Methane Dry Reforming over Ni-Co/Al2O3: Kinetic Modelling in a Catalytic Fixed-bed Reactor

Author(s):  
Yacine Benguerba ◽  
Mirella Virginie ◽  
Christine Dumas ◽  
Barbara Ernst

Abstract The dry reforming of CH4 was investigated in a catalytic fixed-bed reactor to produce hydrogen at different temperatures over supported bimetallic Ni-Co catalyst. The reactor model for the dry reforming of methane used a set of kinetic models: The Zhang et al model for the dry reforming of methane (DRM); the Richardson-Paripatyadar model for the reverse water gas shift (RWGS); and the Snoeck et al kinetics for the coke-deposition and gasification reactions. The effect of temperatures on the performance of the reactor was studied. The amount of each species consumed or/and produced were calculated and compared with the experimental determined ones. It was showed that the set of kinetic model used in this work gave a good fit and accurately predict the experimental observed profiles from the fixed bed reactor. It was found that reaction-4 and reaction-5 could be neglected which could explain the fact that this catalyst coked rapidly comparatively with other catalyst. The use of large amount of Ni-Co will lead to carbon deposition and so to the catalyst deactivation.

2017 ◽  
Vol 42 (4) ◽  
pp. 344-360
Author(s):  
Milad Komasi ◽  
Shohreh Fatemi ◽  
Seyed Hesam Mousavi

Pt–Sn/hierarchical SAPO-34 was synthesised and kinetically modelled as an efficient and selective catalyst for propylene production through propane dehydrogenation. The kinetics of the reaction network were studied in an integral fixed-bed reactor at three temperatures of 550, 600 and 650 °C and weight hourly space velocities of 4 and 8 h−1 with a feed containing hydrogen and propane with relative molar ratios of 0.2, 0.5 and 0.8, at normal pressure. The experiments were performed in accordance with the full factorial experimental design. The kinetic models were constructed on the basis of different mechanisms and various deactivation models. The kinetics and deactivation parameters were simultaneously predicted and optimised using genetic algorithm optimisation. It was further proven that the Langmuir–Hinshelwood model can well predict propane dehydrogenation kinetics through lumping together all the possible dehydrogenation steps and also by assuming the surface reaction as the rate-determining step. A coke formation kinetic model has also shown appropriate results, confirming the experimental data by equal consideration of both monolayer and multilayer coke deposition kinetic orders and an exponential deactivation model.


Energies ◽  
2021 ◽  
Vol 14 (11) ◽  
pp. 3347
Author(s):  
Arslan Mazhar ◽  
Asif Hussain Khoja ◽  
Abul Kalam Azad ◽  
Faisal Mushtaq ◽  
Salman Raza Naqvi ◽  
...  

Co/TiO2–MgAl2O4 was investigated in a fixed bed reactor for the dry reforming of methane (DRM) process. Co/TiO2–MgAl2O4 was prepared by modified co-precipitation, followed by the hydrothermal method. The active metal Co was loaded via the wetness impregnation method. The prepared catalyst was characterized by XRD, SEM, TGA, and FTIR. The performance of Co/TiO2–MgAl2O4 for the DRM process was investigated in a reactor with a temperature of 750 °C, a feed ratio (CO2/CH4) of 1, a catalyst loading of 0.5 g, and a feed flow rate of 20 mL min−1. The effect of support interaction with metal and the composite were studied for catalytic activity, the composite showing significantly improved results. Moreover, among the tested Co loadings, 5 wt% Co over the TiO2–MgAl2O4 composite shows the best catalytic performance. The 5%Co/TiO2–MgAl2O4 improved the CH4 and CO2 conversion by up to 70% and 80%, respectively, while the selectivity of H2 and CO improved to 43% and 46.5%, respectively. The achieved H2/CO ratio of 0.9 was due to the excess amount of CO produced because of the higher conversion rate of CO2 and the surface carbon reaction with oxygen species. Furthermore, in a time on stream (TOS) test, the catalyst exhibited 75 h of stability with significant catalytic activity. Catalyst potential lies in catalyst stability and performance results, thus encouraging the further investigation and use of the catalyst for the long-run DRM process.


