C<sub>1</sub>-Based Route for Vinyl Chloride Synthesis with Environmental and Economic Benefits
Yue Wang, Shihui Zou, Abhinandan Nabera, Xutao Chen, Yang Pan, Kunkun Wei, Yunxin Bao, Jingbo Hu, Yilin Zhao, Chengyuan Liu, Juanjuan Liu, Yong Wang, Yutao Ren, Gonzalo Guillén‐Gosálbez, Javier Pérez‐Ramírez, Jie Fan
Abstract
Selective coupling of C 1 platform molecules to C 2 olefins is a cornerstone for establishing a sustainable chemical industry based on nonpetroleum sources. Vinyl chloride (C 2 H 3 Cl), one of the top commodity petrochemicals, is commercially produced from coal- or oil-derived C 2 hydrocarbon (acetylene and ethylene) feedstocks with a high carbon footprint. Here, we report a C 1 -based route for vinyl chloride synthesis via the selective oxidative coupling of methyl chloride. This is enabled by a solid catalyst, featuring tungstate nanoclusters embedded in a zirconia matrix, which effectively captures ·CH 2 Cl radicals homogeneously generated in CH 3 Cl oxy-pyrolysis and selectively couples them into C 2 H 3 Cl. In situ synchrotron-based vacuum ultraviolet photoionization mass spectrometry provides direct experimental evidence of the homogeneous-heterogeneous reaction mechanism. The process achieves methyl chloride conversion of 10–65% with a high vinyl chloride selectivity (60–75%) at a reaction temperature of 650–750 °C, which is much lower than the traditional pyrolysis (>850 °C). The catalyst delivers stable performance (at a vinyl chloride yield of ca. 30%) with no deactivation observed during a 50 h test. Furthermore, combining with reaction of methanol and HCl to produce methyl chloride, we establish a methanol-to-vinyl chloride (MTV) route with the potential for significant reductions in climate change impact (24%) and cost (38%) compared to the state-of-the-art ethylene-based balanced process. A more remarkable 237% reduction in climate change impacts can be anticipated in the future-oriented green scenario for the MTV process primarily attributed to the utilization of renewable C 1 feedstocks that results in negative net contributions to the overall impacts.