Alexiadis, Vaios

Lødeng, Rune

Ranga, Chanakya

Thybaut, Joris

English

Ghent University Academic Bibliography

CatBior, Lyon, 11-15/12/2017 Anisole hydrodeoxygenation over supported CoMo catalysts: effect of Co/Mo ratio and support on catalyst stability and activity Chanakya Ranga,1 Rune Lødeng,2 Vaios I. Alexiadis,1 and Joris Thybaut1,* https://www.lct.ugent.be 1Laboratory for Chemical Technology Technologiepark 914, 9052 Ghent, Belgium This work is supported by the Innovative Catalyst Design for large-scale sustainable processes (i-CaD) project, which is an ERC consolidator grant, by the European Commission in the 7th Framework Programme (GA no 615456). It also fits in the framework of the FAST industrialization by Catalyst Research and Development (FASTCARD) project, which is a large scale collaborative project supported by European Commission in the 7th Framework Programme (GA no 604277). https://www.sintef.no/en/ 2SINTEF Materials and Chemistry Kinetics and Catalysis Research Team, N-7465 Trondheim, Norway E-mail: chanakya.ranga@ugent.be Rationale: Anisole   Anisole is one of the most common chemical structure found in lignocellulosic biomass and challenging to perform deep HDO  Co addition in systematic way to identify and enhance the stable & active phases of MoO3 catalysts for oxygenate HDO Fast Pyrolysis Catalytic HDO CoMo catalysts in non-sulphided form Aim: Stable catalyst with high HDO selectivity Sequential Incepient Wet Impregnation of Mo and Co  200 300 400 500 600 700 800 900H2 consumption, a.u.Temperature,  CMoZCoMoZ0.25CoMoZ0.5CoMoZ1Operating conditions Temperature (°C) 340 Pressure (MPa) 0.5 Space time (kgcat.s/molanisole) 20-230 H2/anisole (mol.mol-1) 50 Co3O4MoO3Sievening, Calcination at 500 °C impregnation of Mo (Wt.%=12)Drying at 120 °C, Calcination at 550 °C, grindingimpregnation of Co (Wt.%=0-12) MoO3Drying at 120 °C, Calcination at 550 °C, grindingCoMoO4ZrO2/Al2O3/TiO2CoMoZ/A/TCo/Mo ZrO2 Al2O3 TiO20 MoZ MoA -0.25 CoMoZ0.25 CoMoA0.25 -0.5 CoMoZ0.5 CoMoA0.5 CoMoT0.51 CoMoZ1 CoMoA1 -00.10.20.30.40.50.60.70.80.910 10 20 30 40 50mol mol-1TOS (h)00.10.20.30.40 10 20 30 40 50mol mol-1TOS (h)MoZ CoMoZ0.25 CoMoZ0.5 CoMoZ10.000.050.100.150.200 5 10 15 20 25 30 35mol mol-1TOS (h)00.10.20.30.40.50.60.70.80.910 5 10 15 20 25 30 35mol mol-1TOS (h)MoA CoMoA0.25 CoMoA0.5 CoMoA1227229231233235237239Intenisty, a.u.Binding energy, eV41:13:4624:49:27CoMoZ0.5_reduced at 500CCoMoA1.0_reduced at 500C100:0:0Mo6+Mo4+Mo5+CoMoZ0.5/CoMoA1_fresh Co addition: i) Increase in the HDO activity for Mo oxide catalysts, ii) Decrease in catalyst stability and overall conversions  compared to MoZ for CoMoZ catalysts, iii) Increase in catalyst stability and overall conversions compared to MoA for CoMoA catalysts  Higher reduction temperatures favor higher HDO activity for CoMoZ catalysts    Mo5+  stable catalyst and high anisole conversions,   Mo4+  high HDO activity [1] C.Ranga et al., Chemical Engineering Journal, 335 (2018) 120 – 132. XRD H2-TPR MoO3Co3O4CoMoO4 MoO3 crystallites disappear as Co loading increases  Mixed oxide (CoMoO4) crystallizes at higher Co loadings.  Mo6+ reduction temperature increases with Co loading  Mo6+ exists in MoO3, CoMoO4, and also in mixed form with support 20 25 30 35 40Intensity, a.u.2θ, degreesMoZCoMoZ0.25CoMoZ0.5CoMoZ120 25 30 35 40 45 50Intensity, a.u.2θ, degreesCoMoA0.25CoMoA0.5CoMoA1MoACo3O4  CoO Mo6+Oh  Mo4+ Mo6+Th  Mo4+ Co2+  Co Mo4+  Mo 200 300 400 500 600 700 800 900H2 consumption, a.u.Temperature,  CCoMoA0.25CoMoA0.5CoMoA1MoACoMoT0.5 Catalyst stability, Overall conversion enhanced with high Mo5+ quantity  HDO selectivity enhanced with high Mo4+ quantity Anisole conversion HDO selectivity, SHDO  Decrease in catalyst stability while an increase in HDO product selectivity with addition of Co  No significant increase in HDO activity observed at  Co/Mo >0.5   Increase in catalyst stability while a decrease in HDO product selectivity with reduction at < 350 °C    Reduction at higher temperatures (500 °C)  higher HDO activity, low overall conversion [1] O OHOHOOHanisole phenolbenzenemethyl anisoledimethylphenolcresoltolueneH2 CH4H2 H2OH2CH4H2 H2OCH4H2CH4H2hydrodeoxygenationisomerizationtransalkylationCH4H2 Initial anisole conversion: Al2O3 > TiO2 ≈ ZrO2  Total HDO selectivity: ZrO2 > TiO2 > Al2O3 Anisole HDO reaction pathways  Higher conversions and increase in HDO product selectivity with addition of Co  Initial rapid decrease in HDO product selectivity with TOS 00.10.20.30.40.50.60.70.80.91CoMoZ0.5 CoMoT0.5 CoMoA0.5SHDO(mol mol-1)Catalyst surface composition Effect of support 00.10.20.30.40.50.60.70.80.910 10 20 30 40 50anisole conversion (mol mol-1)TOS (h)CoMoT0.5 CoMoZ0.5 CoMoA0.5Pre-treatment effect (CoMoZ0.5) Temperature, C 00.10.20.30.40.50 10 20 30 40 50anisole conversion (mol mol-1)TOS (h)no_pre-treatment 350C 400C 450C 500C00.10.20.30.40.50.60.70.80.910 10 20 30 40 50SHDO(mol mol-1)TOS (h)no_pre-treatment 350C 400C 450C 500C

Anisole hydrodeoxygenation over supported CoMo catalysts: effect of Co/Mo ratio and support on catalyst stability and activity

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Anisole hydrodeoxygenation over supported CoMo catalysts: effect of Co/Mo ratio and support on catalyst stability and activity

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