Oxy-CO2 reforming of methane to syngas over CoOx/MgO/SA-5205 catalyst

The oxy-CO₂ methane reforming reaction (OCRM) has been investigated over CoO_x supported on a MgO precoated highly macroporous silica–alumina catalyst carrier (SA-5205) at different reaction temperatures (700–900 °C), O₂/CH₄ ratios (0.3–0.45) and space velocites (20,000–100,000 cc/g/h). The reaction temperature had a profound influence on the OCRM performance over the CoO/MgO/SA-5205 catalyst; the methane conversion, CO₂ conversion and H₂ selectivity increased while the H₂/CO ratio decreased markedly with increasing reaction temperature. While the O₂/CH₄ ratio did not strongly affect the CH₄ and CO₂ conversion and H₂ selectivity, it had an intense influence on the H₂/CO ratio. The CH₄ and CO₂ conversion and the H₂ selectivity decreased while the H₂/CO increased with increasing space velocity. The O₂/CH₄ ratio and the reaction temperature could be used to manipulate the heat of the reaction for the OCRM process. Depending on the O₂/CH₄ ratio and temperature the OCRM process could be operated in a mildly exothermic, thermal neutral or mildly endothermic mode. The OCRM reaction became almost thermoneutral at an OCRM reaction temperature of 850 °C, O₂/CH₄ ratio of 0.45 and space velocity of 46,000 cc/g/h. The CH₄ conversion and H₂ selectivity over the CoO/MgO/SA-5205 catalyst corresponding to thermoneutral conditions were excellent: 95% and 97%, respectively with a H₂/CO ratio of 1.8.     

Optimization of process parameters and catalyst compositions in carbon dioxide oxidative coupling of methane over CaO–MnO/CeO2 catalyst using response surface methodology

The optimization of process parameters and catalyst compositions for the CO₂ oxidative coupling of methane (CO₂-OCM) reaction over CaO–MnO/CeO₂ catalyst was developed using Response Surface Methodology (RSM). The relationship between the responses, i.e. CH₄ conversion, C₂ hydrocarbons selectivity or yield, with four independent variables, i.e. CO₂/CH₄ ratio, reactor temperature, wt.% CaO and wt.% MnO in the catalyst, were presented as empirical mathematical models. The maximum C₂ hydrocarbons selectivity and yields of 82.62% and 3.93%, respectively, were achieved by the individual-response optimization at the corresponding optimal process parameters and catalyst compositions. However, the CH₄ conversion was a saddle function and did not show a unique optimum as revealed by the canonical analysis. Moreover pertaining to simultaneous multi-responses optimization, the maximum C₂ selectivity and yield of 76.56% and 3.74%, respectively, were obtained at a unique optimal process parameters and catalyst compositions. It may be deduced that both individual- and multi-responses optimizations are useful for the recommendation of optimal process parameters and catalyst compositions for the CO₂-OCM process.     

Mixed alcohols synthesis from carbon monoxide hydrogenation over potassium promoted β-Mo2C catalysts

Potassium-promoted β-Mo₂C catalysts were prepared and their performances in CO hydrogenation were investigated. The main products over β-Mo₂C catalyst were C₁-C₄ hydrocarbons, only ∼4 C-atom% alcohols were obtained. The products of hydrocarbons and alcohols obeyed traditional linear Anderson-Schultz-Flory (A-S-F) distribution. However, modification with K₂CO₃ resulted in a remarkable selectivity shift from hydrocarbons to alcohols. Moreover, it was found that potassium promoter enhanced the ability of chain propagation of β-Mo₂C catalysts and resulted in a higher selectivity to C₂₊OH. For K/β-Mo₂C catalysts, the hydrocarbon products also obeyed traditional linear A-S-F plots, whereas alcohols gave a unique linear A-S-F distribution with remarkable deviation of methanol compared with that on β-Mo₂C catalyst. It could be concluded that potassium promoter might exert a prominent function on the whole chain propagation to produce alcohols. A surface phase on the K/β-Mo₂C catalysts such as the “K-Mo-C” explained the higher value for C₂₊OH, especially could promote the step of C₁OH to C₂OH, or could have a role in producing directly C₂OH, but again this would be speculative. At the same time, the influence of the loadings of K₂CO₃ on the performances of β-Mo₂C catalyst was investigated and the results revealed that the maximum yield of alcohol was obtained at K/Mo molar ratio of 0.2.     

