Conversion of syngas to C2+ oxygenates over Rh-based/SiO2 catalyst: The promoting effect of Fe

The effect of Fe promoter on the catalytic properties of Rh–Mn–Li/SiO₂ catalyst for CO hydrogenation was investigated. The catalysts were comprehensively characterized by means of X-ray diffraction (XRD), N₂ adsorption–desorption, temperature programmed reduction (TPR), temperature programmed desorption (TPD), temperature programmed surface reaction (TPSR), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Activity testing results showed that low loading of Fe (≤0.1 wt%) improved the reactivity and yield of C₂⁺ oxygenates; however, the opposite effect appeared at the high values of Fe (>0.1 wt%). Characterization results suggested that the addition of Fe strengthened the Rh–Mn interaction and increased the desorption/transformation rate of adsorbed CO, which could be responsible for the increase of CO conversion. But on the other hand, the existence of Fe might deposit over the Rh surface, and decreased the number of active sites, resulting in the decrease of CO conversion when the Fe amount was excessive. The selectivity to C₂⁺ oxygenates varied inversely with the reducibility of Rh oxide species. Moreover, it is proposed that the transformation of dicarbonyl Rh⁺(CO)₂ into H–Rh–CO is favorable for the formation of C₂⁺ oxygenates, and the hydrogenation ability of Fe can increase the hydrogenation of acetaldehyde to ethanol.     

Mechanism of formation of C2-oxygenated compounds from CO + H2 reaction over SiO2-supported Rh catalysts

The mechanism of acetaldehyde and ethanol formation from the CO + H₂ reaction below atmospheric pressure has been investigated by combining infrared spectroscopic measurement and ¹³CO and C¹⁸O isotopic tracer studies with reaction kinetics. The rates of acetaldehyde and ethanol formation are markedly dependent on the nature of metal precursors employed. The addition of sodium cations depresses the total catalytic activity, while the selectivity for ethanol is increased by the addition of manganese cations. From the behavior of surface species under reaction conditions, it is concluded that acetaldehyde is formed through the following two steps: (i) CO insertion into C₁ species which are reaction intermediates for not only hydrocarbons but also for the methyl group in acetaldehyde, and (ii) subsequent formation of acetate ions whose one oxygen atom is supplied from the support, finally producing acetaldehyde. Differences in ¹⁸O distribution in acetaldehyde and ethanol during the C¹⁸O + H₂ reaction indicate that ethanol is not produced via direct hydrogenation of acetaldehyde.     

Organometallics derived (Pd + Ln)/SiO2 catalysts for the reactions of synthesis gas conversion

C₃H₆ hydroformylation and CH₃OH synthesis on organometallics derived (Pd + Ln)/ SiO₂ and Pd/SiO₂ catalysts have been studied. The activity and selectivity towards methanol in CO + H₂ reaction were observed to increase for all the modified catalysts while both the hydroformylation activity and selectivity towards oxygenates in C₃H₆ hydroformylation decreased for the catalysts in comparison to those of Pd/SiO₂. The FTIR, TPD data and characteristic catalytic properties of the catalysts studied allow to suggest that C₃H₆ hydroformylation on (Pd + Ln)/SiO₂ catalysts occurs on monometallic Pd clusters without participation of mixed active sites and CO complexes activated thereon.     

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.     

Effect of Vanadium Promotion on Activated Carbon-Supported Cobalt Catalysts in Fischer–Tropsch Synthesis

The effect of vanadium promotion on activated carbon (AC)-supported cobalt catalysts in Fischer–Tropsch synthesis has been studied by means of XRD, TPR, CO-TPD, H₂-TPSR of chemisorbed CO and F-T reaction. It was found that the CO conversion could be significantly increased from 38.9 to 87.4% when 4 wt.% V was added into Co/AC catalyst. Small amount of vanadium promoter could improve the selectivity toward C₁₀–C₂₀ fraction and suppress the formation of light hydrocarbon. The results of CO-TPD and H₂-TPSR of adsorbed CO showed that the addition of vanadium increased the concentration of surface-active carbon species by enhancing CO dissociation and further improved the selectivity of long chain hydrocarbons. However, excess of vanadium increased methane selectivity and decreased C₅⁺ selectivity.     