2020 ◽  
Vol 4 (1) ◽  
pp. 16
Author(s):  
Yuan Zhu ◽  
Kun Chen ◽  
Robert Barat ◽  
Somenath Mitra

In this study, CH4 dry reforming was demonstrated on a novel microwave-synthesized ruthenium (Ru)/carbon nanotube (CNT) catalyst. The catalyst was tested in an isothermal laboratory-packed bed reactor, with gas analysis by gas chromatography/thermal conductivity detection. The catalyst demonstrated excellent dry-reforming activity at modest temperatures (773–973 K) and pressure (3.03 × 105 Pa). Higher reaction temperatures favored increased conversion of CH4 and CO2, and increased H2/CO product ratios. Slight coke deposition, estimated by carbon balance, was observed at higher temperatures and higher feed CH4/CO2. A robust global kinetic model composed of three reversible reactions—dry reforming, reverse water gas shift, and CH4 decomposition—simulates observed outlet species concentrations and reactant conversions using this Ru/CNT catalyst over the temperature range of this study. This engineering kinetic model for the Ru/CNT catalyst predicts a somewhat higher selectivity and yield for H2, and less for CO, in comparison to previously published results for a similarly prepared Pt_Pd/CNT catalyst from our group.


2018 ◽  
Vol 148 (8) ◽  
pp. 2256-2262 ◽  
Author(s):  
Lukas Tillmann ◽  
Jonas Schulwitz ◽  
André van Veen ◽  
Martin Muhler

2020 ◽  
Vol 39 (1) ◽  
pp. 109
Author(s):  
Zuhal Erol ◽  
Saliha Cetinyokus Kilicarslan ◽  
Meltem Dogan

The syntheses of MCM-41 (Mobil Composition of Matter No. 41) supported chromium oxide cat-alysts at different chromium concentrations (4–10 % by mass) were carried out hydrothermally. The aim of this study was to determine the effect of chromium concentration in the catalyst structure on the chro-mate types and chromium oxidation states, as well as the activity of the catalyst in the isobutane dehydro-genation reaction. Inactive α-Cr2O3 crystals for isobutane dehydrogenation were shown to increase in the catalyst structure as the chromium loading increased. The highest amount of Cr6+ on the catalyst surface was detected in the catalyst (H4-MCM-41) with 4 % chromium by mass. Catalytic tests (T = 600 °C, P = atmospheric pressure, WHSV = 26 h–1) were performed under fixed bed reactor conditions. The high-est isobutane conversion (~60 %) and selectivity (~80 %) were observed on the H4-MCM-41 catalyst, which had the highest amount of Cr6+ and monochromate structures. Catalyst deactivation was not due to coke deposition but, rather, was caused by the formation of inactive α-Cr2O3 crystal structures.


2018 ◽  
Vol 4 (1) ◽  
pp. 5 ◽  
Author(s):  
Kasim Samsudeen ◽  
Al fatesh Ahmed ◽  
Mohammad Yahya ◽  
Aidid Ahmed ◽  
Fakeeha Anis

Ni/Al2O3 catalysts were prepared by the wet-impregnation method and calcined at different temperatures (500°C, 600°C and 700°C) to obtain NiAl-1, NiAl-2 and NiAl-3 respectively. NiAl-1, NiAl-2, NiAl-3 represent catalysts calcined at 500°C, 600°C and 700°C respectively. The catalysts were characterized using different techniques, XRD, BET and TGA. XRD results revealed the presence of NiO phase on all the catalysts during calcination, however, the presence of spinel, NiAl2O4, was more pronounced on the catalyst calcined at 600°C (i.e. NiAl-2), indicating the existence of strong metal-support interaction. BET results showed that NiAl-1 has the highest surface area of about 190cm2/g.  All the catalysts were tested for ethanol dry reforming in a tubular stainless steel fixed-bed reactor at 700°C and CO2/ethanol ratio of 3 under atmospheric pressure and were evaluated in terms of reactants conversion and selectivity of H2 to see the effect of the different calcination temperatures on the catalysts’ activities. Ethanol conversion was 100% for all the three catalysts and NiAl-2 has the highest CO2 conversion with an average value of about 57%. The three catalysts have almost the same performance in terms of H2 selectivity. The presence of multi-walled carbon nanofibers (MWCNFs) were confirmed on all the catalysts as revealed by the TGA result. The catalyst calcined at 600°C (i.e. NiAl-2) displayed the best relative catalytic activity