Selective synthesis of light olefins from syngas over potassium-promoted molybdenum carbide catalysts

In the hydrogenation of CO at atmospheric pressure, unsupported molybdenum carbide catalyst produced mostly C₁-C₅ paraffins. Promotion of the catalyst with K₂CO₃ yielded C₂-C₅ hydrocarbons consisting of 80–100% olefins and reduced the methane selectivity. The selectivity of C₂-C₅ olefins among all hydrocarbon products was 50–70 wt% at CO conversions up to 70%.This work has been supported by Korean Science and Engineering Foundation through a contract 88-03-1302.     

Low methane selectivity using Co/MnO catalysts for the Fischer-Tropsch reaction: Effect of increasing pressure and Co-feeding ethene

CO hydrogenation using cobalt/ manganese oxide catalysts is described and discussed. These catalysts are known to give low methane selectivity with high selectivity to C₃ hydrocarbons at moderate reaction conditions (GHSV < 500 h^–1, < 600 kPa). In this study the effect of reaction conditions more appropriate to industrial operation are investigated. CO hydrogenation at 1–2 MPa using catalyst formulations with Co/Mn = 0.5 and 1.0 gives selectivities to methane that are comparable to those observed at lower pressures. At the higher pressure the catalyst rapidly deactivates, a feature that is not observed at lower pressures. However, prior to deactivation rates of CO + CO₂ conversion > 8 mol/1-catalyst h can be observed. Co-feeding ethene during CO hydrogenation is investigated by the reaction of¹³C0-¹²C₂H₄-H₂ mixtures and a significant decrease in methane selectivity is observed but the hydrogenation of ethene is also a dominant reaction. The results show that the co-fed ethene can be molecularly incorporated but in addition it can generate a C, species that can react further to form methane and higher hydrocarbons.     

Synthesis of isoalkanes over Fe–Zn–Zr/HY composite catalyst through carbon dioxide hydrogenation

The reaction path of isoalkanes formation via CO₂ hydrogenation was studied over the Fe–Zn–Zr/HY composite catalyst, which gives high selectivity to isoalkanes. The results indicate that the reverse water–gas shift reaction is not the indispensable step for the synthesis of hydrocarbons. And i-C₄ (iso-butane) is formed from propylene and methanol through MTG (methanol to gasoline) reaction and i-C₅ (iso-pentane) obtained from the reaction of C₂ and C₃ through the additive dimerization. A part of C₁, C₄ is formed on the sole Fe–Zn–Zr catalyst from methanol for the CO₂ hydrogenation over Fe–Zn–Zr/HY composite catalyst.     

Nature of Surface Deposits on Sulfated Zirconia Used as Catalyst in the Benzoylation of Anisole

