Figure 4 - XRD patterns of fresh, pretreated and spend Na2WO4/Mn/SiO2 catalysts Experimental plan An experimental plan of all experiments is listed in 2. 2- Experimental plan of all temperature ramp and dynamic experiments time Catalyst Temp. Max. of Catalyst Reduction Feed Experiment Amount ramp Temp. reduction pretreatment composition (g) (K/min) (K) Feed (min) Purge He, no N2:H2 (9:1, 60 TPR 1 0.06 2 1093 400 heating sccm/min) Oxidation 10 K/min 1023 K N2:H2 (9:1, 60 – TPR 2 0.06 2 1093 400 for 1 h, Purge sccm/min) He Purge He, no He (99.999 %, 20 O2 TPD 1 5 1093 160 heating sccm/min) Oxidation 10 K/min 1023 K He (99.999 %, 20 – O2 TPD 1 5 1093 160 for 1 h, Purge sccm/min) He Oxidation 10 K/min 1023 K 30 sccm/min methane – TPSR CH4 1 1 1073 800 – for 1 h, Purge (99.99 %) He Oxidation 10 K/min 1023 K 30 sccm/min methane – TPSR CH4 1 2 1073 400 – for 1 h, Purge (99.99 %) He Oxidation 10 K/min 1023 K 30 sccm/min methane – TPSR CH4 1 3 1073 265 – for 1 h, Purge (99.99 %) He Oxidation 10 K/min 1023 K 30 sccm/min methane – TPSR CH4 1 4 1073 200 – for 1 h, Purge (99.99 %) He Oxidation 10 K/min 1023 K 30 sccm/min methane – TPSR CH4 1 5 1073 160 – for 1 h, Purge (99.99 %) He
Figure 4 - XRD patterns of fresh, pretreated and spend Na2WO4/Mn/SiO2 catalysts Experimental plan An experimental plan of all experiments is listed in 2. 2- Experimental plan of all temperature ramp and dynamic experiments Experiment Catalyst pretreatment Catalyst Amount (g) Temp. ramp (K/min) Max. Temp. (K) Reduction Feed composition time of reduction Feed (min) TPR 1 Purge He, no heating 0.06 2 1093 N2:H2 (9:1, 60 sccm/min) 400 TPR 2 Oxidation 10 K/min – 1023 K for 1 h, Purge He 0.06 2 1093 N2:H2 (9:1, 60 sccm/min) 400 O2 TPD Purge He, no heating 1 5 1093 He (99.999 %, 20 sccm/min) 160 O2 TPD Oxidation 10 K/min – 1023 K for 1 h, Purge He 1 5 1093 He (99.999 %, 20 sccm/min) 160 TPSR – CH4 Oxidation 10 K/min – 1023 K for 1 h, Purge He 1 1 1073 30 sccm/min methane (99.99 %) 800 TPSR – CH4 Oxidation 10 K/min – 1023 K for 1 h, Purge He 1 2 1073 30 sccm/min methane (99.99 %) 400 TPSR – CH4 Oxidation 10 K/min – 1023 K for 1 h, Purge He 1 3 1073 30 sccm/min methane (99.99 %) 265 TPSR – CH4 Oxidation 10 K/min – 1023 K for 1 h, Purge He 1 4 1073 30 sccm/min methane (99.99 %) 200 TPSR – CH4 Oxidation 10 K/min – 1023 K for 1 h, Purge He 1 5 1073 30 sccm/min methane (99.99 %) 160
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