2011 ◽  
Vol 347-353 ◽  
pp. 3681-3684 ◽  
Author(s):  
Young Ho Kim ◽  
Su Gyung Lee ◽  
Byoung Kwan Yoo ◽  
Han Sol Je ◽  
Chu Sik Park

A SAPO-34 catalyst is well known to be one of the best catalysts for DME to olefins (DTO) reaction. Main products of the reaction were light olefins such as ethylene, propylene and butenes. However, the main problem is rapid deactivation of the SAPO-34 catalyst due to coke deposition during DTO reaction. In this study, various SAPO-34/ZrO2 catalysts added with ZrO2 were prepared for improving the lifetime and their physicochemical properties have been characterized by XRD and SEM. The DTO reaction over various SAPO-34/ZrO2 catalysts was carried out using a fixed bed reactor. All SAPO-34/ZrO2 catalysts showed similar activity and selectivity in the DTO reaction. The SAPO-34(9wt%)/ZrO2 catalyst was showed the best performance for the catalyst lifetime.


Author(s):  
Fahim Fayaz ◽  
Ahmad Ziad Sulaiman ◽  
Sharanjit Singh ◽  
Sweeta Akbari

The effect of CO2 partial pressure on ethanol dry reforming was evaluated over 5%Ce-10%Co/Al2O3 catalyst at = PCO2 = 20-50 kPa, PC2H5OH = 20 kPa, reaction temperature of 973 K under atmospheric pressure. The catalyst was prepared by using impregnation method and tested in a fixed-bed reactor. X-ray diffraction measurements studied the formation of Co3O4, spinel CoAl2O4 and CeO2, phases on surface of 5%Ce-10%Co/Al2O3 catalyst. CeO2, CoO and Co3O4 oxides were obtained during temperature–programmed calcination. Ce-promoted 10%Co/Al2O3 catalyst possessed high BET surface area of 137.35 m2 g-1. C2H5OH and CO2 conversions was improved with increasing CO2 partial pressure from 20-50 kPa whilst the optimal selectivity of H2 and CO was achieved at 50 kPa.


Catalysts ◽  
2020 ◽  
Vol 10 (12) ◽  
pp. 1374
Author(s):  
Andreas Brune ◽  
Andreas Seidel-Morgenstern ◽  
Christof Hamel

This study intends to provide insights into various aspects related to the reaction kinetics of the VOx catalyzed propane dehydrogenation including main and side reactions and, in particular, catalyst deactivation and regeneration, which can be hardly found in combination in current literature. To kinetically describe the complex reaction network, a reduced model was fitted to lab scale experiments performed in a fixed bed reactor. Additionally, thermogravimetric analysis (TGA) was applied to investigate the coking behavior of the catalyst under defined conditions considering propane and propene as precursors for coke formation. Propene was identified to be the main coke precursor, which agrees with results of experiments using a segmented fixed bed reactor (FBR). A mechanistic multilayer-monolayer coke growth model was developed to mathematically describe the catalyst coking. Samples from long-term deactivation experiments in an FBR were used for regeneration experiments with oxygen to gasify the coke deposits in a TGA. A power law approach was able to describe the regeneration behavior well. Finally, the results of periodic experiments consisting of several deactivation and regeneration cycles verified the long-term stability of the catalyst and confirmed the validity of the derived and parametrized kinetic models for deactivation and regeneration, which will allow model-based process development and optimization.


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