Supported molybdenum oxides as effective catalysts for the catalytic fast pyrolysis of lignocellulosic biomass

Murugappan, Karthick; Mukarakate, Calvin; Budhi, Sridhar; Shetty, Manish; Nimlos, Mark R.; Román‐Leshkov, Yuriy

doi:10.1039/c6gc01189f

Cited by 83 publications

(50 citation statements)

References 42 publications

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“…This process can provide high-quality bio-oil with low oxygen content, making it potentially more compatible with the current refining infrastructure. 56 Substantial efforts have been made in the CFP of lignocellulose using a variety of zeolite-based catalysts. For instance, the catalytic performance of a HZSM-5 zeolite was investigated for in-situ CFP of woody biomass in a pilot-scale circulating fluidized-bed reactor.…”

Section: Pristine and Substituted Zeolitesmentioning

confidence: 99%

“…276 Biomass to MoO 3 mass ratio played a pivotal role on the deoxygenation activity of MoO 3 /TiO 2 and MoO 3 /ZrO 2 catalysts (10 wt% MoO 3 loading) for catalytic fast pyrolysis of pine biomass. 56 Owing to adequate amounts of surface reduced Mo species (Mo 3+ and Mo 5+ ), the supported MoO 3 catalysts converted approx. 27 mol% of the original carbon into hydrocarbons, mainly containing aromatics (7 C%), olefins (18 C%), and paraffins (2 C%), outperforming a bulk MoO 3 catalyst.…”

Section: Valorization Of Lignocellulose Biomassmentioning

confidence: 99%

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Advances in porous and nanoscale catalysts for viable biomass conversion

et al. 2019

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Section: Pristine and Substituted Zeolitesmentioning

confidence: 99%

Section: Valorization Of Lignocellulose Biomassmentioning

confidence: 99%

Advances in porous and nanoscale catalysts for viable biomass conversion

et al. 2019

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“…Hydrodeoxygenation (HDO) is an important upgrading strategy for converting lignocellulosic biomass to fuels and chemicals that relies on molecular H 2 to selectively remove oxygen in the form of water. [1][2][3][4][5][6][7][8][9][10][11][12][13] While noble metal catalysts have dominated the HDO landscape, molybdenum trioxide (MoO 3 ) [14][15][16][17][18][19][20] and molybdenum carbide (Mo 2 C) [21][22][23][24][25][26][27][28][29][30][31] have recently emerged as promising earth-abundant alternatives that can selectively cleave C-O bonds under mild conditions. In contrast to state-of-the-art noble metal catalysts, MoO 3 and Mo 2 C catalysts produce unsaturated hydrocarbons, while concurrently minimizing both the saturation of C=C double bonds and the cleavage of C-C bonds.…”

Section: Introductionmentioning

confidence: 99%

Operando NAP-XPS unveils differences in MoO3 and Mo2C during hydrodeoxygenation

et al. 2018

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MoO3 and Mo2C have emerged as remarkable catalysts for the selective hydrodeoxygenation (HDO) of a wide range of oxygenates at low temperatures (i.e.,  673 K) and H 2 pressures (i.e., ≤ 1 bar). While both catalysts can selectively cleave CO bonds, the nature of their active sites remains unclear. Here, we used operando nearambient pressure X-ray photoelectron spectroscopy to reveal important differences in the Mo 3d oxidation states between the two catalysts during the HDO of anisole. This technique revealed that although both catalysts featured a surface oxycarbidic phase, the oxygen content and the underlying phase of the material impacted the reactivity and product selectivity during HDO. MoO3 transitioned between 5+ and 6+ oxidation states during operation, consistent with an oxygen vacancy driven mechanism wherein the oxygenate is activated at undercoordinated Mo sites. In contrast, Mo 2 C showed negligible oxidation state changes during HDO, maintaining mostly 2+ states throughout the reaction.

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“…In large scale systems, fast pyrolysis is implemented using fluidized bed, sprouted bed or ablative reactors (Bridgwater, 2012 ). In the laboratory, fast pyrolysis behavior of biomass is often simulated using Pyroprobe™ or similar instruments (Wang et al, 2014b , 2017 ; Mukarakate et al, 2015 ; Murugappan et al, 2016 ; Mullen et al, 2017 ). High heat transfer, precise control of temperature and short vapor residence time that are required for fast pyrolysis can all be achieved in the Pyroprobe™ instrument (Babu, 2008 ).…”

Section: Introductionmentioning

confidence: 99%

In situ and Ex situ Catalytic Pyrolysis of Microalgae and Integration With Pyrolytic Fractionation

2020

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Microalgae are attractive feedstocks for biofuel production and are especially suitable for thermochemical conversion due to the presence of thermally labile constituents—lipids, starch and protein. However, the thermal degradation of starch and proteins produces water as well as other O- and N-compounds that are mixed-in with energy-dense lipid pyrolysis products. To produce hydrocarbon-rich products from microalgae biomass, we assessed in situ and ex situ catalytic pyrolysis of a lipid-rich Chlorella sp. in the presence of the HZSM-5 zeolite catalyst over a temperature range of 450–550°C. Results show that product yields and compositions were similar under both in situ and ex situ conditions with benzene, toluene and xylene produced as the primary aromatic products. Yields of aromatics increased with increasing temperature and the highest aromatic yield (36.4% g aromatics/g ash-free microalgae) and selectivity (87% g aromatics/g bio-oil) was obtained at 550°C. Also, at this temperature, oxygenates and nitrogenous compounds were not detected among the liquid products during ex situ catalytic pyrolysis. We also assessed the feasibility of a two-step fractional pyrolysis approach integrated with vapor phase catalytic upgrading. In these experiments, the biomass was first pyrolyzed at 320°C to degrade and volatilize starch, protein and free fatty acids. Then, the residual biomass was pyrolyzed again at 450°C to recover products from triglyceride decomposition. The volatiles from each fraction were passed through an ex situ catalyst bed. Results showed that net product yields from the 2-step process were similar to the single step ex situ catalytic pyrolysis at 450°C indicating that tailored vapor phase upgrading can be applied to allow separate recovery of products from the chemically distinct biomass components—(1) lower calorific value starch and proteins and (2) energy-dense lipids.

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Supported molybdenum oxides as effective catalysts for the catalytic fast pyrolysis of lignocellulosic biomass

Abstract: Supported MoO3 catalysts are effective catalytic fast pyrolysis catalysts that can generate ca. 30 C% hydrocarbons, including aromatics, olefins, and paraffins from pine.

Cited by 83 publications

References 42 publications

Advances in porous and nanoscale catalysts for viable biomass conversion

Advances in porous and nanoscale catalysts for viable biomass conversion

Operando NAP-XPS unveils differences in MoO3 and Mo2C during hydrodeoxygenation

In situ and Ex situ Catalytic Pyrolysis of Microalgae and Integration With Pyrolytic Fractionation

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