A new supported Fe-MnO catalyst for the production of light olefins from syngas. II. Effect of support on the secondary reactions of C2H4

The TPSR technique was used to investigate the effect of the support on the secondary reactions of ethylene formed during CO hydrogenation. Based on the results of CO hydrogenation and CO/H₂-TPSR characterization, it was found that different supports induced different secondary reactions, and thus affected the selectivity to light olefins directly. The Fe-MnO/MgO catalyst (based on basic support) causes disproportionation of C₂H₄, and thus, leads to the formation of C₃H₆. The Fe-MnO/Al₂O₃ catalyst (based on acidic support) showed obvious hydrogenation of C₃H₆. The disproportionation of C₂H₄ was also promoted by the Fe-MnO/Al₂O₃ catalyst, but because of its activity for C₃H₆ hydrogenation, a large amount of C₃H₈ was produced. The different C₂H₄ secondary reactions are relevant to different CO/H₂ reaction pathways over the catalyst surface, so the Fe-MnO/MgO catalyst is a desirable catalyst for the production of light olefins from CO/H₂ while the Fe-MnO / Al₂O₃ catalyst was not so.     

Promotion effect of K2O and MnO additives on the selective production of light alkenes via syngas over Fe/silicalite-2 catalysts

The addition of K₂O and MnO promoters enhances catalyst activity and selectivity to light alkenes during CO hydrogenation over silicate-2 (Si-2) supported Fe catalysts. The results of CO hydrogenation and CO-TPD, CO/H₂-TPSR, C₂H₄/H₂-TPSR and C₂H₄/H₂ pulse reaction over Fe/Si-2 catalysts with and without promoters clearly show that the MnO promoter mainly prohibits the hydrogenation of C₂H₄ and C₃H₆. Therefore, it enhances the selectivity to C₂H₄ and C₃H₄ products. Meanwhile further incorporating the K₂O additive into the FeMn/ Si-2 catalyst leads to a remarkable increase in both the capacity and strength of the strong CO adspecies. These produce much more [C_ad] via their dissociation and disproportionation at higher temperatures. This results in an increase in the CO conversion and the selectivity to light olefins. Moreover, the K₂O additive modifies the hydrogenating reactivity of [C_ad] and suppresses the disproportionation of C₂H₄ that occurs as a side-reaction. Both K₂O and MnO promoters play key roles for enhancing the selective production of light alkenes from CO hydrogenation over Fe/Si-2 catalyst.     

Enhanced Production of C2–C4 Olefins Directly from Synthesis Gas

An attempt made for the selective production of C₂–C₄ olefins directly from the synthesis gas (CO + H₂) has led to the development of a dual catalyst system having a Fischer–Tropsch (K/Fe–Cu/AlOx) catalyst and cracking (H-ZSM-5) catalyst operate in consecutive dual reactors. The flow rate (space velocity) and H₂/CO molar ratio of the feed have been optimized for achieving higher CO conversions and olefin selectivities. The selectivity to C₂–C₄ olefins is further enhanced by optimizing the reaction temperature in the second reactor (cracking), where the product exhibited 51% selectivity to C₂–C₄ hydrocarbons rich in olefins (77%) with a stable time-on-stream performance in a studied period of 100 h.     

Improvement of light olefins production over the Co-Ni-Mn nano-catalyst: modeling and optimization of process by RSM

The co-precipitated Co-Ni-Mn nano-catalysts were evaluated for carbon monoxide hydrogenation. The influence of Al₂O₃, SiO₂, Zeolite, Active carbon, MgO supports and then the effect of best chosen support loading on the catalytic behavior and structure of ternary Co-Ni-Mn nano-catalysts were studied. The Co-Ni-Mn/20 wt%SiO₂ sample has shown highest selectivity toward light olefins production. Furthermore the influence of process conditions was investigated. Evaluation tests were performed under process conditions of P = 1–10 bar, T = 523-623 K, and H₂/CO = 0.67–3. The Response Surface Methodology (RSM) method was used for modeling and optimization process and the best conditions for catalyst evaluation were determined (T = 598.16 K, P = 1 atm and H₂/CO = 2.19). Under these conditions the highest selectivity of light olefins, higher CO conversion % and lower selectivity toward methane were achieved. Catalysts characteristics were investigated using XRD, BET, TEM, TGA, DSC, SEM, XPS, and TPR techniques. © 2021 Society of Chemical Industry (SCI).     

