Search Results (46)

This work focuses on the fabrication, characterization, and performance of a structured iron catalyst to produce hydrocarbons by the Fischer–Tropsch synthesis (FTS). The structured catalyst enhances the heat and mass transfer and provides a larger surface area and lower pressure drop. Iron-based structured catalysts indicate more activity in lower H₂/CO ratios and improve carbon conversion as compared to other metals. These catalysts were manufactured using the sponge replication method (powder metallurgy). The performance of the structured iron catalyst was assessed in a fixed-bed reactor under industrially relevant conditions (250 °C and 20 bar). The feed gas was a synthetic syngas with a H₂/CO ratio of 1.2, simulating a bio-syngas derived from lignocellulosic biomass gasification. Notably, the best result was reached under these conditions, obtaining a CO conversion of 84.8% and a CH₄ selectivity of 10.4%, where the catalyst exhibited a superior catalytic activity and selectivity toward desired hydrocarbon products, including light olefins and long-chain paraffins. The resulting structured catalyst reached a one-pass CO conversion of 84.8% with a 10.4% selectivity to CH₄ compared to a traditionally produced catalyst, for which the conversion was 18% and the selectivity was 19%, respectively. The results indicate that the developed structured iron catalyst holds considerable potential for efficient and sustainable hydrocarbon production, mainly C10–C20 (diesel-range hydrocarbons), via Fischer–Tropsch synthesis. The catalyst’s excellent performance and improved stability and selectivity offer promising prospects for its application in commercial-scale hydrocarbon synthesis processes. Full article

The biomass-to-liquid process is a promising alternative for sustainably meeting the growing demand for liquid fuels. This study focuses on the fabrication, characterization, and performance of a structured iron catalyst for producing hydrocarbons through Fischer–Tropsch synthesis (FTS). The catalyst was designed to address some drawbacks of conventional supported catalysts, such as low utilization, poor activity, and instability. The experimental investigation involved the manufacturing and characterization of both promoted and unpromoted iron-based catalysts. The performance of the structured iron catalyst was assessed in a fixed-bed reactor under relevant industrial conditions. Notably, the best results were achieved with a syngas ratio typical of the gasification of lignocellulosic biomass, where the catalyst exhibited superior catalytic activity and selectivity toward desired hydrocarbon products, including light olefins and long-chain paraffins. The resulting structured catalyst achieved up to 95% CO conversion in a single pass with 5% selectivity for CH₄. The results indicate that the developed structured iron catalyst has considerable potential for efficient and sustainable hydrocarbon production via the Fischer–Tropsch synthesis. The catalyst’s performance, enhanced stability, and selectivity present promising opportunities for its application in large-scale hydrocarbon synthesis processes. Full article

Unlike on Fe and Co catalysts, the CO conversion effect on Ru catalyst performance is little reported. This study is undertaken to explore the issue using a series of Ru/NaY catalysts under 200–230 °C, 2.0 MPa, H₂/CO = 2, and 10–60% CO conversion in a 1 L continuous stirred tank reactor (CSTR). The results are comparatively studied with those of Fe and Co catalysts reported previously. The NaY support and four 1.0%, 2.5%, 5.0%, and 7.5% Ru/NaY catalysts were characterized by BET, H₂ chemisorption, H₂O-TPD, XRD, HRTEM, and XANES/EXAFS techniques. The BET and XRD results suggest a high surface area (730 m²/g), high degree of crystallinity of the NaY support, and high dispersion of Ru, while an hcp Ru structure and well-reduced Ru were reflected in the HR-TEM FFT and XANES/EXAFS results. The reaction results indicate that the CO conversion effect on CH₄ and C₅₊ selectivities on the Ru is the same as that on the Fe and Co catalysts, with CH₄ selectivity decreasing and C₅₊ selectivity increasing with increasing CO conversion. However, the CO conversion effect on olefin formation for the Ru catalyst was found to be opposite to that of the Fe and Co; increasing CO conversion enhanced olefin formation but suppressed secondary reactions of 1-olefins. The H₂O cofeeding experiments showed that H₂O impacted olefin formation by suppressing hydrogen adsorption and hydrogenation. The H₂O-TPD experiment evidenced a much stronger H₂O adsorption capacity (6.8 mmol/g-cat) on Ru followed by Co (1 mmol/g-cat), and then Fe (0.2 mmol/g-cat)., which showed only a very low H₂O adsorption capacity.This finding may explain the opposite CO conversion effect on olefin formation observed on the Ru catalyst, and may also explain why low CH₄ selectivity (i.e., 3%) occurred on the Ru catalyst and high CH₄ selectivity (i.e., 6–8%) occurred on the Co catalyst, both of which possess low water gas shift (WGS) activity. Full article

