Sustainable Production of Emerging Diesel Additive from Butene by Palladium-Catalyzed Alkoxycarbonylation

Abstract

Pentanoic esters are a new class of biofuels (additives) and are typically produced from biomass-derived levulinic acid/esters via hydrogenation-cyclization/ring-opening/ hydrogenation three-step transformations. Here, a one-step and atom-economic alkoxycarbonylation route is developed to produce pentanoic esters from widely available 1-butene. Based on the screening of 21 monophosphine and 26 diphosphine ligands, a Pd/ diphosphine ligand (bis(2-diphenylphosphinophenyl) ether, DPEphos) system gives 91% yield of linear and branched ethyl pentanoate (78/22 ratio) with a turnover number (TON) up to 26100 and demonstrates outstanding recycle potential. The apparent activation energy (E a ) of 1-butene alkoxycarbonylation in the presence of this catalytic system was estimated to be 89.4 kJ/mol via kinetic measurements. More importantly, homogeneously blending 10 vol % of the resultant esters in pure diesel can improve the low-temperature fluidity and pumpability of diesel and decrease the emission of exhaust pollutants of diesel without affecting the power performance of diesel engines. Compared with pure diesel, the CO, NO x , HC, and soot emission of blend diesel at 2500 rpm are reduced by 28%, 9%, 6%, and 42%, respectively. This work provides a promising route to produce high-performance fuel additive and simultaneously broadens the comprehensive utilization of C4 olefin.

Synergistic Catalysis for Promoting Ring-Opening Hydrogenation of Biomass-Derived Cyclic Oxygenates

“…Similarly, γ-valerolactone, as an important biomass platform molecule of five-membered lactone, has been used for sustainably producing valued chemicals and fuels . Notably, its ring-opening hydrogenation by selective cleavage of the alkoxyl C–O bond has been identified as a promising route to produce valeric acid and its esters, which have been considered as green fuel additives identified by a 250 000 km road trial by Shell company and our recent study. , …”

“…11 Notably, its ring-opening hydrogenation by selective cleavage of the alkoxyl C−O bond has been identified as a promising route to produce valeric acid and its esters, which have been considered as green fuel additives identified by a 250 000 km road trial by Shell company and our recent study. 12,13 One common strategy for the hydrogenation transformation of oxygen-containing groups involves selective C−O bond cleavage followed by the addition of hydrogen, thus requiring a catalyst with bifunctional and even multifunctional sites for coordination (for homogeneous molecular catalyst)/adsorption (for heterogeneous solid catalyst) and activation of the "taskspecific" groups and hydrogen. 14 The synergy of these different sites plays a critical role in modulating product selectivity and promoting catalytic activity.…”

A Review on Biodiesel Production, Analysis, and Emission Characteristics from Non‐Edible Feedstocks

“…As the biodiesel sample cools, its flow behavior can be visually observed using glass pour point equipment. To determine the flow characteristics of a biodiesel sample as it cools, an automatic pour point equipment can be used under computer control [149] . The measured temperature at which the fuel begins to exhibit viscous behavior (the “pour point”).…”

“…To determine the flow characteristics of a biodiesel sample as it cools, an automatic pour point equipment can be used under computer control. [149] The measured temperature at which the fuel begins to exhibit viscous behavior (the "pour point"). Measurements of pour point should be made in line with a standardized procedure for the most reliable and consistent outcomes.…”

Artificial multi-enzyme cascades and whole-cell transformation for bioconversion of C1 compounds: Advances, challenge and perspectives

“…Capturing and transforming CO 2 into value-added products is considered a sustainable approach to consume atmospheric greenhouse gases, yet currently only one-carbon (C1) compounds can be produced efficiently via electrosynthesis [ 3 ]. In this context, massive efforts have been devoted to constructing native or synthetic methylotrophic cell factories for bioconversion of C1 compounds to fuels and value-added chemicals [ [3] , [4] , [5] ]. However, they are frequently inefficient and suffer from a series of drawbacks for biomanufacturing, including complicated regulation, slow kinetics and carbon/energy inefficiencies.…”