The objective of this work was to study the effect of supercritical water on coke formed on ZSM-5 during its use as a dodecane cracking catalyst. ZSM-5 coking was quantified at different reaction times, finding that the presence of supercritical water reduced coke formation by an order of magnitude or more. Coked samples were analyzed using several methods, including temperature programmed oxidation (TPO), attenuated total reflectance infrared (ATR-IR) spectroscopy, carbon-13 nuclear magnetic resonance (13C NMR), diffuse reflectance ultraviolet-visible spectroscopy (DR-UV-vis) and UV-Raman. Coked produced in the absence of SCW was formed by polycyclic aromatic hydrocarbons (PAHs) with more than 4 aromatic rings containing alkyl side chains. Coke produced in the presence of SCW was formed by aromatics with 1 to 3 aromatic rings. The characteristics of coke formed in the absence of water on ZSM-5 that had been pretreated in SCW were intermediate to those of coke formed on fresh ZSM-5 in the presence and absence of water, suggesting that the presence of water influences coke properties. It was also verified that SCW can decrease coke formation due to its effect on Bronsted acidity of the catalyst and ability to promote coke gasification. The effect of coke deposits produced in the presence and absence of SCW on the rate of ethanol dehydration, a model reaction studied under diffusion-controlled conditions, indicated that SCD/SWC coke deactivated less the catalyst than SCD coke.

Previous studies have successfully used near and supercritical water (SCW) for cracking and desulfurization of heavy crude oil and bio-oil, suppressing coke formation as a low-value by-product. Some of these studies benefited from using zeolite catalysts to increase the activity and selectivity toward targeted products; however, in depth studies are required to identify the role of water on zeolite catalysis under supercritical condition. Using three common zeolites, ZSM-5, HY, and β for supercritical water cracking of dodecane at 400°C, 24±2 MPa (in a 100 ml batch reactor), we showed that ZSM-5 is the only catalyst that partially retains its crystalline structure and activity under hydrothermal conditions. Further characterization of the ZSM-5 (used under 50/50 wt% SCW/dodecane feed) revealed 95% decrease in Brønsted acid site (BAS) density and 80% decrease in microporous area after 2 h reaction time. However, compared to the runs where SCW was absent, the apparent dodecane cracking rate constant in SCW decreased only by a factor of 2.6. Examining catalytic activity of ZSM-5 degradation products and re-using ZSM-5 showed that the unexpected activity cannot be ascribed to ZSM-5 degradation products. Using a group-type model, we showed that SCW accelerated gas and suppressed coke formations. Additionally a coke gasification pathway was suggested to account for formation of CO and CO2 in the presence of SCW. Additional experiments with two different ZSM-5 particle sizes suggested that dodecane cracking reaction is diffusion-limited in the absence of SCW and reaction-limited in its presence. Zero length chromatography of calcined and hydrothermally treated ZSM-5 showed 10 times greater apparent diffusivity for un-treated catalyst. This, according to Weisz-Prater analysis, suggested a 250 times greater dodecane surface concentration in the absence of SCW. We successfully optimized the water content of feed (5-15 wt%) to decrease the destructive effects of SCW on the structure, increase the selectivity toward BTEX products and eliminate coke formation.

Previous studies have successfully used near and supercritical water (SCW) for cracking and desulfurization of heavy crude oil and bio-oil, suppressing coke formation as a low-value by-product. Some of these studies benefited from using zeolite catalysts to increase the activity and selectivity toward targeted products; however, in depth studies are required to identify the role of water on zeolite catalysis under supercritical condition. Using three common zeolites, ZSM-5, HY, and β for supercritical water cracking of dodecane at 400°C, 24±2 MPa (in a 100 ml batch reactor), we showed that ZSM-5 is the only catalyst that partially retains its crystalline structure and activity under hydrothermal conditions. Further characterization of the ZSM-5 (used under 50/50 wt% SCW/dodecane feed) revealed 95% decrease in Brønsted acid site (BAS) density and 80% decrease in microporous area after 2 h reaction time. However, compared to the runs where SCW was absent, the apparent dodecane cracking rate constant in SCW decreased only by a factor of 2.6. Examining catalytic activity of ZSM-5 degradation products and re-using ZSM-5 showed that the unexpected activity cannot be ascribed to ZSM-5 degradation products. Using a group-type model, we showed that SCW accelerated gas and suppressed coke formations. Additionally a coke gasification pathway was suggested to account for formation of CO and CO2 in the presence of SCW. Additional experiments with two different ZSM-5 particle sizes suggested that dodecane cracking reaction is diffusion-limited in the absence of SCW and reaction-limited in its presence. Zero length chromatography of calcined and hydrothermally treated ZSM-5 showed 10 times greater apparent diffusivity for un-treated catalyst. This, according to Weisz-Prater analysis, suggested a 250 times greater dodecane surface concentration in the absence of SCW. We successfully optimized the water content of feed (5-15 wt%) to decrease the destructive effects of SCW on the structure, increase the selectivity toward BTEX products and eliminate coke formation.