Insight and comprehensive study of Ni-based catalysts supported on various metal oxides for CO2 methanation.

In this study, nickel supported on various metal oxides were prepared by simple impregnation and the performance for CO2 methanation was tested. The oxide supports were all prepared by thermal decomposition of metal salts to provide comparable oxide properties such as surface area. Among the investigated oxides, nickel supported on CeO2 and Y2O3 showed the highest CO2 conversion of 90% at 320 °C with highest CH4 selectivity of 99%. The order of catalyst activity (XCO2@320°C) was reported: Ni/CeO2 ~ Ni/Y2O3 > > Ni/La2O3 > Ni/ZrO2 > Ni/Al2O3 > Ni/MgO > Ni/CaO > > Ni/MnO. The physicochemical properties of the catalysts were analyzed by TEM, BET, XRD, ICP, H2-TPR, CO2-TPD, H2 chemisorption, TGA, Raman, and XPS. From the characterization results, the catalyst activity was independent to specific surface area of catalyst and crystallite size of Ni. The amount of oxygen vacancies and weak-to-medium basic sites exhibited major roles for enhancing catalyst activity. The CeO2 and Y2O3 as reducible oxide supports not only provided abundant oxygen vacancies / basic sites, but also promoted Ni dispersion with appropriate interaction between metal and support, resulting in higher reducibility at low temperature. The reduction of catalyst at high temperature can significantly improve the performance of Ni supported on non-reducible MgO. However, the Ni/CeO2 and Ni/Y2O3 reduced at high temperature suffered from coalescence of CeO2 and Y2O3, though Ni crystallite sizes are well preserved from sintering.

The improvement of heat transfer using Co/SiO2 spiral structured catalyst for green diesel production by Fischer-Tropsch synthesis.

In this study, the improvement of heat transfer was applied to eliminate hotspots of a highly exothermic reaction, Fischer-Tropsch synthesis (FTS), by means of two facile methods: (I) adding high thermal conductive materials media diluted in catalysts (SiC and Al chips), and (II) using structured reactors equipped with well-designed structured catalysts with advantages of heat dissipation/removal. The 20%Co/SiO2 catalyst powder prepared by simple impregnation was employed for constructing structured catalysts and granular packed bed catalysts. The structured catalyst was prepared by coating method of Co/SiO2 slurry on an aluminum spiral and plate substrate. The catalytic performance of as-prepared catalysts was then tested for FTS in a fixed-bed reactor at 210-230 °C, 20 bar. Both gaseous and liquid products were collected and analyzed. The heat transfer improvement of packed bed catalytic system and structured catalytic system were compared and discussed. As a result, the structured catalytic system with spiral structured catalyst can provide the best improvement of heat/mass transfer, resulting in enhanced diesel selectivity, though the oil production rate was unsatisfactory. Meanwhile, among the packed bed catalytic systems, SiC media possessed the best heat removal material, producing the highest oil yield. In addition, the fresh and spent catalysts were analyzed by several techniques including TEM, SEM, XRD, BET, ICP-OES, H2-TPR, and TGA to relate the physicochemical properties of the prepared catalysts and its FTS performance.

Simultaneous production of syngas and carbon nanotubes from CO2/CH4 mixture over high-performance NiMo/MgO catalyst.

