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Fischer–Tropsch (FT) synthesis was carried out in a 3D printed stainless steel (SS) microchannel microreactor using bimetallic Co-Ru catalysts on three different mesoporous silica supports. CoRu-MCM-41, CoRu-SBA-15, and CoRu-KIT-6 were synthesized using a one-pot hydrothermal method and characterized by Brunner–Emmett–Teller (BET), temperature programmed reduction (TPR), SEM-EDX, TEM, and X-ray photoelectron spectroscopy (XPS) techniques. The mesoporous catalysts show the long-range ordered structure as supported by BET and low-angle XRD studies. The TPR profiles of metal oxides with H2 varied significantly depending on the support. These catalysts were coated inside the microchannels using polyvinyl alcohol and kinetic performance was evaluated at three different temperatures, in the low-temperature FT regime (210–270 °C), at different Weight Hourly Space Velocity (WHSV) in the range of 3.15–25.2 kgcat.h/kmol using a syngas ratio of H2/CO = 2. The mesoporous supports have a significant effect on the FT kinetics and stability of the catalyst. The kinetic models (FT-3, FT-6), based on the Langmuir–Hinshelwood mechanism, were found to be statistically and physically relevant for FT synthesis using CoRu-MCM-41 and CoRu-KIT-6. The kinetic model equation (FT-2), derived using Eley–Rideal mechanism, is found to be relevant for CoRu-SBA-15 in the SS microchannel microreactor. CoRu-KIT-6 was found to be 2.5 times more active than Co-Ru-MCM-41 and slightly more active than CoRu-SBA-15, based on activation energy calculations. CoRu-KIT-6 was ~3 and ~1.5 times more stable than CoRu-SBA-15 and CoRu-MCM-41, respectively, based on CO conversion in the deactivation studies. Keywords: Fischer-Tropsch synthesis; mesoporous silica based catalysts; kinetic studies; 3-D printed microchannel microreactor
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Scale-up of high-pressure F-T synthesis in 3D printed stainless steel microchannel microreactors: Experiments and modeling
Scale-up of Fischer-Tropsch (F-T) synthesis using microreactors is very important for a paradigm shift in the production of fuels and chemicals. The scalability of microreactors for F-T Synthesis was experimentally evaluated using 3D printed stainless steel microreactors, containing seven microchannels of dimensions 1000 µm × 1000 µm × 5cms. Mesoporous silica (KIT-6), with high surface area, containing ordered mesoporous structure was used to incorporate 10% cobalt and 5% ruthenium using a one-pot hydrothermal method. Bimetallic Co-Ru-KIT-6 catalyst was used for scale-up of F-T Synthesis. The performance of the catalysts was evaluated and examined for three different scale-up configurations (stand-alone, two, and four microreactors assembled in parallel) at both atmospheric pressure and 20 bar at F-T operating temperature of 240 °C using a syngas molar ratio (H2:CO) of 2. All three configurations of microreactors yielded not only comparable CO conversion (85.6–88.4%) and methane selectivity (~14%) but also similar selectivity towards lower gaseous hydrocarbons like ethane, propane, and butane (6.23–9.4%) observed in atmospheric F-T Synthesis. The overall selectivity to higher hydrocarbons, C5 + is in the range of 75–82% at 20 bars. A CFD model was used to investigate the effect of different design features and numbering up approaches on the performance of the microchannel reactor. The effect of the reactor inlet, the mixing internals and the channel designs on the dead zone %, the quality index factor, the cooling requirement and the maximum dimensionless temperature within the microreactor were quantified. There is no significant effect of increasing the channel width on the microreactor performance and operation of the microchannel reactor at lower Nusselt number that results in higher CO conversion. Increasing the channel width reduced the maximum temperature exhibited in the channel. Finally, the effect of increasing the y/x stacking ratio, i.e. having more reactor units in parallel compared to series, was investigated. Increasing the y/x ratio increased the cooling requirement and the maximum dimensionless temperature increase within the unit decreased the productivity. To minimize the productivity losses, numbering up in series is the better approach; however further analysis must be done to delineate heat removal requirements.
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- Award ID(s):
- 1736173
- PAR ID:
- 10317285
- Editor(s):
- M.A. Bañares E. Groppo, PhD
- Date Published:
- Journal Name:
- Catalysis today
- ISSN:
- 0920-5861
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/doi.org/10.1016/j.cattod.2021.09.038
