Prospects of Producing Higher Alcohols from Carbon Dioxide: A Process System Engineering Perspective

Abstract

Higher alcohols are promising products for large-scale CO 2 utilization due to their potential large volume use as chemical energy carriers and fuel additives. Although the catalysts for these transformations are still in early stages of development, it is advantageous to examine their expected process level performance to guide further scientific progress. Here, we performed prospective techno-economic and environmental evaluations of 1-propanol, 1butanol, 1-pentanol, and 1-hexanol syntheses from captured CO 2 and green H 2 via the syngas route (i.e., CO 2 to syngas to higher alcohol) for the best case (ideal) conversion and selectivity. While 1-pentanol and 1hexanol plants show economic viability, the costs of manufacturing the other two alcohols exceed their respective revenues. In all the four processes, the cost of raw materials, utilities, and wastewater treatment accounts for about 83%, 12%, and 5% of the cost of manufacturing, respectively (neglecting CAPEX). Sensitivity analysis shows that the cost of H 2 has to drop to about 2100 and 1700 $ t −1 from the current level of ca. 2500 $ t −1 for 1-propanol and 1-butanol processes to break even. In all four processes, the fraction of H 2 feed lost to byproduct water ranges from 55 to 60%, which is an inherent issue with thermocatalytic hydrogenation of CO 2 . Although a standalone green 1-propanol plant is not presently viable, a hybrid process combining a recently studied synthesis route (using ethylene and CO 2 -derived syngas) and the novel route based solely on CO 2 can minimize the carbon footprint without sequestration and also be profitable at the prevailing hydrogen cost.

Thermocatalytic CO2conversion by siliceous matter: a review

“…Then, the produced alcohols can be separated from water. 60 3CO + 6H 2 → CH 3 CH 2 CH 2 OH + 2H 2 O|Δ H 298 K = −407 kJ mol −1 4CO + 8H 2 → CH 3 (CH 2 ) 2 CH 2 OH + 2H 2 O|Δ H 298 K = −558 kJ mol −1 4CO + 8H 2 → CH 3 (CH 2 ) 3 CH 2 OH + 2H 2 O|Δ H 298 K = −710 kJ mol −1 4CO + 8H 2 → CH 3 (CH 2 ) 4 CH 2 OH + 2H 2 O|Δ H 298 K = −862 kJ mol −1 …”

“…Carbon dioxide can also be converted to various value-added ne/specialty chemicals such as epoxides (ethylene oxide, epoxy butene, and epoxy propylbenzene), ethers, aldehydes/ketones, and carboxylic acids. Some of these overall general reactions are as follows: 60 Ethers:…”