The effects of CO₂, CO and H₂ co-reactants on CH₄ pyrolysis reactions catalyzed by Mo/H-ZSM-5 were investigated as a function of reaction temperatures and co-reactant and CH₄ concentrations. Total CH₄ conversion rates were not affected by CO₂ co-reactants, except at high CO₂ pressures, which led to the oxidation of the active MoC _x species, but CH _x intermediates formed in rate-determining C–H bond activation steps increasingly formed CO instead of hydrocarbons as CO₂ concentrations increased. CO formation rates increased with increasing CO₂ partial pressure; all entering CO₂ molecules reacted with CH₄ within the catalyst bed to form two CO molecules at 950-1033 K. In contrast, hydrocarbon formation rates decreased linearly with increasing CO₂ partial pressure and reached undetectable levels at CO₂/CH₄ ratios above 0.075 at 950 K. CO formation continued for a short period of time at these CO₂/CH₄ molar ratios, but then all catalytic activity ceased, apparently as a result of the conversion of active carbide structures to MoO _x . The removal of CO₂ from the CH₄ stream led to gradual catalyst reactivation via reduction-carburization processes similar to those observed during the initial activation of MoO _x /H-ZSM-5 precursors in CH₄. The CO₂/CH₄ molar ratios required to inhibit hydrocarbon synthesis were independent of CH₄ pressure because of the first-order kinetic dependencies of both CH₄ and CO₂ activation steps. These ratios increased from 0.075 to 0.143 as reaction temperatures increased from 950 to 1033 K. This temperature dependence reflects higher activation energies for reductant (CH₄) than for oxidant (CO₂) activation, leading to catalyst oxidation at higher relative oxidant concentrations as temperature increases. The scavenging of CH _x intermediates by CO₂-derived species leads also to lower chain growth probabilities and to a significant inhibition of catalyst deactivation via oligomerization pathways responsible for the formation of highly unsaturated unreactive deposits. CO co-reactants did not influence the rate or selectivity of CH₄ pyrolysis reactions on Mo/H-ZSM-5; therefore, CO formed during reactions of CO₂/CH₄ mixtures are not responsible for the observed effects of CO₂ on reaction rates and selectivities, or in catalyst deactivation rates during CH₄ reactions. H₂ addition studies showed that H₂ formed during CH₄/CO₂ reactions near the bed inlet led to inhibited catalyst deactivation in downstream catalyst regions, even after CO₂ co-reactants were depleted.     

Comparative Study on CO2 Hydrogenation to Higher Hydrocarbons over Fe-Based Bimetallic Catalysts

This paper reports on notable promotion of C₂ ⁺ hydrocarbons formation from CO₂ hydrogenation induced by combining Fe and a small amount of selected transition metals. Al₂O₃-supported bimetallic Fe–M (M = Co, Ni, Cu, Pd) catalysts as well as the corresponding monometallic catalysts were prepared, and examined for CO₂ hydrogenation at 573 K and 1.1 MPa. Among the monometallic catalysts, C₂ ⁺ hydrocarbons were obtained only with Fe catalyst, while Co and Ni catalysts yielded higher CH₄ selectively than other catalysts. The combination of Fe and Cu or Pd led to significant bimetallic promotion of C₂ ⁺ hydrocarbons formation from CO₂ hydrogenation, in addition to Fe–Co formulation discovered in our previous work. CO₂ conversion on Ni catalyst nearly reached equilibrium for CO₂ methanation which makes this catalyst suitable for making synthetic natural gas. Fe–Ni bimetallic catalyst was also capable of catalyzing CO₂ hydrogenation to C₂ ⁺ hydrocarbons, but with much lower Ni/(Ni+Fe) atomic ratio compared to other bimetallic catalysts. The addition of a small amount of K to these bimetallic catalysts further enhanced CO₂ hydrogenation activity to C₂ ⁺ hydrocarbons. K-promoted Fe–Co and Fe–Cu catalysts showed better performance for synthesizing C₂ ⁺ hydrocarbons than Fe/K/Al₂O₃ catalyst which has been known as a promising catalyst so far.     