Calorimetric study of the reversibility of CO pollutant adsorption on high loaded Pt/carbon catalysts used in PEM fuel cells

A major obstacle to the broader use of fuel cells is the poisoning of supported Pt catalysts by the CO present in virtually all feeds. In this paper, the microcalorimetry technique was employed to study and compare the CO adsorption properties of different commercial carbon-supported platinum catalysts with high Pt loading, aimed to be used in proton exchange membrane fuel cells (PEMFCs) applications. Combined with other techniques of characterization, such as BET, XRD, TPD-MS and TPR, adsorption microcalorimetry has permitted a better understanding of the studied systems. The pore architecture of Pt/C catalysts was found to influence the kinetics of heat release during CO adsorption. The accessibility of CO molecules to the adsorption sites increased with the mesoporosity of the catalyst. The degree of catalyst poisoning by CO upon successive air/H₂/CO cycles varied between 2 and 30% for the different studied samples. These results confirm that the surface chemistry of the catalyst, and in particular the Pt deposition method, affects the surface site energy distribution and consequently the adsorptive properties towards H₂ and CO. It was found that both H₂ and CO are chemisorbed on the investigated samples. Pt/C powders exhibit higher differential heats of carbon monoxide adsorption in comparison with hydrogen adsorption. A reaction between pre-adsorbed H₂ and CO from the gas phase takes place on Pt/C catalysts as a result of competitive adsorption.     

Characterization of K-Fe/silicalite catalyst prepared via SMAI

Highly dispersed supported metal catalyst K-Fe/silicalite are prepared via SMAI method, and characterized by TEM, XRD, XPS and magnetic measurements techniques. Its catalytic properties in the CO hydrogenation making olefin reaction are also studied. The results show that the iron on the surface of the catalyst which has superparamagnetism, almost existed as the Fe⁰ before reacting. The catalyst exhibited high activity and selectivity for light olefins in CO+H₂.     

Carbon Monoxide Hydrogenation on Cobalt/Zeolite Catalysts

The synthesis of hydrocarbons from catalytic hydrogenation of CO/H₂ was investigated over Co/zeolite catalysts at 1 atm, 493–553 K, H₂/CO = 2, and GHSV = 1200. Various zeolites, such as NaA, NaX, NaY, KL and NaMordenite, were used as the supports. The catalysts were prepared by impregnation and were characterized by H₂/CO chemisorption and temperature-programmed reduction (TPR). Based on TPD measurements, the CO/H₂ adsorption ratio can be used as an index for the extent of metal-zeolite interaction. The stronger the metal-zeolite interaction is, the higher the Co/H₂ adsorption ratio on metal is. The activity and selectivity of cobalt supported in zeolites were affected by complex factors such as framework structure, Si/Al ratio, and the complementary cations. The activity of the catalyst is in the order: Co/KL > Co/NaX > Co/NaY > Co/NaMordenite > Co/NaA. All of the Co/zeolite catalysts had a very high selectivity to C₂–C₄ olefins, which would decrease with increasing reaction temperature. Cobalt oxide supported in zeolite was difficult to reduce. Increasing the reduction temperature could increase the reducibility of cobalt and resulted in the increase of activity.     

Tuning millisecond chemical reactors for the catalytic partial oxidation of cyclohexane

It is demonstrated that millisecond partial oxidation of cyclohexane can be tuned by varying the catalyst and operating conditions to generate product distributions that favor (1) oxygenates, (2) olefins, or (3) syngas (H₂ and CO). High selectivities to parent oxygenates require low conversions using low-temperature catalysts, such as Ag or Co. Olefins are favored by Pt or Pt-Sn and H₂ addition eliminates the production of CO and CO₂, thereby increasing olefin selectivities. For syngas, Rh is the catalyst of choice. Finally, a Pt-10% Rh single gauze gives high selectivities to both oxygenates and olefins.Conventional methods for the partial oxidation of cyclohexane are liquid-phase processes that are plagued by poor conversions, high recycle costs, long residence times (minutes to hours), and expensive catalysts. In contrast, with a cyclohexane–oxygen feed at C₆H₁₂/O₂=2, a Pt-10% Rh single gauze catalyst can give total selectivities exceeding 80% to oxygenates and olefins at 25% cyclohexane conversion and complete oxygen conversion. The products consist of nearly 60% selectivity to the C₆ products, cyclohexene and 5-hexenal. The temperature profile attained in the single-gauze reactor allows the preservation of these highly non-equilibrium products.Alternative catalysts for cyclohexane oxidation to oxygenates and olefins include α-alumina monoliths coated with Pt, Rh, Pt-Rh, Pt-Sn, Co, Mo or Ag. The Co, Mo and Ag catalysts give very high selectivities to C₆ oxygenates but are hindered by poor conversions (<5%) of both cyclohexane and oxygen at these millisecond contact times. H₂ addition to cyclohexane oxidation feed mixtures over Pt and Pt-Sn is shown to significantly increase the selectivities to C₆ olefins while reducing the formation of CO and CO₂.Cyclohexane oxidation in air over Rh monoliths enables the production of high yields (>95%) of syngas. This process could find applications in the automotive industry as the production of hydrogen from liquid fuels becomes important.     