The conversion of carbon dioxide into fuels and fine chemicals is a highly desirable route for mitigating flue gas emissions. However, achieving selectivity toward olefins remains challenging and typically requires high temperatures and pressures. Herein, we address this challenge using 12 nm copper nanoparticles supported on FeOx micro-rods, which promote the selective hydrogenation of CO₂ to light olefins (C₂–C₄) under atmospheric pressure. This catalyst achieves up to 27% conversion and 52% selectivity toward C₂–C₄ olefins, along with the production of C₂–C₄ paraffins, C₅+ hydrocarbons (with all C₁₊ products totalling to up to about 75%), and methane, while suppressing CO formation to just 1% at 340 °C. The enhanced performance of the Cu/FeOx pre-catalyst is attributed to the efficient in situ generation of iron carbides (Fe₅C₂) in the presence of copper nanoparticles, as confirmed by ex situ XRD analysis. Copper facilitates the reduction of FeOx to form Fe₅C₂, a crucial intermediate for shifting the reaction equilibrium toward higher hydrocarbons. The hydrogenation of CO₂ to higher hydrocarbons proceeds through the reverse water–gas shift reaction coupled with Fischer–Tropsch synthesis. Full article

This study investigates the hydroformylation of C₅₊ olefins derived from Fischer–Tropsch synthesis (FTS) using Rh-based catalysts supported on zeolites (MFI, MEL) and SiO₂. A series of catalysts were synthesized through two different methods: a one-pot hydrothermal crystallization process, which results in highly dispersed Rh species encapsulated within the zeolite framework (Rh@MFI, Rh@MEL), and an impregnation method that produces larger Rh nanoparticles exposed on the support surface (Rh/MFI, Rh/MEL, Rh/SiO₂). Characterization techniques such as BET, TEM, and FTIR were employed to evaluate different catalysts, revealing significant differences in the dispersion and accessibility of Rh species. Owing to its more accessible mesoporous structure, Rh/SiO₂ with a pore size of 5.6 nm exhibited the highest olefin conversion rate (>90%) and 40% selectivity to C₆₊ aldehydes. In contrast, zeolite-encapsulated catalysts exhibited higher selectivity for C₆₊ aldehydes (~50%) due to better confinement and linear aldehyde formation. This study also examined the influence of FTS byproducts, including paraffins and short-chain olefins, on the hydroformylation reaction. Results showed that long-chain paraffins had a negligible effect on olefin conversion, while the presence of short-chain olefins, such as propene, reduced both olefin conversion and aldehyde selectivity due to competitive adsorption. This work highlights the critical role of catalyst design, olefin diffusion, and feedstock composition in optimizing hydroformylation performance, offering insights for improving the efficiency of syngas-to-olefins and aldehydes processes. Full article

Fischer–Tropsch synthesis (FTS) in a 3D-printed stainless steel (SS) microchannel microreactor was investigated using Fe@SiO₂ catalysts. The catalysts were prepared by two different techniques: one pot (OP) and autoclave (AC). The mesoporous structure of the two catalysts, Fe@SiO₂ (OP) and Fe@SiO₂ (AC), ensured a large contact area between the reactants and the catalyst. They were characterized by N₂ physisorption, H₂ temperature-programmed reduction (H₂-TPR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron microscopy (XPS), and thermogravimetric analysis–differential scanning calorimetry (TGA-DSC) techniques. The AC catalyst had a clear core–shell structure and showed a much greater surface area than that prepared by the OP method. The activities of the catalysts in terms of FTS were studied in the 200–350 °C temperature range at 20-bar pressure with a H₂/CO molar ratio of 2:1. The Fe@SiO₂ (AC) catalyst showed higher selectivity and higher CO conversion to olefins than Fe@SiO₂ (OP). Stability studies of both catalysts were carried out for 30 h at 320 °C at 20 bar with a feed gas molar ratio of 2:1. The Fe@SiO₂ (AC) catalyst showed higher stability and yielded consistent CO conversion compared to the Fe@SiO₂ (OP) catalyst. Full article