Electrochemical promotion of the CO2 hydrogenation reaction using thin Rh, Pt and Cu films in a monolithic reactor at atmospheric pressure

A monolithic electropromoted reactor (MEPR) with up to 22 thin Rh/YSZ/Pt or Cu/TiO₂/YSZ/Au plate cells was used to investigate the hydrogenation of CO₂ at atmospheric pressure and temperatures 220–380 °C. The Rh/YSZ/Pt cells lead to CO and CH₄ formation and the open-circuit selectivity to CH₄ is less than 5%. Both positive and negative applied potentials enhance significantly the total hydrogenation rate but the selectivity to CH₄ remains below 12%. The Cu/TiO₂/YSZ/Au cells produce CO, CH₄ and C₂H₄ with selectivities to CH₄ and C₂H₄ up to 80% and 2%. Both positive and negative applied potential significantly enhance the hydrogenation rate and the selectivity to C₂H₄. It was found that the addition of small (0.5 kPa) amounts of CH₃OH in the feed has a pronounced promotional effect on the reaction rate and selectivity of the Cu/TiO₂/YSZ/Au cells. The selective reduction of CO₂ to CH₄ starts at 220 °C (vs 320 °C in absence of CH₃OH) with near 100% CH₄ selectivity at open-circuit and under polarization conditions at temperatures 220–380 °C. The results show the possibility of direct CO₂ conversion to useful products in a MEPR via electrochemical promotion at atmospheric pressure.     

Porous MoxCy/SiO2 Material for CO2 Hydrogenation

The synthesis and characterization of an inexpensive porous Mo_xC_y/SiO₂ material is presented, which was obtained by mixing ammonium hexamolybdate, sucrose, and a mesoporous silica (SBA-15), with a subsequent heat treatment under inert atmosphere. This porous material presented a specific surface area of 170 m²/g. The catalytic behavior in CO₂ hydrogenation was compared with that of Mo₂C and α-MoC_1?x obtained from ammonium hexamolybdate and sucrose, using different Mo/C ratios. CO₂ hydrogenation tests were performed at moderate (100 kPa) and high pressures (2.0 MPa), and it was found that only CO, H₂O and CH₄ are formed at moderate pressures by the three materials, while at higher pressures, methanol and hydrocarbons (C₂H₆, C₃H₈) are also obtained. Differences in selectivity were observed at the high pressure tests. Mo₂C presented higher selectivity to CO and methanol compared with MoC_1?x, which showed preferential selectivity to hydrocarbons (CH₄, C₂H₆). The porous Mo_xC_y/SiO₂ material showed the highest CO₂ hydrogenation activity at high temperatures (270 and 300 °C), being a promising material for the conversion of CO₂ to CO and CH₄.

     

Hydrogenation of carbon dioxide over alumina supported Fe-K catalysts

The hydrogenation of CO₂ has been studied over Fe/alumina and Fe-K/alumina catalysts. The addition of potassium increases the chemisorption ability of CO₂ but decreases that of H₂. The catalytic activity test at high pressure (20 atm) reveals that remarkably high activity and selectivity toward light olefins and C₂₊ hydrocarbons can be achieved with Fe-K/alumina catalysts containing high concentration of K (K/Fe molar ratio = 0.5, 1.0). In the reaction at atmospheric pressure, the highly K-promoted catalysts give much higher CO formation rate than the unpromoted catalyst. It is deduced that the remarkable catalytic properties in the presence of K are attributable to the increase in the ability of CO₂ chemisorption and the enhanced activity for CO formation, which is the preceding step of C₂₊ hydrocarbon formation.     

Effect of Structural Promoters on Fe-Based Fischer–Tropsch Synthesis of Biomass Derived Syngas