Direct conversion of biogas via the integrative process of dry reforming of methane (DRM) and catalytic methane decomposition (CDM) has received a great attention as a promising green catalytic process for simultaneous production of syngas and carbon nanotubes (CNTs). In this work, the effects of reaction temperature of 700-1100 °C and CH4/CO2 ratio of biogas were investigated over NiMo/MgO catalyst in a fixed bed reactor under industrial feed condition of pure biogas. The reaction at 700 °C showed a rapid catalyst deactivation within 3 h due to the formation of amorphous carbon on catalyst surface. At higher temperature of 800-900 °C, the catalyst can perform the excellent performance for producing syngas and carbon nanotubes. Interestingly, the smallest diameter and the highest graphitization of CNTs was obtained at high temperature of 1000 °C, while elevating temperature to 1100 °C leads to agglomeration of Ni particles, resulting in a larger size of CNTs. The reaction temperature exhibits optimum at 800 °C, providing the highest CNTs yield with high graphitization, high syngas purity up to 90.04% with H2/CO ratio of 1.1, and high biogas conversion (XCH4 = 86.44%, XCO2 = 95.62%) with stable performance over 3 h. The typical composition biogas (CH4/CO2 = 1.5) is favorable for the integration process, while the CO2 rich biogas caused a larger grain size of catalyst and a formation of molybdenum oxide nanorods (MoO3). The long-term stability of NiMo/MgO catalyst at 800 °C showed a stable trend (> 20 h). The experimental findings confirm that NiMo/MgO can perform the excellent activity and high stability at the optimum condition, allowing the process to be more promising for practical applications.

Development of Ni-Mo carbide catalyst for production of syngas and CNTs by dry reforming of biogas.

Biogas has been widely regarded as a promising source of renewable energy. Recently, the direct conversion of biogas over heterogeneous catalysts for the simultaneous production of syngas and carbon nanotubes exhibits a high potential for full utilization of biogas with great benefits. Involving the combined dry reforming of methane and catalytic decomposition of methane, the efficiency of process is strongly depended on the catalyst activity/stability, mainly caused by carbon deposition. In this study, Ni-Mo catalyst is engineered to provide a life-long performance and perform high activity in the combined process. The surface modification of catalysts by a controlled carburization pretreatment is proposed for the first time to produce a carbide catalyst along with improving the catalyst stability as well as the reactivity for direct conversion of biogas. The performance of as-prepared carbide catalysts is investigated with comparison to the oxide and metallic ones. As a result, the Ni-Mo2C catalyst exhibited superior activity and stability over its counterparts, even though the condensed nanocarbon was largely grown and covered on the surface. In addition, up to 82% of CH4 conversion and 93% of CO2 conversion could remain almost constant at 800 °C throughout the entire test period of 3 h under a high flowrate inlet stream of pure biogas at 48,000 cm3 g-1 h-1. The XPS spectra of catalysts confirmed that the presence of Mo2C species on the catalyst surface could promote the stability and reactivity of the catalyst, resulting in higher productivity of carbon nanotubes over a longer time.

One-Step Synthesis of Fragment-Reduced Graphene Oxide as an Electrode Material for Supercapacitors.

We herein report for the first time a simple environmentally friendly hydrothermal method for one-step synthesis of fragment-reduced graphene oxide (FrGO) under mild conditions without the addition of reducing agents, and we applied it as an electrode material for a supercapacitor. The characterization results show that the introduction of Al2O3 as a spacer and HCl as an etchant results in a macroporous/mesoporous structure, increases the fragmentation of the FrGO microtopography, shortens the electron/ion transport path, and increases the contact between the electrode material and the electrolyte. Compared to the traditional hydrothermal reduced graphene materials, FrGO shows a larger specific capacitance. The results indicate that suitable hydrothermal temperature and time can effectively promote the retention of more oxygen-containing functional groups on the graphene surface. The first-principles density functional theory (DFT) calculation results show that the electrostatic potential in carbonyl group graphene is more negative, favored by the H+ adsorption, and provides the system with a pseudocapacitive effect. Under optimized conditions, FrGO (1:4, 180 °C, 3 h) exhibits 417 F/g at 1 A/g with an outstanding capacitance retention of 78.51% at 50 A/g and exhibits remarkable stability over 20 000 charge/discharge cycles. The proposed FrGO-based synthesis method can be used to guide the development of electrode materials for various supercapacitor devices.

Synthesis of 2,5-dimethylhexene by isobutene dimerization with H2S co-feeding.