Carbon-carbon bond formation on metal oxides: From single crystals toward catalysis

Previous work in our laboratory indicated that carbonyl metathesis of aldehydes can be accomplished as a gas-solid reaction on a reduced TiO₂(001) single crystal under ultrahigh vacuum (UHV). This reaction requires the presence of cations in lower oxidation states on the surface, but does not require Ti⁰ as suggested by previous studies in the liquid phase. In the course of attempts to carry out this reaction catalytically, TPD experiments on TiO₂ single crystals and powders were conducted. In addition to the aldolization of acetaldehyde to crotonaldehyde, carbonyl metathesis of acetaldehyde to butene was observed. Benzaldehyde TPD on reduced TiO₂ powder gave substantial amounts of styrene (PhCH=CH₂) which is most likely formed by disproportionation of stilbene (PhCH=CHPh), the metathesis product observed in single crystal studies. Addition of Ti metal to titania resulted in the formation of large amounts of toluene (by unimolecular reduction) rather than stilbene or styrene (by bimolecular reductive coupling). More importantly, it was possible to form 1-phenylpropene (PhCH=CH-CH₃), a cross-coupling product, by the co-metathesis of benzaldehyde and acetaldehyde on reduced titania, ceria and iron oxide powders during TPD at atmospheric pressure. These studies represent an extension of stoichiometric reactions observed on single crystals in UHV toward novel catalysis. While carbonyl metathesis has still not been accomplished catalytically, its observation during TPD of aldehydes on dihydrogen-reduced oxides has demonstrated the feasibility of each of the steps required to close a catalytic cycle.     

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.     

K/Fe/β-Mo2C: A novel catalyst for mixed alcohols synthesis from carbon monoxide hydrogenation

A novel K/Fe/β-Mo₂C catalyst was prepared by a temperature programmed reaction method, it exhibited high yield of alcohol, especially high C₂₊OH selectivity for mixed alcohol synthesis from CO hydrogenation.     

Influence of alkali metal (Li and Cs) addition to Mo2N catalyst for CO hydrogenation to hydrocarbons and oxygenates

The aim of this work is to understand the catalytic behaviour of Li and Cs promoted Mo₂N for CO hydrogenation to hydrocarbons and oxygenates at the reaction conditions 275–325 °C, 7 MPa, and 30 000 h^?1 GHSV. Molybdenum nitrides were synthesized via temperature programmed treatment of ammonium heptamolybdate (AHM) and alkali metal (AM) precursors under continuous gaseous ammonia flow. Unpromoted Mo₂N and AM‐Mo₂N catalysts were characterized using BET‐pore size, X‐ray diffraction, TPD‐mass of CO, HR‐TEM, and XPS techniques. Nominal loadings of 1, 5, and 10 wt% of Li and Cs were selected for these studies. At a 10 % CO conversion level, the total oxygenate selectivity of 28, 11, and 6.5 % was observed on 5Cs‐Mo₂N, 5Li‐Mo₂N, and unpromoted Mo₂N, respectively. The decreased oxygenate selectivity for unpromoted Mo₂N was mainly associated with CO dissociative hydrogenation on Mo^δ+ sites. On the other hand, improved molecular CO insertion into ?C_xH_y intermediate accelerates the total oxygenate formation on the Cs‐Mo‐N catalyst. However, during nitridation, crystal structure changes were observed in Li‐Mo‐N and the obtained oxygenates selectivity was attributed to the Li₂MoO₄ phases. At lower AM loadings, the active sites corresponding to oxygenates formation were inadequate, and at higher AM loadings, surface metallic molybdenum decreased the total oxygenate selectivity.

