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According to the project leader Professor Su Weike of Zhejiang University of Technology, chloroform, anhydrides, carbonates, isocyanates, and acid chlorides are key intermediates for medicines, pesticides, dyes, and polymers. The traditional production processes of these five products use highly toxic and highly toxic reagents. Among these reagents, phosgene is a chemical weapon. Thionyl chloride, phosphorus trichloride, phosphorus oxychloride, and phosphorus pentachloride are the precursors of chemical weapons. Half of the eight pollution incidents in the global chemical industry in the last century Both are related to thionyl chloride.
How to make the synthesis of these key intermediates green and clean has become a major issue facing the field of fine chemicals. After undertaking this task, Zhejiang University of Technology first identified the key points to tackle, namely starting from the green chemistry technology, starting from the three aspects of the replacement of toxic and hazardous materials, high-efficiency catalyst technology, and comprehensive utilization of resources, to achieve high efficiency, safety, and environmental friendliness. Low-cost alternatives to toxic or highly toxic raw materials for the green production of chloroformamides, anhydrides, carbonates, isocyanates and acid chlorides.
Su Weike said that in the field of research, foreign countries generally use nucleophilic activation reagents, the cost of replacement is high, and there are still hidden dangers of safety and environmental protection. After years of research, they used BTC to replace phosgene and other raw materials in the synthesis of acid chloride series products, achieving efficient catalysis, enabling the preparation of key intermediates such as penicillin to achieve mild reaction conditions, low energy consumption, high yield, and high product quality. The advanced level of similar foreign products. At the same time, hydrogen chloride, a by-product, will also be used for the preparation of industrial hydrochloric acid, thus realizing resource utilization.
After the replacement of toxic raw materials was achieved, the research team began to develop the green synthetic process of intermediates. In the synthesis of acid anhydrides, carbonates, isocyanates, and acid chlorides, the research group replaced traditional auxiliary reagents with catalytic reactions, improved the reaction rate and selectivity, and shortened the reaction steps; the use of green catalyst trifluoromethanesulfonate instead of non-recyclable three The aluminum chloride catalyst significantly reduced the amount of “three wastes†from the source of the process, increased resource utilization, and achieved a greener catalyst and reaction process.
Through nearly 20 years of efforts, Su Weike and others have used the catalytic reaction to replace the equivalent reaction based on the principle of atomic economics. They finally invented a green chemical synthesis technology that uses BTC to replace phosgene to synthesize these five key intermediates. The technology and equipment for producing high-purity hydrochloric acid using hydrogen chloride as a by-product have been developed so that the utilization rate of chlorine atoms approaches 100%, and the utilization of by-products is realized. It not only provided technical support for reducing the consumption of fine chemicals, but also promoted the development of pharmaceutical and other related industries.
At present, the technical achievements have been applied in the production of dozens of products of more than 10 companies such as Zhejiang Limin Chemical Co., Ltd., and more than 20 production lines have been transformed and constructed, and 6000 tons of products have been accumulated in the past 3 years. 600 million yuan, profits and taxes of 200 million yuan, and achieved remarkable social and economic benefits.
To support the development of fine chemicals "green umbrella"
—— The second-prize award of the National Technological Invention Award replaces the development of green chemistry technology for phosgene and thionyl chloride and other toxic materials. The refinement rate is an important indicator of the development level of a country’s chemical industry. How to minimize the harm to the environment while vigorously developing the fine chemical industry has always been the focus of chemical science and technology. A green synthesis and new process of key intermediates promoted by the industry experts as “promoting the sustainable development of the pharmaceuticals, pesticides and dyes industry†won the second prize of the National Technological Invention Award at the beginning of the new year. The new process for the synthesis of chloroformamide from toxic and hazardous materials such as phosgene and thionyl chloride by bis(trichloromethyl)carbonate (BTC) completed by Zhejiang University of Technology not only eliminates environmental pollution from the source, but also The use of water decreased by 60%, the average energy consumption decreased by 30%, and the integrated production cost decreased by 40%.