This study investigates the effect of hydrogen sulfide (H2S) co-feeding on the synthesis of 2,5-dimethyl-1-hexene, 2,5-dimethyl-2-hexene, and 2,5-dimethylhexane (2,5-DMHs), useful compounds, using the dimerization of isobutene under mild pressure conditions. The dimerization of isobutene did not proceed in the absence of H2S, whereas the desired products of 2,5-DMHs were produced under H2S co-feeding conditions. The effect of reactor size on the dimerization reaction was then examined, and the optimal reactor was discussed. To enhance the yield of 2,5-DMHs, we changed the reaction conditions of the temperature, molar ratio of isobutene to H2S (iso-C4[double bond, length as m-dash]/H2S) in the feed gas, and the total feed pressure. The optimum reaction condition was at 375 °C and 2/1 of iso-C4[double bond, length as m-dash]/H2S. The product of 2,5-DMHs monotonously increased by an increment of total pressure from 1.0 to 3.0 atm with a fixed iso-C4[double bond, length as m-dash]/H2S ratio at 2/1.

Effect of Ga substitution with Al in ZSM-5 zeolite in methanethiol-to-hydrocarbon conversion.

The catalytic properties of conventional H-[Al]-ZSM-5 and gallium-substituted H-[Ga]-ZSM-5 were evaluated in the conversion of methanethiol to ethylene (CH3SH → 1/2C2H4 + H2S). Dimethyl sulfide (DMS), aromatics, and CH4 were formed as byproducts on the H-[Al]-ZSM-5 catalyst. The introduction of Ga into the ZSM-5 structure provided a high ethylene yield with relatively high selectivity for olefins. Based on the temperature-programmed desorption of NH3 and pyridine adsorption on zeolites, the strength of acid sites was decreased by introducing Ga into the ZSM-5 structure. Undesirable reactions seemed less likely to occur at weakly acidic sites. The suppression of the formation of dimethyl sulfide (CH3SH → 1/2C2H6S + 1/2H2S) and the sequential reaction of ethylene to produce aromatics provided a high yield of ethylene over H-[Ga]-ZSM-5.

Upgradation of methane in the biogas by hydrogenation of CO2 in a prototype reactor with double pass operation over optimized Ni-Ce/Al-MCM-41 catalyst.

The upgradation of methane in biogas by hydrogenation of CO2 has been currently recognized as a promising route for efficient full utilization of renewable biogas with potential benefits for storage of renewable hydrogen energy and abatement of greenhouse gas emission. As a main constituent of biogas, CO2 can act as a backbone for the formation of additional CH4 by hydrogenation, then producing higher amounts of biomethane. In this work, the upgradation process was investigated in a prototype reactor of double pass operation with vertical alignment using an optimized Ni-Ce/Al-MCM-41 catalyst. The experimental results show that the double pass operation that removes water vapor during the run can significantly increase CO2 conversion, resulting in higher CH4 production yield. As a result, the purity of biomethane increased by 15% higher than a single pass operation. In addition, search for optimum condition of the process was carried out within an investigated range of conditions including flowrate (77-1108 ml min-1), pressure (1 atm-20 bar), and temperature (200-500 °C). The durability test for 458 h was performed using the obtained optimum condition, and it shows that the optimized catalyst can perform excellent stability with negligible influence by the observed change in catalyst properties. The comprehensive characterization on physicochemical properties of fresh and spent catalysts was performed, and the results were discussed.

Highly stable Fe/CeO2 catalyst for the reverse water gas shift reaction in the presence of H2S.

This study focused on evaluating the catalytic properties for the reverse water gas shift reaction (RWGS: CO2 + H2 → CO + H2O ΔH 0 = 42.1 kJ mol-1) in the presence of hydrogen sulfide (H2S) over a Fe/CeO2 catalyst, commercial Cu-Zn catalyst for the WGS reaction (MDC-7), and Co-Mo catalyst for hydrocarbon desulfurization. The Fe/CeO2 catalyst exhibited a relatively high catalytic activity to RWGS, compared to the commercial MDC-7 and Co-Mo catalysts. In addition, the Fe/CeO2 catalyst showed stable performance in the RWGS environment that contained high concentrations of H2S. The role of co-feeding H2S was investigated over the Fe/CeO2 catalyst by the temperature programmed reaction (TPR) of CO2 and H2 in the presence of H2S. The result of TPR indicated that the co-feeding H2S might enhance RWGS performance due to H2S acting as the hydrogen source to reduce CO2.