     

The effect of synthesis gas composition on the Fischer–Tropsch synthesis over Co/γ-Al2O3 and Co–Re/γ-Al2O3 catalysts

The Fischer–Tropsch synthesis over Co/γ-Al₂O₃ and Co–Re/γ-Al₂O₃ was investigated in a fixed-bed reactor at 20 bar and 483 K using feed gases with molar H₂/CO ratios of 2.1, 1.5 and 1.0 simulating synthesis gas derived from biomass. With lower H₂/CO ratios in the feed, the CO conversion and the CH₄ selectivity decreased, while the C₅₊ selectivity and olefin/paraffin ratio for C₂–C₄ increased slightly. The water–gas shift activity was low for both catalysts, resulting in high molar usage ratios of H₂/CO (close to 2.0), even at the lower inlet ratios (i.e. 1.5 and 1.0). For both catalysts, the drop in the production rate of hydrocarbons when shifting from an inlet ratio of 2.1 to 1.5 was significant mainly because the H₂/CO usage ratio did not follow the change in the inlet ratio. The hydrocarbon selectivities were rather similar for inlet H₂/CO ratios of 2.1 and 1.5, while significantly deviating from those for an inlet ratio of 1.0. With the studied catalysts, it is possible to utilize the advantages of an inlet ratio of 1.0 (higher selectivity to C₅₊, lower selectivity to CH₄, no water–gas shifting of the bio-syngas needed prior to the FT reactor) if a low syngas conversion is accepted.     

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.     

Unusually High Selectivity to C2+ Alcohols on Bimetallic CoFe Catalysts During CO Hydrogenation

Silica-supported cobalt and iron catalysts (10% Co and 5% or 1% Fe) were prepared and tested in a flow reactor in the hydrogenation of CO, using H₂/CO = 2:1 (molar) ratio in the feed, an overall pressure of 20 bar, and temperatures of 493, 513 and 533 K. Activity and product distribution were found to depend strongly on the composition of the catalysts. Thus, the Fe-free catalyst was selective toward C₅₊ formation (67% selectivity to C₅₊) and a low methanation rate, while the Co-free counterpart was less selective toward C₅₊, with a simultaneous increase in the formation of lighter fractions and alcohols. The behavior of the bimetallic CoFe catalysts was different. In the bimetallic CoFe10/5-c catalyst, selectivity to alcohols increased with respect to the monometallic Co10-c, and this was moderately high (15% to C₃₊ OH alcohols). In the bimetallic CoFe10/1-c sample, selectivity to alcohols was fairly high (29%), and ethanol reached the highest proportion (17%) among the alcohols. Surface and structural information concerning the activated catalysts, derived from X-ray diffraction, temperature-programmed reduction, Mössbauer, and photoelectron spectroscopy, revealed the appearance of a CoFe phase under the conditions employed during the catalyst activation. In the bimetallic cobalt–iron catalysts, this CoFe phase is suggested to be responsible for the rather high selectivity toward alcohol formation.     

The Mechanism Studies of Ethanol Oxidation on PdO Catalysts by TPSR Techniques

The paper studies the direct oxidation of ethanol and CO on PdO/Ce_0.75Zr_0.25O₂ and Ce_0.75Zr_0.25O₂ catalysts. Characterization of catalysts is carried out by temperature-programmed desorption (TPD), temperature-programmed surface reaction (TPSR) techniques to correlate with catalytic properties and the effect of supports on PdO. The simple Ce_0.75Zr_0.25O₂ is in less active for ethanol and CO oxidation. After loaded with PdO, the catalytic activity enhances effectively. Combined the ethanol and CO oxidation activity with CO-TPD and ethanol-TPSR profiles, we can find the more intensive of CO₂ desorption peaks, the higher it is for the oxidation of CO and ethanol. Conversion versus yield plot shows the acetaldehyde is the primary product, the secondary products are acetic acid, ethyl acetate and ethylene, and the final product is CO₂. A simplified reaction scheme (not surface mechanism) is suggested that ethanol is first oxidized to form intermediate of acetaldehyde, then acetic acid, ethyl acetate and ethylene formed going with the formation of acetaldehyde, acetic acid, ethyl acetate; finally these byproducts are further oxidized to produce CO₂. PdO/Ce_0.75Zr_0.25O₂ catalyst has much higher catalytic activity not only for the oxidation of ethanol but also for CO oxidation. Thus the CO poison effect on PdO/Ce_0.75Zr_0.25O₂ catalysts can be decreased and they have the feasibility for application in direct alcohol fuel cell (DAFC) with high efficiency.     

