Natural magnesium oxide (MgO) catalysts: A cost-effective sustainable alternative to acid zeolites for the in situ upgrading of biomass fast pyrolysis oil

Stefanidis, Stylianos D.; Karakoulia, Stamatia A.; Kalogiannis, Konstantinos G.; Iliopoulou, Eleni F.; Delimitis, A.; Yiannoulakis, H.; Zampetakis, T.; Lappas, Angelos A.; Triantafyllidis, Konstantinos S.

doi:10.1016/j.apcatb.2016.05.031

Cited by 203 publications

(74 citation statements)

References 39 publications

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“…In comparison, zirconia/titania exhibited good selectivity towards hydrocarbons and yielded higher organic liquid product than alumina. Natural derived basic magnesium oxide (MgO) catalyst effectively reduced the oxygen content of the produced bio-oil and exhibited similar or even better catalytic performance in bio-oil upgrading compared to that of an industrial ZSM-5 catalyst, although the coke yield of MgO catalyst was a bit higher than that of ZSM-5 [57]. The reduction of acids and deoxygenation of bio-oils via ketonization and aldol condensation reactions occurred in the basic sites of MgO catalysts, and the preferred pathway for removing oxygen was mainly via CO 2 formation instead of CO and/or water.…”

Section: Oxides Catalystsmentioning

confidence: 99%

Application, Deactivation, and Regeneration of Heterogeneous Catalysts in Bio-Oil Upgrading

et al. 2016

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Abstract:The massive consumption of fossil fuels and associated environmental issues are leading to an increased interest in alternative resources such as biofuels. The renewable biofuels can be upgraded from bio-oils that are derived from biomass pyrolysis. Catalytic cracking and hydrodeoxygenation (HDO) are two of the most promising bio-oil upgrading processes for biofuel production. Heterogeneous catalysts are essential for upgrading bio-oil into hydrocarbon biofuel. Although advances have been achieved, the deactivation and regeneration of catalysts still remains a challenge. This review focuses on the current progress and challenges of heterogeneous catalyst application, deactivation, and regeneration. The technologies of catalysts deactivation, reduction, and regeneration for improving catalyst activity and stability are discussed. Some suggestions for future research including catalyst mechanism, catalyst development, process integration, and biomass modification for the production of hydrocarbon biofuels are provided.

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Section: Oxides Catalystsmentioning

confidence: 99%

Application, Deactivation, and Regeneration of Heterogeneous Catalysts in Bio-Oil Upgrading

et al. 2016

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“…[9,10] Mullen et al [11] loaded Fe species on HZSM-5 for upgrading of the bio-oil in catalytic fast pyrolysis of biomass and found that the yield of aromatic hydrocarbon was increased to a great extent. [14] Stefanidis et al [15] compared the cata-lytic performances of MgO with ZSM-5 for the upgrading of bio-oil, and found that MgO had high ability for retarding the formations of PAHs and hard coke. [12] Iliopoulou et al [13] reported that the addition of Co on ZSM-5 strongly enhanced aromatization reactions, which resulted in an increase in the selectivity towards aromatics in the upgraded bio-oil.…”

Section: Introductionmentioning

confidence: 99%

Bifunctional Mg−Cu‐Loaded β‐Zeolite: High Selectivity for the Conversion of Furfural into Monoaromatic Compounds