Biomass gasification and subsequent conversion of this syngas to liquid hydrocarbons using Fischer–Tropsch (F–T) synthesis is a promising source of hydrocarbon fuels. However, biomass-derived syngas is different from syngas obtained from other sources such as steam reforming of methane. Specifically the H₂/CO ratio is less than 1/1 and the CO₂ concentrations are somewhat higher. Here, we report the use of Fe-based F–T catalysts for the conversion of syngas produced by the air-blown, atmospheric pressure gasification of southern pine wood chips. The syngas from the gasification step is compressed and cleaned in a series of sorbents to produce the following feed to the F–T step: 2.78 % CH₄, 11 % CO₂, 15.4 % H₂, 21.3 % CO, and balance N₂. The relatively high level of CO₂ suggests the need to use catalysts that are active for CO₂ hydrogenation as well is resistant to oxidation in presence of high levels of CO₂. The work reported here focuses on the effect of these different structural promoters on iron-based F–T catalysts with the general formulas 100Fe/5Cu/4K/15Si, 100Fe/5Cu/4K/15Al and 100Fe/5Cu/4K/15Zn. Although the effect of Si, Al or Zn on iron-based F–T catalysts has been examined previously for CO+CO₂ hydrogenation, we have found no direct comparison of these three structural promoters, nor any studies of these promoters for a syngas produced from biomass. Results show that catalysts promoted with Zn and Al have a higher extent of reduction and carburization in CO and higher amount of carbides and CO adsorption as compared to Fe/Cu/K/Si. This resulted in higher activity and selectivity to C₅+ hydrocarbons than the catalyst promoted with silica.     

Hydrogenation of carbon dioxide on cobalt catalysts – activation,deactivation, influence of carbon monoxide

A batch reactor directly combined with an ultrahigh vacuum apparatus, which is equipped with facilities for catalyst preparation and Auger electron spectroscopy, was used to answer some questions which had arisen in recent studies concerning carbon dioxide hydrogenation on pure metallic and supported Co catalysts. Both oxygen incorporated during oxidation/reduction cycles and carbon deposited when CO₂ is hydrogenated penetrate deep into the bulk. This kind of carbon can easily be hydrogenated. CO strongly hinders the reduction of the oxidized Co surface in the H₂/CO₂ reaction mixture (4 : 1). CO hydrogenation is favoured over CO₂ hydrogenation and leads to a higher percentage of C₂ to C₄ hydrocarbons as compared with CH₄ formation.     

Selective synthesis of alcohols from syngas and hydroformylation of ethylene over supported cluster-derived cobalt catalysts

Hydroformylation of ethylene and CO hydrogenation were studied over cobalt-based catalysts derived from reaction of Co₂(CO)₈ with ZnO, MgO and La₂O₃ supports. At 433 K a similar activity sequence was reached for both reactions: Co/ ZnO > Co/La₂O₃ > Co/MgO. This confirms the deep analogy between hydroformylation and CO hydrogenation into alcohols. In the CO hydrogenation the selectivity towards alcohol mixture (C₁-C₃) was found to be near 100% at 433 K for a conversion of 6% over the Co/ZnO catalyst; this catalyst showed oxo selectivity higher than 98% in the hydroformylation of ethylene. Magnetic experiments showed that no metallic cobalt particles were formed at 433 K. It is suggested that the active site for the step that is common to both reactions is related to the surface homonuclear Co²⁺/[Co(CO)₄]^– ion-pairing species.     

C,CO and CO2 hydrogenation on cobalt foil model catalysts: evidence for the need of CoO reduction

The hydrogenation of C, CO, and CO₂ has been studied on polycrystalline cobalt foils using a combination of UHV studies and atmospheric pressure reactions in temperature range from 475 to 575 K at 101 kPa total pressure. The reactions produce mainly methane but with selectivities of 98, 80, and 99 wt% at 525 K for C, CO, and CO₂, respectively. In the C and CO₂ hydrogenation the rest is ethane, whereas in CO hydrogenation hydrocarbons up to C₄ were detected. The activation energies of methane formation are 57, 86, and 158 kJ/mol from C, CO, and CO₂, respectively. The partial pressure dependencies of the CO and CO₂ hydrogenation indicate roughly first order dependence on hydrogen pressure (1.5 and 0.9), negative first order on CO (–0.75) and zero order on CO₂ (–0.05). Post reaction spectroscopy revealed carbon deposition from CO and oxygen deposition from CO₂ on the surface above 540 K. The reduction of cobalt oxide formed after dissociation of C-O bonds on the surface is proposed to be the rate limiting step in CO and CO₂ hydrogenation.     

