Innovative reactive distillation process for the eco-friendly Poly(oxymethylene) dimethyl ethers synthesis from methylal and trioxane

Poly(oxymethylene) dimethyl ethers (PODEn) is a promising excellent additive for diesel fuels. The PODEn production by traditional reactor conform to Schulz − Flory distribution resulting in low product yield and large circulating material flow, which leads to high energy consumption and cost. This study presents a novel reactive distillation (RD) process for the PODEn synthesis by polymerization reaction from trioxane and methylal. A rigorous simulation model of the RD process was developed for the plant design and scale-up. Also, a sensitivity analysis was performed to determine the influence of key operating parameters on the RD process performance. The production composition analysis indicates that the RD process can effectively control the degree of polymerization and obtain high selectivity for any target product(s). The techno-economic analysis shows that the process is feasible, with over 96% and 13% reduction in CapEx and OpEx, over 68% savings in total annual costs as compared to the reaction-separation technology. Higher conversion and selectivity can be obtained by RD, within lower recirculation rate (only 12281 kg/h instead of 2950 kg/h) as compared to the conventional process.