Among the alkali metals, potassium is known to significantly shift selectivity toward value-added, heavier alkanes and olefins in iron-based Fischer–Tropsch synthesis catalysts. The aim of the present contribution is to shed light on the mechanism of action of alkaline promoters through a systematic study of the structure–reactivity relationships of a series of Fe oxide FTS catalysts promoted with Group I (Li, Na, K, Cs) alkali elements. Reactivity data are compared to structural data based on in situ, synchrotron-based XRD and XPS, as well as temperature-programmed studies (TPR-H₂, TPC-CO, TPD-CO₂, and TPD-H). It has been observed that the alkali elements induced higher carburization rates, higher basicities, and lower adsorbed hydrogen coverages. Catalyst stability followed the trend Na-Fe > unpromoted > Li-Fe > K-Fe > Cs-Fe, being consistent with the ability of the alkali (Na) to prevent active site loss by catalyst reoxidation. Potassium was the most active in promoting high α hydrocarbon formation. It is active enough to promote CO dissociative adsorption (and the formation of FeCx active phases) and decrease the surface coverage of H-adsorbed species, but it is not so active as to cause premature catalyst deactivation by the formation of a carbon layer resulting in the blocking active sites. Full article

Coal-to-liquid technology is a key technology to ensuring national energy security, with the Fischer–Tropsch synthesis process at its core. However, in actual production, Fischer–Tropsch wax residue exhibits the characteristics of spontaneous combustion due to heat accumulation, posing a fire hazard when exposed to air for extended periods. This significantly threatens the safe production operations of coal-to-liquid chemical enterprises. This study primarily focuses on the experimental investigation of the oxidative spontaneous combustion process of three typical types of wax residues produced during Fischer–Tropsch synthesis. Differential Scanning Calorimetry (DSC) was used to test the thermal flow curves of the three wax residue samples. Kinetic analysis was performed using the Kissinger–Akahira–Sunose (KAS) and Flynn–Wall–Ozawa (FWO) methods to calculate their apparent activation energy. This study analyzed the thermal behavior characteristics, exothermic properties, and kinetic parameters of three typical wax residue samples, exploring the ease of reaction between wax residues and oxygen and their tendency for spontaneous combustion. The results indicate that Wax Residue 1 is rich in low-carbon chain alkanes and olefins, Wax Residue 2 contains relatively fewer low-carbon chain alkanes and olefins, while Wax Residue 3 primarily consists of high-carbon chain alkanes and olefins. This leads to different thermal behavior characteristics among the three typical wax residue samples, with Wax Residue 1 having the lowest heat release and average apparent activation energy and Wax Residue 3 having the highest heat release and average apparent activation energy. These findings suggest that Wax Residue 1 has a higher tendency for spontaneous combustion. This research provides a scientific basis for the safety management of the coal chemical industry, and further exploration into the storage and handling methods of wax residues could reduce fire risks in the future. Full article