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.     

IR and TPD study of fresh and carbon-deposited Co/Al2O3 catalysts

Surface properties of the Co/Al₂O₃ catalyst have been studied under fresh reduction and carbon-deposition conditions using Infrared Spectroscopy(IR) and Temperature-Programmed Desorption(TPD). The Co/Al₂O₃ catalyst is difficult to reduce completely showing evidence of partial reduction even after H₂ reduction at 525(C for 21 hours. The catalyst surface is also relatively complex ana it shows many bands in the TPD chromatogram of surface-adsorbed CO. When carbon is deposited on the catalyst by CO disproportionation at 250(C, the catalyst surface is markedly modified showing a new IR band of adsorbed CO at 2073 cm^-1. The surface carbon is chemically active enough to combine with oxygen from the catalyst to produce gaseous CO at temperatures above 300(C.     

An active iron catalyst containing sulfur for Fischer-Tropsch synthesis

A precipitated iron catalyst containing sulfur for Fischer-Tropsch (F-T) synthesis was prepared by means of a novel method using a ferrous sulfate as precursor. Both fixed bed reactor (FBR) and continues stirred tank slurry reactor (STSR) were used to test long-term F-T reaction behaviors over the catalyst. A stability test (1600 h) in FBR showed that the catalyst was active even after 1500 h of time-on-stream with CO conversion of 78% and with C₅⁺ hydrocarbon selectivity of 72 wt% at 250 °C, 2.0 MPa, 2.0 NL/g-cat/h, and H₂/CO=2.0. The test (550 h) in STSR indicated that the catalyst exhibited relatively high activity with CO conversion of 70-76% and C₅⁺ selectivity of 83-86 wt% in hydrocarbon products under the conditions of 260 °C, 2.0 MPa, 2.0 NL/g-cat/h, and H₂/CO=0.67. The deactivation rate of the catalyst was low, accompanied by surprisingly low methane selectivity of 2.0-2.9 wt%. It is shown that a small amount of sulfur (existing as SO₄²⁻) may promote the catalyst by increasing activity and improving the heavier hydrocarbon selectivity. It is also comparable with other typical iron catalysts for F-T synthesis.     

Fischer�CTropsch Synthesis: Influence of CO Conversion on Selectivities, H2/CO Usage Ratios, and Catalyst Stability for a Ru Promoted Co/Al2O3 Catalyst Using a Slurry Phase Reactor

The effect of CO conversion on hydrocarbon selectivities (i.e., CH₄, C₅₊, olefin and paraffin), H₂/CO usage ratios, CO₂ selectivity, and catalyst stability over a wide range of CO conversion (12?C94%) on 0.27%Ru?C25%Co/Al₂O₃ catalyst was studied under the conditions of 220 °C, 1.5 MPa, H₂/CO feed ratio of 2.1 and gas space velocities of 0.3?C15 NL/g-cat/h in a 1-L continuously stirred tank reactor (CSTR). Catalyst samples were withdrawn from the CSTR at different CO conversion levels, and Co phases (Co, CoO) in the slurry samples were characterized by XANES, and in the case of the fresh catalysts, EXAFS as well. Ru was responsible for increasing the extent of Co reduction, thus boosting the active site density. At 1%Ru loading, EXAFS indicates that coordination of Ru at the atomic level was virtually solely with Co. It was found that the selectivities to CH₄, C₅₊, and CO₂ on the Co catalyst are functions of CO conversion. At high CO conversions, i.e. above 80%, CH₄ selectivity experienced a change in the trend, and began to increase, and CO₂ selectivity experienced a rapid increase. H₂/CO usage ratio and olefin content were found to decrease with increasing CO conversion in the range of 12?C94%. The observed results are consistent with water reoxidation of Co during FTS at high conversion. XANES spectroscopy of used catalyst samples displayed spectra consistent with the presence of more CoO at higher CO conversion levels.     