Development of high-performance nickel-based catalysts for production of hydrogen and carbon nanotubes from biogas.

Selecting a suitable catalyst for implementing the simultaneous production of hydrogen-rich syngas and multi-walled carbon nanotubes through the integration of dry reforming and methane decomposition reactions has recently gained great interests. In this study, a series of bimetallic (NiMo/MgO) and trimetallic (CoNiMo/MgO, FeNiMo/MgO, CoFeMo/MgO) catalysts was prepared and evaluated for a catalytic activity of CH4 and CO2 conversions of biogas in a fixed bed reactor at 800 °C and atmospheric pressure. Among the investigated catalysts, the bimetallic NiMo/MgO catalyst showed the outstanding catalytic performance with 86.4% CH4 conversion and 95.6% CO2 conversion as well as producing the highest syngas purity of 90.0% with H2/CO ratio = 1.1. Moreover, the characterization of the synthesized solid products proved that the well-aligned structured morphology, high purity, and excellent textural properties of CNTs were obtained by using NiMo/MgO catalyst. On the other hand, using trimetallic catalysts which have the composition of Co and Fe leads to the severe deactivation. This could be attributed the catalyst oxidation with CO2 in biogas, resulting in the transformation of metals into large metal oxides. The integrative process with NiMo/MgO catalyst is regarded as a promising pathway, which has a high potential for directly converting biogas into the high value-added products and providing a green approach for managing the enormous amounts of wastes.

Natural Kaolin-Based Ni Catalysts for CO2 Methanation: On the Effect of Ce Enhancement and Microwave-Assisted Hydrothermal Synthesis.

Natural kaolin-based Ni catalysts have been developed for low-temperature CO2 methanation. The catalysts were prepared via a one-step co-impregnation of Ni and Ce onto a natural kaolin-derived metakaolin using a microwave-assisted hydrothermal method as an acid-/base-free synthesis method. The influences of microwave irradiation and Ce promotion on the catalytic enhancement including the CO2 conversion, CH4 selectivity, and CH4 yield were experimentally investigated by a catalytic test of as-prepared catalysts in a fixed-bed tubular reactor. The relationship between the catalyst properties and its methanation activities was revealed by various characterization techniques including X-ray fluorescence, X-ray diffraction, Brunauer-Emmett-Teller, scanning electron microscopy, selected area electron diffraction, transmission electron microscopy, elemental mapping, H2 temperature-programmed reduction, and X-ray absorption near-edge structure analyses. Among the two enhancement methods, microwave and Ce promotion, the microwave-assisted synthesis could produce a catalyst containing highly dispersed Ni particles with a smaller Ni crystallite size and higher catalyst reducibility, resulting in a higher CO2 conversion from 1.6 to 7.5% and a better CH4 selectivity from 76.3 to 79.9% at 300 °C. Meanwhile, the enhancement by Ce addition exhibited a great improvement on the catalyst activities. It was experimentally found that the CO2 conversion increased approximately 7-fold from 7.5 to 52.9%, while the CH4 selectivity significantly improved from 79.9 to 98.0% at 300 °C. Though the microwave-assisted synthesis could further improve the catalyst activities of Ce-promoted catalysts, the Ce addition exhibited a more prominent impact than the microwave enhancement. Cerium oxide (CeO2) improved the catalyst activities through mechanisms of higher CO2 adsorption capacity with its basic sites and the unique structure of CeO2 with a reversible valence change of Ce4+ and Ce3+ and high oxygen vacancies. However, it was found that the catalyst prepared by microwave-assisted synthesis and Ce promotion proved to be the optimum catalyst in this study. Therefore, the present work demonstrated the potential to synthesize a nickel-based catalyst with improved catalytic activities by adding a small amount of Ce as a catalytic promoter and employing microwave irradiation for improving the Ni dispersion.