Synthesis of Butyl-Exchanged Polyoxymethylene Ethers as Renewable Diesel Blendstocks with Improved Fuel Properties

Arellano-Trevino, Martha A.; Bartholet, Danielle; To, Anh The; Bartling, Andrew W.; Baddour, Frederick G.; Alleman, Teresa L.; Christensen, Earl D.; Fioroni, Gina M.; Hays, Cameron; Luecke, Jon; Zhu, Junqing; McEnally, Charles S.; Pfefferle, Lisa D.; Reardon, Kenneth F.; Foust, Thomas D.; Ruddy, Daniel A.

doi:10.1021/acssuschemeng.0c09216

Title: Synthesis of Butyl-Exchanged Polyoxymethylene Ethers as Renewable Diesel Blendstocks with Improved Fuel Properties

Journal Article · Tue Apr 27 00:00:00 UTC 2021 · ACS Sustainable Chemistry & Engineering

DOI: https://doi.org/10.1021/acssuschemeng.0c09216 · OSTI ID:1782442

^[1]; Bartholet, Danielle ^[2]; To, Anh The ^[1]; Bartling, Andrew W. ^[1];

^[1];

^[1]; Hays, Cameron ^[1];

^[1]; Zhu, Junqing ^[3]; McEnally, Charles S. ^[3]; Pfefferle, Lisa D. ^[3]; Reardon, Kenneth F. ^[2];

^[1];

^[1]

National Renewable Energy Lab. (NREL), Golden, CO (United States)
Colorado State Univ., Fort Collins, CO (United States)
Yale Univ., New Haven, CT (United States)

Methyl-terminated polyoxymethylene ethers (MM-POMEs), having the formula CH3O–(CH2O)n–CH3 (n = 3–5), are a high-cetane, low-sooting group of oxygenates that have recently attracted attention as potential diesel blendstocks. Despite these attractive fuel properties, MM-POMEs have shortcomings due to their low energy density and high water solubility. Guided by a computational fuel property assessment for POMEs with longer end-groups, the most promising improvements in the desired compression ignition fuel properties were observed for butyl-terminated POMEs. Here, an acid-catalyzed transacetalization reaction was developed to exchange the methyl end-groups of MM-POMEs (n = 3–6) with butyl end-groups. The reaction utilizes an ion-exchange resin as the acid catalyst at mild reaction conditions of 60 °C and atmospheric pressure. Approximately 100 mL of butyl-exchanged POMEs in the diesel boiling range were produced, enabling laboratory-scale fuel property testing. The butyl-terminated POME mixture possesses the advantaged fuel properties of the parent MM-POMEs (low-soot, high-cetane) while exhibiting improved energy density (lower heating value (LHV) of 30 MJ/kg) and substantially reduced water solubility (7.3 g/L) compared to the parent MM-POME mixture (LHV of 19 MJ/kg , water solubility of 258 g/L).

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Research Organization:: Colorado State University; National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Bioenergy Technologies Office

Grant/Contract Number:: AC36-08GO28308; EE0008726

OSTI ID:: 1782442

Report Number(s):: NREL/JA--5100-79006; MainId:32923; UUID:105473ec-c2f0-48dd-90a7-3661d1d79f38; MainAdminID:19896

Journal Information:: ACS Sustainable Chemistry & Engineering, Journal Name: ACS Sustainable Chemistry & Engineering Journal Issue: 18 Vol. 9; ISSN 2168-0485

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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