A Review of Molybdenum Catalysts for Synthesis Gas Conversion to Alcohols: Catalysts,Mechanisms and Kinetics

Recent literature on synthesis gas conversion to higher alcohols over Mo-based catalysts is reviewed. Density functional theory calculations show that Mo-CO adsorption is weakened by C, P, or S ligands and this facilitates CO dissociation, either directly on Mo₂C, or by H-assisted dissociation on MoS₂, Mo₂C, and MoP. Consequently, Mo-based catalysts have high hydrocarbon selectivity unless they are promoted with alkali metals and/or Group VIII metals. Promoted MoS₂ and MoP have alcohol selectivities of ～80 C atom % (CO₂-free basis) at typical operating conditions (5–8 MPa, H₂/CO = 2–1, 537–603 K), whereas on promoted Mo₂C, alcohol selectivities are ～60%. The kinetics of the synthesis gas conversion reactions over Mo-based catalysts have mostly been described by empirical power law models and the alcohol and hydrocarbon product distributions are consistent with a CO insertion mechanism for chain growth.     

Olefin hydroformylation and selective hydrogenation of acetaldehyde on Mo-promoted Rh/SiO2 catalysts derived from metal salt and heteronuclear cluster precursors

Molybdenum promoted Rh/SiO₂ catalysts have been prepared by using the heteronuclear cluster (C₅H₅)₃RhMo₂(CO)₅ as well as metal salt precursors. The promoting effect of molybdenum has been studied for the hydroformylation of ethene and propene and the hydrogenation of acetaldehyde. It has been found that molybdenum, especially on the cluster-derived catalyst, increases both the hydrogenation and the hydroformylation rate of the olefins. No specific influence on the CO insertion reaction could be obtained. As an explanation, the promotion of the initial step to form intermediate surface alkyl groups has been proposed as the rate determining step for ethene hydroformylation. The promotion of the alcohol formation by bimetallic centers having Rh and Mo in close vicinity has been supported by the results of the hydrogenation of acetaldehyde.     

Synthesis of alcohols from CO and H2 on a Fe/A1203 catalyst at 8-30 bars pressure

We have investigated the effect of the temperature and pressure on the activity and selectivity in the production of alcohols and hydrocarbons from CO/H₂ on supported iron catalysts. The tests were performed in a differential microreactor in the 8-30 bars range and between 200 and 275°. The results show that pressure increases the rate of production of hydrocarbons and alcohols. At low temperatures (200-225°), a high methanol selectivity is observed, up to 40%. Homologous linear alcohols are also obtained and their yield is increased upon raising the reaction temperature. However the alcohol-selectivity diminishes on account of a higher conversion into hydrocarbons. The influence of temperature upon the relative hydrocarbon and alcohol formation as well as the Schulz-Flory distributions suggest that a comlmon precursor exists between hydrocarbons and higher alcohols (C₃-C₁₁). Furthermore, the enhancement of the production of n pentanol-1 by adding n-butene-1 to the H₂/CO mixture indicates that CO insertion in a metal-alkyl like bond must occur during the synthesis, and probably constitutes the reaction pathway to alcohols. That supposes the existence of a molecularly adsorbed CO which supposedly is stable at the prevailing pressures. The presence of adsorbed CO also explains the observed methanol selectivity.