Efficient methanol synthesis: Perspectives, technologies and optimization strategies

The conversion of H2 and CO2 to liquid fuels via Power-to-Liquid (PtL) processes is gaining attention. With their higher energy densities compared to gases, the use of synthetic liquid fuels is particularly interesting in hard-to-abate sectors for which decarbonisation is difficult. However, PtL poses new challenges for the synthesis: away from syngas-based, continuously run, large-scale plants towards more flexible, small-scale concepts with direct CO2-utilisation. This review provides an overview of state of the art synthesis technologies as well as current developments and pilot plants for the most prominent PtL routes for methanol, DME and Fischer–Tropsch-fuels. It should serve as a benchmark for future concepts, guide researchers in their process development and allow a technological evaluation of alternative reactor designs. In the case of power-to-methanol and power-to-FT-fuels, several pilot plants have been realised and the first commercial scale plants are planned or already in operation. In comparison power-to-DME is much less investigated and in an earlier stage of development. For methanol the direct CO2 hydrogenation offers advantages through less by-product formation and lower heat development. However, increased water formation and lower equilibrium conversion necessitate new catalysts and reactor designs. While DME synthesis offers benefits with regards to energy efficiency, operational experience from laboratory tests and pilot plants is still missing. Furthermore, four major process routes for power-to-DME are possible, requiring additional research to determine the optimal concept. In the case of Fischer–Tropsch synthesis, catalysts for direct CO2 utilisation are still in an early stage. Consequently, today's Fischer–Tropsch-based PtL requires a shift to syngas, benefiting from advances in co-electrolysis and reverse water-gas shift reactor design.

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Power-to-liquid via synthesis of methanol, DME or Fischer–Tropsch-fuels: a review

Methanol Synthesis from CO/CO2/H2over Cu/ZnO/Al2O3at Differential and Finite Conversions

A review of cleaner production methods for the manufacture of methanol

https://digitalcommons.unl.edu/cgi/viewcontent.cgi?article=1063&context=chemengall

Chemical storage of wind energy by renewable methanol production: Feasibility analysis using a multi-criteria decision matrix

Kinetics of methanol synthesis over commercial copper/zinc oxide/alumina catalysts

The kinetic model for the synthesis of bis(2-ethylhexyl) phthalate from phthalic anhydride and 2-ethylhexanol in the presence of methane sulfonic acid as a catalyst has been derived, based on the investigation carried out in an isothermal, semibatch reactor. The first step, the formation of mono(2-ethylhexyl) phthalate, is very fast and irreversible. The second step, the esterification of monoester with 2-ethylhexanol, is relatively slow and needs a catalyst. The second reaction appears to be of the first order with respect to mono(2-ethylhexyl) phthalate and does not depend on the concentration of alcohol.

Synthesis of bis(2-ethylhexyl) phthalate over methane sulfonic acid catalyst. Kinetic investigations

Kinetic investigations on the syntheses of higher aliphatic alcohol (C7, C9, C11) phthalates have been conducted in an isothermal, semibatch reactor. The first stage of the process, the formation of monoester, is very fast and irreversible. The second stage, the esterification of monoester towards diester, is slow and catalyst should be used. These reactions appear to be first order with respect to monoester and do not depend on the concentration of alcohol.

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Kinetic investigations on the esterification of phthalic anhydride with n-heptyl, n-nonyl or n-undecyl alcohol over sulfuric acid catalyst

Investigations in an isothermal, semibatch reactor have been conducted to find out kinetic parameters for the synthesis of dibutyl phthalate (DBP) and diisobutyl phthalate (DIBP) from phthalic anhydride and butyl alcohol or isobutyl alcohol,. The first stage, the formation of monoester, is very fast and irreversible. The second stage of the process, the esterification of monoester to diester, is slow. This reaction rate appears to be first-order with respect to the monoester and the rate does not depend on the concentration of alcohol.

Henryk Moroz

Papers

Kinetics of methanol synthesis over commercial copper/zinc oxide/alumina catalysts

Synthesis of bis(2-ethylhexyl) phthalate over methane sulfonic acid catalyst. Kinetic investigations

Kinetic investigations on the esterification of phthalic anhydride with n-heptyl, n-nonyl or n-undecyl alcohol over sulfuric acid catalyst

Kinetics of the synthesis of butyl phthalates over methane sulfonic acid catalyst