The main objective of the present work was the evaluation of commercial ZSM-5 catalysts (diluted with a silica-alumina matrix) in the in situ upgrading of lignocellulosic biomass pyrolysis vapours and the validation of their bench-scale reactor performance in a pilot scale circulating fluidized bed (CFB) pyrolysis reactor. The ZSM-5 based catalysts were tested both fresh and at the equilibrium state, and were further promoted with cobalt (Co, 5% wt%) using conventional wet impregnation techniques. All the tested catalysts had a significant effect on product yields and bio-oil composition, both at bench-scale and pilot scale experiments, producing less bio-oil but of better quality. Incorporation of Co exhibited no additional effect on water or coke production induced by ZSM-5, compared to non-catalytic fast pyrolysis. On the other hand, Co addition significantly increased the formation of CO 2 compared to the CO increase which was favored by the use of ZSM-5 alone. These changes in CO 2 /CO yields are indicative of the different decarbonylation/decarboxylation mechanism that applies for Co 3 O 4 compared to ZSM-5 zeolite, due to the differences in their acidic properties (mainly type of acid sites). Co-promoted ZSM-5 catalysts simultaneously enhanced the production of aromatics and phenols with a more pronounced performance in the pilot-scale experiments resulting in the formation of a three phase bio-oil, rather than the usual two phase catalytic pyrolysis oil (aqueous and organic phases). The third phase produced is even lighter than the aqueous phase and consists mainly of aromatic hydrocarbons and phenolic compounds. Addition of Co in ZSM-5 is thus suggested to strongly enhance aromatization reactions that result in selectivity increase towards aromatics in the bio-oil produced. Possible routes of catalyst deactivation in the pilot plant's continuous operation process have been suggested and are related to pore blocking and masking of acid sites by formed coke (reversible deactivation), partial framework dealumination of the fresh zeolitic catalyst, and accumulative ash deposition on the catalyst that depends on the nature of biomass (content of ash). † Electronic supplementary information (ESI) available. See
Zirconia-supported tungsten oxide (WO(x)/ZrO(2)) is considered an important supported metal oxide model acid catalyst, for which structure-property relationships have been studied for numerous acid-catalyzed reactions. The catalytic activity for xylene isomerization, alcohol dehydration, and aromatic acylation follows a volcano-shape dependence on tungsten surface density. However, WO(x)/ZrO(2) has not been studied for more acid-demanding reactions, like n-pentane isomerization, with regard to surface density dependence. In this work, WO(x)/ZrO(2) was synthesized using commercially available amorphous ZrO(x)(OH)(4-2x) and model crystalline ZrO(2) as support precursors. They were analyzed for n-pentane isomerization activity and selectivity as a function of tungsten surface density, catalyst support type, and calcination temperature. Amorphous ZrO(x)(OH)(4-2x) led to WO(x)/ZrO(2) (WZrOH) that exhibited maximum isomerization activity at ∼5.2 W·nm(-2), and the crystalline ZrO(2) led to a material (WZrO(2)) nearly inactive at all surface densities. Increasing the calcination temperature from 773 to 973 K increased the formation of 0.8-1 nm Zr-WO(x) clusters detected through direct imaging on an aberration-corrected high-resolution scanning transmission electron microscope (STEM). Calcination temperature further increased catalytic activity by at least two times. Brønsted acidity was not affected but Lewis acidity decreased in number, as quantified via pyridine adsorption infrared spectroscopy. WO(x)/ZrO(2) exhibited isomerization activity that peaked within the first 2 h time-on-stream, which may be due to Zr-WO(x) clusters undergoing an activation process.
Ce-Co and La-Co mixed oxides were synthesised by two different methods: exotemplating and evaporation. The obtained catalysts were evaluated for volatile organic compounds (VOCs) abatement, using toluene as model molecule. The materials were characterised by N 2 adsorption at -196 ºC, X-ray diffraction (XRD), scanning © 2014. This manuscript version is made available under the Elsevier user license http://www.elsevier.com/open-access/userlicense/1.0/ electron microscopy (SEM), H 2 temperature programmed reduction (H 2 -TPR) and NH 3 temperature programmed desorption (NH 3 -TPD) in order to reveal the structure-activity relationship. The results obtained showed the superiority of mixed oxides compared to single oxides in toluene oxidation. Ce-Co mixed oxides were more active than La-Co samples. For Ce-Co materials, the exotemplating method produced catalysts which were more active than those prepared by the evaporation procedure. The former showed the best catalytic performances, with full conversion of toluene into CO 2 at about 250 o C.Temperatures higher than 320 o C were required with single oxides. Characterization studies revealed strong interactions between Ce (or La) and Co, leading to a fine dispersion of oxide phases in binary systems. As a result, both the surface area and reducibility of the catalysts increase, which can be accounted for the higher performance of the mixed oxides. Furthermore, NH 3 -TPD studies showed a linear relationship between acidity and VOC oxidation activity. In fact, a high concentration of weak acid sites is required for high toluene oxidation activity. The results can be explained in terms of a Mars-van Krevelen type of mechanism, involving the adsorption of toluene and its subsequent oxidation by lattice and/or surface oxygen.
Hierarchical zeolites have been identified as special catalytic materials with improved catalytic properties. In this study, hierarchical bifunctional ZSM5 based catalysts were prepared by desilication for controlled mesoporosity development and have been modified by Co doping. Their performance in the catalytic pyrolysis of oak in a lab scale reactor was evaluated. Desilicated counterparts were proven more active in deoxygenation of bio oil, while carbon deposition on the catalysts reduced compared to non-desilicated counterparts. Increased Lewis acidity favors decarboxylation reactions, while higher olefins as well as PAH content indicate easier diffusion within and from the porous network and interactions in the mesopores. The conversion of bulky lignin molecules (alkoxy phenols) is enhanced by the mesopores, while acidity is of secondary importance. Coke deposition inside the pores is more profound in the desilicated catalysts due to larger pore size. Carbon deposition on the catalysts is reduced in the following order: HZSM5 > Co/HZSM5 > Ds-HZSM5 > Co/Ds-HZSM5. GC-MS characterization of the CH 2 Cl 2 soluble coke indicated that for the desilicated counterparts the main coke precursors are the bulky lignin molecules which are partially deoxygenated.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.