Partial oxidation of ethanol over Pd/CeO2 and Pd/Y2O3 catalysts

The effect of the support nature on the performance of Pd catalysts during partial oxidation of ethanol was studied. H₂, CO₂ and acetaldehyde formation was favored on Pd/CeO₂, whereas CO production was facilitated over Pd/Y₂O₃ catalyst. According to the reaction mechanism, determined by DRIFTS analyses, some reaction pathways are favored depending on the support nature, which can explain the differences observed on products distribution. On Pd/Y₂O₃ catalyst, the production of acetate species was promoted, which explain the higher CO formation, since acetate species can be decomposed to CH₄ and CO at high temperatures. On Pd/CeO₂ catalyst, the acetaldehyde preferentially desorbs and/or decomposes to H₂, CH₄ and CO. The CO formed is further oxidized to CO₂, which seems to be promoted on Pd/CeO₂ catalyst.     

Effect of partial metal reduction on the catalytic property of cobalt

Effect of partial metal reduction on the catalytic property of cobalt has been studied for Co/ Al₂O₃ catalyst reduced to different extents. The sample catalysts have been tested for CO and H₂ adsorption, CO hydrogenation, and Temperature Programmed Surface Reaction (TPSR). Major effect of the incomplete metal reduction on the surface property of cobalt is that hydrogen adsorption is significantly suppressed. This behavior is responsible to enhanced olefin production and retarded CO dissociation as observed for the catalysts of lower metal reduction. Changes in the kinetic parameters of CO hydrogenation on partially reduced cobalt may be explained from its gas adsorption behavior.     

Effect of the nature of the support of a cobalt catalyst on the synthesis of hydrocarbons from CO,H<Subscript>2</Subscript>, and C<Subscript>2</Subscript>H<Subscript>4</Subscript>

The effect of the nature of the support of a Co catalyst on the synthesis of hydrocarbons from CO, H₂, and C₂H₄ was studied in this work. It was found that the introduction of ethylene into synthesis gas resulted in an increase in the yield of liquid hydrocarbons. In this case, the conversion of C₂H₄ was complete and the degree of its involvement into the synthesis of C₅₊ hydrocarbons depended on the concentration of this component in the starting mixture and the nature of the support. Specific features of the adsorption of CO and C₂H₄ on the used Co catalysts were determined using a temperature-programmed desorption method.     

Characterization of fused Fe-Cu based catalyst for higher alcohols synthesis and DRIFTS investigation of TPSR

Fused Fe-Cu based catalyst for higher alcohols synthesis (HAS) is characterized by XRD, TG-DTA, H₂-TPD and DRIFTS of CO adsorption. The results of XRD reveal that the fused Fe-Cu based catalyst consists of Cu₂O, CuFeO₂ and CuFe₂O₄ species. After reduction, the metallic Fe and Cu are the main species, but minor CuFeO₂ and CuFe₂O₄ species are also present. H₂-TPD shows that in comparison with the pure Fe- or Cu-based sample, the ability of Fe-Cu based catalyst for activation of H₂ is higher and the stronger metal-hydrogen bonds are formed. DRIFTS of CO adsorption indicates that CO is adsorbed on both metal and metal ion sites, where the dissociation of CO to C* and O* species and the formation of CO₂ are observed. In situ DRIFTS investigation of CO + H₂-TPSR over the Fe-Cu based catalyst shows that the dissociative activation of H₂ is more difficult than the activation of CO, and carbonaceous and hydrocarbon fragment species only appears after the dissociative activation of H₂. In addition, HAS over the Fe-Cu based catalyst is very complicated, where various intermediates including = CH₂, − CHO, − OOCH, − OH and − C(= O)-R exist.     

