TY - JOUR
T1 - Catalytic Conversion of Free Fatty Acids to Bio-Based Aromatics
T2 - A Model Investigation Using Oleic Acid and an H-ZSM-5/Al2O3Catalyst
AU - He, Songbo
AU - Klein, Frederike Gerda Hiltje
AU - Kramer, Thomas Sjouke
AU - Chandel, Anshu
AU - Tegudeer, Zhuorigebatu
AU - Heeres, Andre
AU - Heeres, Hero Jan
PY - 2021/1/25
Y1 - 2021/1/25
N2 - The catalytic conversion of oleic acid to aromatics (benzene, toluene, and xylenes, BTX) over a granular H-ZSM-5/Al2O3 catalyst (φ 1.2-1.8 mm, 10 g loading) was investigated in a continuous bench-scale fixed-bed reactor (10 g oleic acid h-1). A peak carbon yield of aromatics of 27.4% was obtained at a catalyst bed temperature of 550 °C and atmospheric pressure. BTX was the major aromatics formed (peak carbon yield was 22.7%), and a total BTX production of 1000 mg g-1 catalyst was achieved within a catalyst lifetime of 6.5 h for the fresh catalyst. The catalyst was deactivated due to severe coke deposition (ca. 22.1 wt % on the catalyst). The used catalyst was reactivated by an ex situ oxidative regeneration at 680 °C in air for 12 h. The regenerated catalyst was subsequently recycled, and in total, 7 cycles of reaction-regeneration were performed. A gradual decrease in the peak carbon yield of BTX was observed with reaction-regeneration cycles (e.g., to 16.3% for the catalyst regenerated for 6 times). However, the catalyst lifetime was remarkably prolonged (e.g., >24 h), leading to a significantly enhanced total BTX production (e.g., 3000 mg g-1 catalyst in 24 h). The fresh, used, and regenerated catalysts were characterized by N2 and Ar physisorption, XRD, HR-TEM-EDX, 27Al, and 29Si MAS ssNMR, NH3-TPD, TGA, and CHN elemental analysis. Negligible changes in textural properties, crystalline structure, and framework occurred after one reaction-regeneration cycle, except for a slight decrease in acidity. However, dealumination of the H-ZSM-5 framework was observed after 7 cycles of reaction-regeneration, leading to a decrease in microporosity, crystallinity, and acidity. Apparently, these changes are not detrimental for catalyst activity, and actually, the lifetime of the catalyst increases, rationalized by considering that coke formation rates are retarded when the acidity is reduced.
AB - The catalytic conversion of oleic acid to aromatics (benzene, toluene, and xylenes, BTX) over a granular H-ZSM-5/Al2O3 catalyst (φ 1.2-1.8 mm, 10 g loading) was investigated in a continuous bench-scale fixed-bed reactor (10 g oleic acid h-1). A peak carbon yield of aromatics of 27.4% was obtained at a catalyst bed temperature of 550 °C and atmospheric pressure. BTX was the major aromatics formed (peak carbon yield was 22.7%), and a total BTX production of 1000 mg g-1 catalyst was achieved within a catalyst lifetime of 6.5 h for the fresh catalyst. The catalyst was deactivated due to severe coke deposition (ca. 22.1 wt % on the catalyst). The used catalyst was reactivated by an ex situ oxidative regeneration at 680 °C in air for 12 h. The regenerated catalyst was subsequently recycled, and in total, 7 cycles of reaction-regeneration were performed. A gradual decrease in the peak carbon yield of BTX was observed with reaction-regeneration cycles (e.g., to 16.3% for the catalyst regenerated for 6 times). However, the catalyst lifetime was remarkably prolonged (e.g., >24 h), leading to a significantly enhanced total BTX production (e.g., 3000 mg g-1 catalyst in 24 h). The fresh, used, and regenerated catalysts were characterized by N2 and Ar physisorption, XRD, HR-TEM-EDX, 27Al, and 29Si MAS ssNMR, NH3-TPD, TGA, and CHN elemental analysis. Negligible changes in textural properties, crystalline structure, and framework occurred after one reaction-regeneration cycle, except for a slight decrease in acidity. However, dealumination of the H-ZSM-5 framework was observed after 7 cycles of reaction-regeneration, leading to a decrease in microporosity, crystallinity, and acidity. Apparently, these changes are not detrimental for catalyst activity, and actually, the lifetime of the catalyst increases, rationalized by considering that coke formation rates are retarded when the acidity is reduced.
KW - Bioaromatics
KW - BTX
KW - Fatty Acids
KW - Oleic Acid
KW - Vegetable Oil
KW - ZSM-5
UR - http://www.scopus.com/inward/record.url?scp=85099945648&partnerID=8YFLogxK
U2 - 10.1021/acssuschemeng.0c06181
DO - 10.1021/acssuschemeng.0c06181
M3 - Article
AN - SCOPUS:85099945648
SN - 2168-0485
VL - 9
SP - 1128
EP - 1141
JO - ACS Sustainable Chemistry and Engineering
JF - ACS Sustainable Chemistry and Engineering
IS - 3
ER -