Commercial silica support pellets were impregnated and calcined to contain cobalt oxide and ruthenium oxide for Fischer-Tropsch synthesis (FTS). The precatalyst pellets were split evenly into two groups, the control precatalyst (c-precat) and silylated precatalyst (s-precat), which were treated with 1H,1H, 2H, 2H-perfluorooctyltriethoxysilane (PFOS) in toluene. The samples of powderized s-precat were superhydrophobic, as determined by the water droplet contact angle (>150°) and sliding angle (<1°). Thermal analysis revealed the PFOS groups to be thermally stable up to 400 °C and temperature programmed reduction (TPR) studies showed that H₂ reduction of the cobalt oxide to cobalt was enhanced at lower temperatures relative to the untreated c-precat. The two active catalysts were examined for their FTS performance in a tubular fixed-bed reactor after in situ reduction at 400 °C for 16 h in flowing H₂ to give the active catalysts c-cat and s-cat. The FTS runs were performed under identical conditions (255 °C, 2.1 MPa, H₂/CO = 2.0, gas hourly space velocity (GHSV) 510 h^–1) for 5 days. Each catalyst was examined in three runs (n = 3) and the mean values with error data are reported. S-cat showed a higher selectivity for C₅₊ products (64 vs. 54%) and lower selectivity for CH₄ (11 vs. 17%), CO₂ (2 % vs. 4 %), and olefins (8% vs. 15%) than c-cat. S-cat also showed higher CO conversion, at 37% compared to 26%, leading to a 64% increase in the C₅₊ productivity measured as g C₅₊ products per g catalyst per hour. An analysis of the temperature differential between the catalyst bed and external furnace temperature showed that s-cat was substantially more active (DT_initial = 29 °C) and stable over the 5-day run (DT_final = 22 °C), whereas the attenuated activity of c-cat (DT_initial = 16 °C) decayed steadily over 3 days until it was barely active (DT_final < 5 °C). A post-run surface analysis of s-cat revealed no change in the water contact angle or sliding angle, indicating that the FTS operation did not degrade the PFOS surface treatment. Full article

Cobalt carbides have been recognized as an active phase for the production of light olefins and alcohols in Fischer–Tropsch synthesis. In this study, in situ X-ray diffraction experiments were performed to investigate the stability and catalytic performance over a single-phase Co₃C catalyst under reaction conditions. The in situ X-ray diffraction results indicated that the Co₃C phase remained stable with no significant changes until the temperature reached 300 °C. The high stability can be attributed to the twinning structure of the single-phase Co₃C catalyst. The catalytic evaluation results showed that the single-phase Co₃C catalyst had higher activity with high selectivity to long-chain products due to the unique surface structure of Co₃C. This work provides guidance for the rational design of efficient cobalt carbide catalysts for Fischer–Tropsch synthesis reactions. Full article

The extensive release of carbon dioxide (CO₂) into the atmosphere is associated with the detrimental impacts of the global environmental crisis. Consequently, the valorization of CO₂ from industrial processes holds great significance. Transforming CO₂ into high added-value products (e.g., CH₄, C₁-C₃ deoxygenated products) has attracted considerable attention. This is feasible through the reverse water–gas shift (RWGS) and Fischer–Tropsch synthesis (FTS) reactions; CO is initially formed and then hydrogenated, resulting in the production of hydrocarbons. Iron-based materials have a remarkable ability to catalyze both RWGS and FTS reactions, enhancing the olefinic nature of the resulting products. Within this context, iron-based nanoparticles, unsupported and supported on zeolite, were synthesized and physico-chemically evaluated, applying multiple techniques (e.g., BET, XRD, FT-IR, Raman, SEM/TEM, DLS, NH₃-TPD, CO₂-TPD). Preliminary experiments show the potential for the production of C₂₊ deoxygenated products. Among the tested samples, supported Fe₃O₄ and Na-Fe₃O₄ (A) nanoparticles on HZSM-5 are the most promising for promoting CO₂ valorization into products with more than two carbon atoms. Results demonstrate that product distribution is highly affected by the presence of acid sites, as low-medium acid sites and medium acidity values enable the formation of C₂₊ hydrocarbons. Full article

Syngas conversion is a useful technology for converting nonpetroleum carbon resources into chemicals such as olefins. Iron- and cobalt-based catalysts, as two major categories, have been extensively studied in Fischer–Tropsch synthesis to olefins (FTO) reactions. Although both iron and cobalt catalysts have shown distinct merits and shortcomings, they are also complementary in their properties and catalytic performances when combined with each other. Herein, Na-modified CoFe bimetallic catalysts were fabricated using a co-precipitation method. It was found that there was a synergistic effect between Co and Fe that promoted a CO dissociation rate and carburization, and an appropriate Co/Fe ratio was conducive to improvements in their catalytic performances. The desired olefins selectivity reached 66.1 C% at a CO conversion of 37.5% for a Co2Fe1 catalyst, while the methane selectivity was only 4.3 C%. In addition, no obvious deactivation was found after nearly 160 h, indicating their potential industrial application. Full article