Effect of chlorine on the selectivity of a fischer-tropsch catalyst composed of iron/vanadium oxides

Fischer-Tropsch catalysts (Fe/V oxides with ZnO and K₂CO₃ as promoters) were exposed to CHCl₃, thereby producing surface and bulk chlorides. The effect of this exposure on activity and selectivity was studied in a continuous recycle reactor at a total pressure of 10 bar (CO/H₂ in most experiments: ca 1:1) in a temperature range between 200 and 343°C. CHCl₃ was introduced in amounts of up to 1 × 10^?2 mol chlorine per g catalyst. The catalyst samples were characterized by internal surface area, pore-size distribution and adsorption capacities for CO, H₂ and C₂H₄. Prior to synthesis, the catalysts were reduced by H₂. Catalyst exposure to CHCl₃ resulted in a decrease of activity and considerable changes in product distribution. Hydrogenation and isomerization of 1-olefins were partly suppressed; the chain length of the products was slightly increased. Deactivation of the catalysts due to chlorine addition was partly reversible during operation, while olefin formation was not significantly altered with time-on-stream. The effect of chlorine on activity and selectivity is explained by dissociation of CO as the chain initiating step and CO insertion into a carbon/metal bond as a possible chain propagation step. Since adsorption capacity for H₂ decreases on the addition of chlorine, this may also contribute to lower activity and change in selectivity, compared to the unexposed catalyst.     

CO methanation toward the production of synthetic natural gas over highly active Ni/TiO2 catalyst

The sonochemical synthesis and characterization of highly active and stable Ni nanoparticles supported on TiO₂ as a CO methanation catalyst for the production of synthetic natural gas are reported. The catalyst synthesized by sonication showed higher activity for CH₄ formation than the catalyst synthesized via the conventional wet impregnation method. The activation energy was found to be 79 and 94 kJ mol^?1 for the catalyst synthesized with sonication and wet impregnation method, respectively. The combined results of x‐ray photoelectron spectroscopy and x‐ray diffraction show that the enhancement in activity of the sample synthesized by sonication method is due to partial substitution of Ni in TiO₂ lattice. This creates oxide vacancies and facilitates hydrogen adsorption and spillover from nickel to support. H₂‐ temperature‐programmed reduction study corroborates the intimate contact of Ni with support, thus rendering strong metal support interactions. The mechanism involving Langmuir–Hinshelwood kinetics with hydrogen‐assisted CO dissociation was used to correlate experimental data. © 2013 American Institute of Chemical Engineers AIChE J, 60: 1027–1035, 2014     

Comprehensive kinetic study for Fischer–Tropsch reaction over KMoFe/CNTs nano-structured catalyst

The kinetics of the Fischer–Tropsch (FT) reaction was evaluated through detailed experimentation with a KMo bimetallic promoted Fe catalyst supported on carbon nanotubes (CNTs). The kinetic tests were conducted in a fixed-bed reactor under operating conditions of P = 6.9–41.3 bar, T = 543–563 K, H₂/CO = 1, gas hourly specific velocity (GHSV) = 2000 h⁻¹. This study aimed to investigate the mechanism prevailing in CO activation and the rate equation for CO consumption during FT reactions over a 0.5K5Mo10Fe/CNTs catalyst. To evaluate the synergistic effects of Fe, Mo, and K phases on the catalyst activity, both fresh and spent catalysts were thoroughly characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy and energy-dispersive spectroscopy (SEM-EDS), X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) to ascertain the different phases (active sites) present and relevant interactions. Based on the adsorption of carbon monoxide and hydrogen, 22 possible mechanisms for monomer formation were proposed for FT synthesis in accordance with the Langmuir–Hinshelwood–Hougen–Watson (LHHW) and Eley–Rideal (ER) adsorption theories. The best fit kinetic model was identified through a multi-variable non-linear regression analysis. The selected mechanistic model was based on carbide formation approach, where H₂-assisted adsorption of CO was considered for the derivation. Kinetic parameters such as activation energy, adsorption enthalpies of H₂, and CO were estimated to be 65.0, −13.0, and −54.0 kJ/mol, respectively. Considering the developed kinetic model, the effects of reaction temperature and pressure were assessed on Fischer–Tropsch synthesis (FTS) product distribution. Additionally, the kinetic model was compared with the typical Anderson–Schulz–Flory model, suggesting the effects of water-gas-shift and the existence of additional formation pathway such as secondary re-adsorption of olefins for heavier hydrocarbons.     

