Novel Two-Step Process for the Production of Renewable Aromatic Hydrocarbons from Triacylglycerides

Abstract

A two-step process was developed for the production of aromatic hydrocarbons from triglyceride (TG) oils. In the first reaction step, TG (soybean) oil was noncatalytically cracked and purified by distillation to produce an organic liquid product (OLP). The resulting OLP was then converted into aromatic compounds in a second reaction using a zeolite catalyst, HZSM-5. In this second reaction, three main factors were found to influence the yield of aromatic hydrocarbons: the SiO2:Al2O3 ratio in the HZSM-5, the reaction temperature and the OLP-to-catalyst ratio. Upon cursory optimization, up to 58 w/w% aromatics were obtained. Detailed analyses revealed that most of the alkenes and carboxylic acids, and even many of the unidentified/unresolved compounds, which are characteristic products of noncatalytic TG cracking, were reformed into aromatic hydrocarbons. Instead of BTEX compounds, which are the common products of C2–C8 alkene and other feedstock reforming with HZSM-5, longer-chain alkylbenzenes dominated the reformate (along with medium-size n-alkanes). Another novel feature of the two-step process was a sizable (up to 13 w/w%) concentration of alicyclic hydrocarbons, both cyclohexanes and cyclopentanes. Thus, this novel two-step process may provide a new route for the production of renewable aromatic hydrocarbons as an important coproduct with transportation fuel products.

An Initial Study of the Catalytic Reforming of Crop Oil‐Derived 1‐Alkenes with HZSM‐5 to Aromatic Hydrocarbons

“…This may explain the shift of the aromatic homology profile from C 7 –C 8 for smaller‐size alkene feedstocks to C 8 –C 10 for 1‐tetradecene. Corroborating this hypothesis, C 9 –C 11 aromatics were found to be predominant when the carboxylic acids of triacylglycerols, which are also large molecules, were treated with zeolites under similar conditions (Benson et al, ; Fegade et al, ).…”

Renewably sourced phenolic resins from lignin bio‐oil

“…Biomass‐derived polymers are attractive alternatives to those derived from petroleum as they offer a route to fully sustainable materials. Among the currently available biomass based polymers, those that bear renewably sourced aromatic units are rare, owing to the difficulty of acquiring aromatic monomers from biomass . Nevertheless, when aromatic ring structures are incorporated into a polymer, they grant desirable physical properties to the material .…”

Application of pyrrolidone building blocks in developing renewable 2-oxazolines based thermosets

“…The chemical reaction named as the Michael addition reaction was introduced in the year of 1884 by the research of Arthur Michael, inspired by the work of Conard and Kuthzeit 53 . Initially, the Michael addition was considered as the addition of an enolate ion into the β-carbon atom of an α,β-unsaturated carbonyl compound 53 .…”

“…The chemical reaction named as the Michael addition reaction was introduced in the year of 1884 by the research of Arthur Michael, inspired by the work of Conard and Kuthzeit 53 . Initially, the Michael addition was considered as the addition of an enolate ion into the β-carbon atom of an α,β-unsaturated carbonyl compound 53 . Over the years, the Michael addition is not confined to the addition of only carbanions, as variety of nucleophiles bearing heteroatoms like nitrogen, oxygen, sulphur, and phosphor proved suitable Michael donors (scheme 1.1).…”

“…Though the use of 2,5furandicarboxylic acid based bis(2-oxazoline) is preferred from renewability aspects, its susceptibility towards cross-linking does not allow for the generation of noncrosslinked polymers which are required as reference in this study. Instead, for a better control over the cross-linking process, in this work we make use of IAox derived from isophthalic acid, which could become a future renewable building block as synthesis routes are emerging with, for example, renewable xylenes 51 , isoprene 52 , or triacylglycerides 53 as starting compounds. Lastly, in addition to the thermomechanical behavior we report on a potential route for chemical recycling of the BP-C8 monomer after hydrolysis of the thermosets.…”