et al. 2018

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MgÀCu-loaded b-zeolite was prepared as an acidÀbase bifunctional catalyst for the conversion of furfural to monoaromatic compounds. It is found that this catalyst exhibited high selectivity towards benzene, toluene and xylenes (BTXs) production with anti-polycyclic-aromatic-hydrocarbon formation as well as anti-coking ability when compared with Culoaded b-zeolite and the parent b-zeolite. The product distribution indicated that addition of Cu species significantly promoted the deoxygenation and aromatization of an intermediate product of furan while Mg apparently suppressed the polyaromatization. Especially, an optimum loading amount of 0.5 wt%Mg-1 wt%Cu on b-zeolite was obtained, which showed lower catalytic deoxygenation temperature and interestingly, only benzene was detected in the liquid product at a reaction temperature over 700 8C. Also, 0.5 wt%Mg-1 wt%Cu/b-zeolite exhibited long-term stability for 10 cycles with 100 % of furfural conversion to monoaromatic compounds. The physicochemical properties of b-zeolite after Cu and Mg loadings were characterized using N 2 sorption, XRD, SEM-EDX, TEM, H 2 -TPR, UV-Vis, XPS, NH 3 -TPD and CO 2 -TPD techniques. The significant changing of acidity and basicity of b-zeolite were found after Cu and Mg loadings, which should be the main factors for the improvement of activity, selectivity and stability of the developed catalyst.[a] Dr. and 750 8C, respectively. This indicates that 1 wt%Cu/ b-zeolite and 0.5 wt%Mg-1wt%Cu/b-zeolite had high selectivity for the benzene production from furfural conversion at a reaction temperature over 700 8C. Based on these results, it can be concluded that the tuning of acid and basic sites of b-zeolite and the interaction of metal species on b-zeolite by co-doping of Mg with Cu, the changing of reaction temperature as well as WHSV can effectively control the product distribution from the furfural conversion.According to the presented results, the possible mechanism for the catalytic conversion of furfural over MgÀCu-doped bzeolite can be proposed following based on previous liter-Figure 4. Effect of WHSV on product yields and aromatic distributions in liquid products obtained from the catalytic deoxygenation of furfural at a reaction temperature of 600 8C and a TOS of 1 h using (A,B) b-zeolite, (C,D) 1wt%Cu/b-zeolite and (E,F) 0.5 wt%Mg-1 wt%Cu/b-zeolite.

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“…[14] However,i n1 962 the transformation of 2,2,5,5-tetramethyladipic acid into the corresponding ketone was reported to take place in 52 %t o7 2% yield in the presence of KF or BaO. This is manifested in the number of catalytic studies that have appeared recently [17][18][19][20][21] and in the experimental and theoretical evaluations of the mechanism. Given that this intermediate would immediately deprotonate other carboxylic acids and produce formally hydrodecarboxylation products (cf.…”

Section: Introductionmentioning

confidence: 99%

Ketone Formation from Carboxylic Acids by Ketonic Decarboxylation: The Exceptional Case of the Tertiary Carboxylic Acids

Oliver-Tomas

Renz

Corma

2017

Chemistry A European J

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For the reaction mechanism of the ketonic decarboxylation of two carboxylic acids, a β-keto acid is favored as key intermediate in many experimental and theoretical studies. Hydrogen atoms in the α-position are an indispensable requirement for the substrates to react by following this mechanism. However, isolated observations with tertiary carboxylic acids are not consistent with it and these are revisited and discussed herein. The experimental results obtained with pivalic acid indicate that the ketonic decarboxylation does not occur with this substrate. Instead, it is consumed in alternative reactions such as disintegration into isobutene, carbon monoxide, and water (retro-Koch reaction). In addition, the carboxylic acid is isomerized or loses carbon atoms, which converts the tertiary carboxylic acid into carboxylic acids bearing α-proton atoms. Hence, the latter are suitable to react through the β-keto acid pathway. A second substrate, 2,2,5,5-tetramethyladipic acid, reacted by following the same retro-Koch pathway. The primary product was the monocarboxylic acid 2,2,5-trimethyl-4-hexenoic acid (and its double bond isomer), which might be further transformed into a cyclic enone or a lactone. The ketonic decarboxylation product, 2,2,5,5-tetramethylcyclopentanone was observed in traces (<0.2 % yield). Therefore, it can be concluded that the observed experimental results further support the proposed mechanism for the ketonic decarboxylation via the β-keto acid intermediate.

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Natural magnesium oxide (MgO) catalysts: A cost-effective sustainable alternative to acid zeolites for the in situ upgrading of biomass fast pyrolysis oil

Cited by 203 publications

References 39 publications

Application, Deactivation, and Regeneration of Heterogeneous Catalysts in Bio-Oil Upgrading

Application, Deactivation, and Regeneration of Heterogeneous Catalysts in Bio-Oil Upgrading

Bifunctional Mg−Cu‐Loaded β‐Zeolite: High Selectivity for the Conversion of Furfural into Monoaromatic Compounds

Ketone Formation from Carboxylic Acids by Ketonic Decarboxylation: The Exceptional Case of the Tertiary Carboxylic Acids

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