The use of combination of zeolites to pursue integrated refined pyrolysis oil from kraft lignin

Abstract

A mixture of Y and M type zeolites were applied to pyrolyze kraft softwood (SW) lignin with the objective of studying the combination effect of different types of zeolite on pyrolysis. The chemical structures of the subsequent pyrolysis oils were examined. Nuclear Magnetic Resonance (NMR) spectroscopy including 13 C, 31 P of phosphitylated bio-oils, Heteronuclear Single-Quantum Correlation (HSQC)-NMR, and Gel Permeation Chromatography (GPC) were used to characterize the pyrolysis oils. The yields of pyrolysis products (light oil, heavy oil and char) from the zeolites combination 'Y + M' catalyzed pyrolysis ranged between the pyrolysis oil yields from zeolite Y or M catalyzed pyrolysis. 31P NMR analysis of the phosphitylated bio-oils revealed that the mixture of 'Y + M' during pyrolysis could decrease the carboxyl groups by 84%, which is close to the effect of the M zeolite. The yields of hydroxyl groups and other functional groups in the 'Y + M' generated bio-oil was between the individual Y and M generated oils. The molecular weight of the pyrolysis oil using a zeolite mixture of 'Y + M' was similar to the individual zeolite Y assisted pyrolysis. These results show that the zeolite mixture of 'Y + M' manifests additive characteristics for pyrolysis.

Effect of using regenerated combined FAU and MOR zeolites as catalysts during the pyrolysis of kraft lignin

“…In addition, a previous study supported that the quantity of every pyrolysis product (heavy oil, light oil, char, and gas) for the combination of the 'Y + M' sample catalyzed pyrolysis remained between the individual Y and M zeolites catalyzed pyrolysis (Huang et al 2014). This phenomenon was observed after the regeneration of each cycle.…”

“…No studies have been reported yet to show the catalytic effects of different regeneration times using the combined zeolites and their effect on pyrolysis of lignin. In previous studies, (Huang et al 2014) combined 'Y + M', individual Y and M zeolites were used to catalyze the lignin pyrolysis and the results showed that the combined 'Y + M' sample had a catalytic performance that was in between the individual Y and M zeolites.…”

“…Based on previous work (Huang et al 2014), in this paper, a comparative study of regenerating these zeolites (individual Y and M and combined 'Y + M' sample) and their reuse in the catalytic pyrolysis of kraft lignin was carried out. The goals of this study include: 1) to evaluate the effect of regenerating the combined 'Y + M' sample on the key parameters of zeolites in the lignin pyrolysis, such as: Brunauer, Emmet, and Teller (BET) and micropore surface area (MSA) and total acid sites (TAS) of zeolites; and 2) to study the performance of these regenerated zeolites during the subsequent lignin pyrolysis.…”

Factors Affecting the Sensitivity of Hydroxyl Group Content Analysis of Biocrude Products via Phosphitylation and 31P NMR Spectroscopy

“…Hydroxyl group types in a wide range of biomass-derived products have been effectively quantified by phosphitylation and 31 P NMR analysis. This analytical technique was first described by Schiff et al in 1986 and then further developed and practically applied by Argyropoulos et al to study lignin and wood chemistry. , In addition to its use in lignin characterization, − the above method has also been widely applied in the study of hydroxyl compounds in tannins and flavonoids, , extra-virgin olive oil, biodiesel, pyrolysis oil, − hydrothermal liquefaction (HTL) biocrude, and upgraded bio-oil . The quantitative reaction between hydroxyl groups and a phosphitylating agent, such as 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (TMDP), in the presence of a Brønsted base (Scheme ) has been employed for this purpose. , Reaction of hydroxyl groups with TMDP replaces hydroxyl protons with a nonionizable phosphorus-containing moiety (PO 2 C 6 H 12 ).…”

Catalytic Rapid Pyrolysis of Quercus variabilis over Nanoporous Catalysts

“…A number of papers on catalytic rapid pyrolysis of wood over porous materials have recently been published over the world [11][12][13][14][15][16][17][18][19][20]. Various characteristics of porous materials, for example, quantity and strength of acid sites, surface area, pore size, and crystallinity, have been shown to influence the reforming of bio-oil.…”