Higher Hydrocarbon Production through Oxidative Coupling of Methane Combined with Hydrogenation of Carbon Oxides

In the production of higher hydrocarbons, combining oxidative coupling of methane (OCM) with hydrogenation of the formed carbon oxides in a separate reactor provides an alternative to the currently applied methane conversion to syngas followed by Fischer‐Tropsch synthesis. The effects of CH₄:O₂ feed ratio in the OCM reactor and partial pressures of H₂ or/and H₂O in the hydrogenation reactor were analyzed to maximize production of C₂₊ hydrocarbons and reduce CO_x formation. The highest C₂₊ yield was achieved with low CH₄:O₂ feed ratio for OCM and removal of the formed water before entering the hydrogenation reactor.     

Increase in the thermal stability during the methanation of CO2 over a Rh catalyst prepared from an amorphous alloy

The hydrogenation of CO₂ was investigated over a Rh catalyst prepared from an amorphous Rh₂₀Zr₈₀ alloy. After the reaction, the catalyst was regenerated by oxidation in air and reduction in H₂. It was observed that the reaction activity increased with the repetition of regeneration. We also prepared the Rh/ZrO₂ catalyst by the conventional impregnation method. The difference in the turnover frequency between the alloy-precursor catalyst and the conventionally prepared catalyst was small. For the alloy-precursor catalyst, however, the conversion and CH₄ selectivity were stable at 723 K, whereas the conversion and CH₄ selectivity decreased with time-on-stream even at 673 K for the catalyst prepared by the conventional impregnation method.     

Pulse studies of CH4 interaction with NiO/Al2O3 catalysts

Pulse studies of the interaction of CH₄ and NiO/Al₂O₃ catalysts at 500°C indicate that CH₄ adsorption on reduced nickel sites is a key step for CH₄ oxidative conversion. On an oxygen-rich surface, CH₄ conversion is low and the selectivity of CO₂ is higher than that of CO. With the consumption of surface oxygen, CO selectivity increases while the CO₂ selectivity falls. The conversion of CH₄ is small at 500°C when a pulse of CH₄/O₂ (CH₄O₂=21) is introduced to the partially reduced catalyst, indicating that CH₄ and O₂ adsorption are competitive steps and the adsorption of O₂ is more favorable than CH₄ adsorption     

Near 100% CO selectivity in CH4 direct catalytic oxidation at low temperatures (<700‡C) under unsteady state conditions

Almost 100% CO selectivity was achieved with small pulses of CH₄/O₂ (2/1), using very short residence times over a reduced NiO/La₂O₃ catalyst. One concludes that CH₄ conversion depends on its dissociation, whereas CO selectivity is mainly dependent on the strength of oxygen binding to the catalyst. Over the reduced catalyst, the oxygen species oxidize with difficulty (because of their strong binding to metal Ni) CO to CO₂, whereas over the unreduced catalyst (which contains Ni oxide), the oxygen species easily oxidize (because they are weakly adsorbed) CO to CO₂.     

Effect of CO2 in the feed stream on the deactivation of Co/γ-Al2O3 Fischer–Tropsch catalyst

The influence of CO₂ on the deactivation of Co/γ-Al₂O₃ Fischer–Tropsch (FT) catalyst in CO hydrogenation has been investigated. The presence of CO₂ in the feed stream reveals a negative effect on catalyst stability and in the formation of heavy hydrocarbons. The CO₂ acts as a mild oxidizing agent on cobalt metal during Fischer–Tropsch synthesis. During FT synthesis on Co/γ-Al₂O₃ of 70 h, the CO conversion and C₅₊ selectivity in the presence of CO₂ decreased more significantly than in the absence of CO₂. CO₂ is found to be responsible for the partial oxidation of surface cobalt metal at FT synthesis environment with the co-existence of generated water.