Kinetic Analysis of the Hydrocarbon Total Oxidation Using Individually Measured Adsorption Isotherms

The partial and total oxidation of C₂H₄, C₃H₆ separately and in mixtures, and CO on a CrO_x/γ‐Al₂O₃ catalyst was studied to describe the reaction kinetics. Based on catalytic cycles mechanistic kinetic models of all reactions were derived. For reduction of adjustable parameters individually measured adsorption isotherms were used to parameterize adsorption constants in the kinetic models. The complex reaction network was decomposed in three sub‐networks to support parameter estimation, to quantify and validate kinetic rate approaches. The best fit for hydrocarbon reactions was achieved by an Eley‐Rideal and for CO by a Mars‐van Krevelen approach.     

The promotional effect of K on the catalytic activity of Ni/MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> for the combined H<Subscript>2</Subscript>O and CO<Subscript>2</Subscript> reforming of coke oven gas for syngas production

A K-promoted 10Ni-(x)K/MgAl₂O₄ catalyst was investigated for the combined H₂O and CO₂ reforming (CSCR) of coke oven gas (COG) for syngas production. The 10Ni-(x)K/MgAl₂O₄ catalyst was prepared by co-impregnation, and the K content was varied from 0 to 5 wt%. The BET, XRD, H₂-chemisorption, H₂-TPR, and CO₂-TPD were performed for determining the physicochemical properties of prepared catalysts. Except under the condition of a K/Ni=0.1 (wt%/wt%), the Ni crystal size and dispersion decreased with increasing K/Ni. The coke resistance of the catalyst was investigated under conditions of CH₄: CO₂: H₂: CO:N₂=1 : 1 : 2 : 0.3 : 0.3, 800 °C, 5 atm. The coke formation on the used catalyst was examined by SEM and TG analysis. As compared to the 10Ni/MgAl₂O₄ catalyst, the Kpromoted catalyst exhibited superior activity and coke resistance, attributed to its strong interaction with Ni and support, and the improved CO₂ adsorption characteristic. The 10Ni-1K/MgAl₂O₄ catalyst exhibited optimum activity and coke resistance with only 1wt% of K.     

Reforming of Methane with Carbon Dioxide over a Catalyst Consisting of Ruthenium Metal and Cerium Oxide Supported on Mordenite

Reforming of CH₄ with CO₂ proceeds at 400 °C over a catalyst consisting of ruthenium metal and CeO₂ highly dispersed on mordenite. The catalyst, Ru-CeO₂/MZ, is highly active for the reforming of CH₄ under the conditions at which a carbon formation reaction is thermodynamically apt to take place. The reforming selectively forms H₂ and CO. An increase in the weight of the catalyst resulting from carbon deposits was scarcely observed. IR spectra for the catalyst indicate that the reforming proceeds via the formation of the intermediate species such as Ru-CO and Ru-CH_x on the surface of ruthenium. The data of H₂ adsorption support the idea that ruthenium is highly dispersed in Ru-CeO₂/MZ.     

Co/CeO2-ZrO2 catalysts prepared by impregnation and coprecipitation for ethanol steam reforming

Co/CeO₂-ZrO₂ catalysts for the ethanol steam reforming were prepared by wet incipient impregnation and coprecipitation methods. These catalysts were characterized by nitrogen adsorption, TEM-EDX, XRD, H₂-TPR, and CO chemisorption techniques. It was found that the catalyst reducibility was influenced by the preparation methods; catalysts with different reduction behaviors in the pre-reduction showed different catalytic activities toward hydrogen production. The H₂-TPR studies suggested the presence of metal–support interactions in Co/CeO₂-ZrO₂ catalysts during their hydrogen pre-reduction, a necessary treatment process for catalysts activation. These interactions were influenced by the preparation methods, and the impregnation method is a favorable method to induce a proper metal–support effect that allows only partial reduction of the cobalt species and leads to a superior catalytic activity for the hydrogen production through ethanol steam reforming. At 450 °C, the impregnated catalyst gives a hydrogen production rate of 147.3 mmol/g-s at a WHSV of 6.3 h⁻¹ (ethanol) and a steam-to-carbon ratio of 6.5.     

Dehydrogenation of Methane over Mo/ZSM-5. Effects of Additives in the Methane Stream

The dehydrogenation of methane was carried out over a Mo/ZSM-5 catalyst. It was revealed that the purity of the methane was very critical for the evaluation of the catalyst activity. In order to study the phenomenon, the effects of the addition of O₂, CO₂, CO or H₂ to the feed were investigated. A small amount of O₂ increased the amounts of aromatic compounds and CO produced. The addition of H₂ scarcely affected the conversion of methane, but it prevented the deactivation of the catalyst, i.e., benzene production remained constant during a 6 h test.