaceutical intermediates, and it is used in the electrolytes for new energy vehicles as well. On September 10, 2020, Ningbo Juhua Chemical Technology Co., Ltd. announced that the 50,000-ton-per-year industrial facility for the phase-catalyzed hydroformylation of ethylene and subsequent hydrogenation to produce n-propanol had been successfully commissioned in its entirety from the first attempt, with qualified products being produced. This successful drive set two precedents: it was the first industrial application of a single-atom catalyst, as well as the first industrial application of the heterogeneous catalytic formylation technology for olefins. This project was jointly developed, designed, and constructed over 3 years by Ningbo Juhua Company, the Dalian Institute of Chemical Physics of the Chinese Academy of Sciences, and China Global Shanghai Company. Extensive optimizations and improvements were made in aspects such as process route selection, process flow design, equipment selection, and automatic control; a number of advanced control technologies that filled gaps in the industry were adopted, ultimately enabling a successful commissioning of the entire process in just one attempt. This device possesses entirely domestic independent intellectual property rights, and it is also the world’s first industrial-scale device for the polyphase catalytic hydroformylation of ethylene. Its main processing technology was developed by the team led by Researcher Ding Yunjie from the Dalian Institute of Chemical Physics, Chinese Academy of Sciences. For the first time, a bifunctional polymer consisting of a carrier with high surface area, a multi-level pore structure, and high thermal stability, along with a ligand, along with the precious metal heterogeneous single-site catalyst loaded on it, was used to address the global challenge of loss of precious metals and ligands during the heterogenization of homogeneous catalysis for olefin hydroformylation, a problem that had remained unsolved for over 70 years. Furthermore, compared with the homogeneous formylation process previously used in the industry, this technology employs a fixed-bed reaction system; the loss of active precious metals and organic ligands is negligible. The catalyst can be separated from the reactants and products with almost no cost, and no organic solvents are used in the reaction system, resulting in products with few impurities and high purity. This device represents the world’s first industrial application of single-atom catalysts, and it is the practical realization of the single-atom catalysis theory first proposed internationally by Academician Zhang Tao, Vice President of the Chinese Academy of Sciences. A single-atom catalyst is a special type of supported metal catalyst in which all metal components on the support are present in a single-atom dispersed form, with no metal–metal bonds between atoms. Unlike previous homogeneous catalysts, whose active centers are nanoparticles composed of nearly a hundred metal atoms, the utilization rate of precious metal atoms in single-atom catalysts is close to 100%. China’s production capacity for n-propanol is around 138,000 tons, while consumption in 2019 reached 195,000 tons; thus, the existing production capacity is insufficient to meet market demand. The successful commissioning of this facility will significantly reverse the unfavorable situation in China’s n-propanol market.
The hydroformylation of olefins is a reaction that converts olefins, hydrogen, and carbon monoxide into aldehyde compounds; the utilization rate of raw materials in this process is close to 100%, which makes it significant for the optimal use of resources. Aldehydes can be further converted into chemicals such as alcohols, acids, and esters, which serve as key raw materials for high-value fine chemicals like detergents, plasticizers, surfactants, as well as pharmaceuticals and fragrances. Currently, the global annual production capacity for aldehydes and alcohols produced through olefin hydroformylation and related hydrogenation technologies amounts to around 24 million tons. Of this amount, the production of butyl octyl alcohol via propylene hydroformylation reaches about 16 million tons, with China’s consumption alone accounting for 5 million tons. However, the homogeneous olefin hydroformylation catalytic process faces issues such as difficulties in separating the catalyst from the product, loss of precious metals and ligands, ineffective utilization of a large amount of low-grade reaction heat, and the extensive use of solvents. To address the aforementioned issues in the industrial production of homogeneous formylation, Ding Yunjie’s research team has spent many years studying the technology of converting homogeneous catalysis into a heterogeneous form. They have successfully developed a heterogeneous catalytic technique that enables the in-situ creation of homogeneous catalytic active sites on metal nanocrystals through modification with organic ligands; however, this technique has the drawback of low utilization efficiency of precious metals. In 2012, the research team led by Ding Yunjie and Yan Li designed and synthesized, at the molecular level, vinyl-functionalized organic ligand monomers containing phosphorus or nitrogen atoms. They then prepared organic polymer materials that utilized highly exposed phosphorus or nitrogen atoms as structural units, featuring a large specific surface area and a multi-level pore structure. Such polymer materials possess both carrier and ligand functions, and they can form single-atom catalysts with multiple coordination structures and high stability when combined with hydrogen formylated active metal single atoms (rhodium and cobalt ions). In 2017, the pilot-scale technology for the production of propionaldehyde/n-propanol via the polyphase hydroformylation of ethylene passed the technical evaluation organized by the China Petroleum and Chemical Industry Federation. At the end of 2018, construction began on an industrial facility with a capacity of 50,000 tons per year for the hydroformylation of ethylene to produce propionaldehyde/n-propanol, and it was successfully put into operation on August 27, 2020.
Ten years of rapid development in chemical technology – praising the prosperous and strong China of today