In recent years, the non-petroleum production of light olefins has been the research focus of Fischer–Tropsch olefin synthesis (FTO). Iron-based catalysts have attracted much attention because of their low price, high catalytic activity, and wide temperature range. In this paper, traditional modification, hydrophobic modification, and amphiphobic modification of the catalyst are summarized and analyzed. It was found that traditional modification (changing the pore size and surface pH of the catalyst) will reduce the dispersion of Fe, change the active center of the catalyst, and improve the selectivity of light olefins (for example, SiO₂: 32%). However, compared with functional methods, these traditional methods lead to poor stability and high carbon dioxide selectivity (for example, SiO₂: 34%). Hydrophobic modification can inhibit the adsorption and retention of water molecules on the catalyst and reduce the local water pressure near the iron species in the nuclear layer, thus inhibiting the further formation of CO₂ (for example, SiO₂: 5%) of the WGSR. Amphiphobic modification can not only inhibit the WGSR, but also reduce the steric hindrance of the catalyst, increase the diffusion rate of olefins, and inhibit the reabsorption of olefins. Follow-up research should focus on these issues. Full article

The effect of the different supports and catalyst-reducing agents on the Fischer–Tropsch (FT) reaction was investigated. The large surface area SiO₂ support with a smaller pore volume deposited fine, evenly distributed Co₃O₄. Cubic-shaped Co₃O₄ appeared in clusters on the TiO₂ support, whereas Co₃O₄ existed as single large particles on the Al₂O₃ support. The activity data obtained were discussed in terms of cluster size, particle size, particle shape, and mass transport limitations. The SiO₂-supported catalysts showed a higher activity for the formation of paraffinic products when reduced in H₂ at 250 °C. This is attributed to the formation of the CoO-Co active bond, which enhanced the activation of CO and the hydrogenation reactions. A higher activity was observed for the TiO₂-supported catalyst at a higher reduction temperature (350 °C) when the mass of Co metal was higher. It afforded more paraffinic products due to enhanced secondary hydrogenation of olefins at higher reaction rates. The large Co₃O₄ supported on Al₂O₃ showed the least activity at both reduction temperatures due to strong metal-support interactions. The H₂-reduced catalysts exhibited superior activity compared to all the syngas-reduced catalysts. Syngas reduction led to surface carbon deposition and the formation of surface carbides which suppressed the hydrogenation reactions and are selective to olefinic products. Full article

The direct CO₂ Fischer–Tropsch synthesis (CO₂-FTS) process has been proven as one of the indispensable and effective routes in CO₂ utilization and transformation. Herein, we present a core-shell structured Na/Fe@Co bimetallic catalyst to boost CO₂ conversion and light hydrocarbon (C₂ to C₄) selectivity, as well as inhibit the selectivity of CO. Compared to the Na/Fe catalyst, our Na/Fe@CoCo-3 catalyst enabled 50.3% CO₂ conversion, 40.1% selectivity of light hydrocarbons (C₂-C₄) in all hydrocarbon products and a high olefin-to-paraffin ratio (O/P) of 7.5 at 330 °C and 3.0 MPa. Through the characterization analyses, the introduction of CoCo Prussian Blue Analog (CoCo PBA) not only increased the reducibility of iron oxide (Fe₂O₃ to Fe₃O₄), accelerated the formation of iron carbide (Fe_xC_y), but also adjusted the surface basic properties of catalysts. Moreover, the trace Co atoms acted as a second active center in the CO₂-FTS process for heightening light hydrocarbon synthesis from CO hydrogenation. This work provides a novel core-shell structured bimetallistic catalyst system for light hydrocarbons, especially light olefin production from CO₂ hydrogenation. Full article