Coke Formation Research Articles

Efficient propane dehydrogenation catalyzed by Ru nanoparticles anchored on a porous nitrogen-doped carbon matrix

Propane dehydrogenation (PDH) is a vital industrial process for producing propene, utilizing primarily Cr-based or Pt-based catalysts. These catalysts often suffer from challenges such as the toxicity of Cr, the high costs of noble metals like Pt, and deactivation issues due to sintering or coke formation at elevated temperatures. We introduce an exceptional Ru-based catalyst, Ru nanoparticles anchored on a nitrogen-doped carbon matrix (Ru@NC), which achieves a propane conversion rate of 32.2% and a propene selectivity of 93.1% at 550 °C, with minimal coke deposition and a low deactivation rate of 0.0065 h−1. Characterizations using techniques like TEM and XPS, along with carefully-designed controlled experiments, reveal that the notable performance of Ru@NC stems from the modified electronic state of Ru by nitrogen dopant and the microporous nature of the matrix, positioning it as a top contender among state-of-the-art PDH catalysts.

Steam Reforming of Tar Impurities from Biomass Gasification with Ni-Co/Mg(Al)O Catalysts—Operating Parameter Effects

The elimination of tar impurities from biomass gasification by catalytic steam reforming can provide clean syngas for downstream biofuel synthesis (Fischer–Tropsch). The effects of key operating parameters in CH4/tar steam reforming were investigated. Ni-Co/Mg(Al)O catalyst performance was tested at model conditions (10/35/25/25/5 wt% CH4/H2/CO/CO2/N2), changing the temperature (650–800 °C), steam-to-carbon ratio (2–5), tar loading (10–30 g/Nm3), and tar composition (toluene, 1-methylenaphthalene, and phenol). Complete tar elimination was achieved under all conditions, at the expense of catalyst deactivation by coke formation. Post-operation coke characterization was obtained with TPO-MS, Raman spectroscopy, and STEM analysis, providing vital insight into coke morphology and location. Critical low-temperature and high-tar loading limits were identified, where rapid deactivation was accompanied by increasing amounts of hard coke species. A coke classification scheme is proposed, including strongly adsorbed surface carbon species (soft coke A), initial scattered carbon filaments (hard coke B1.1), filament clusters and fused filaments (B2), and strongly deactivating bulk encapsulating coke (B3), formed through progressive filament cluster graphitization. High-molecular-weight tar was found to enhance the formation of strongly deactivating metal-particle-encapsulating coke (B1.2). The results contribute to the understanding of coke formation in the presence of biomass gasification tar impurities.

Preparation of presulfided oil-soluble NiMo catalyst for slurry bed hydrocracking of vacuum residue

Here, a method is proposed for constructing presulfided oil-soluble NiMo catalysts using tetrathiomolybdate nickel ammonium as a precursor via a chelating ligand exchange strategy. Leveraging the close chemical bonding between Ni and Mo atoms, the NiMo catalyst can undergo in-situ self-sulfidation to generate active NiMoS sites and a composite structure of Ni3S2 and MoS2 nano phase in tight contact, thus exhibiting strong synergistic effects. The NiMo catalyst exhibited outstanding performance in hydrocracking of vacuum residue (VR) achieving a 64.7 wt% VR conversion while maintaining a coke yield of 0.51 wt%, as well as the excellent hydrogenation activity of polycyclic aromatic hydrocarbons. Combined with density functional theory calculations, it was further revealed that the presence of Ni reduces the energy barrier for H2 dissociation on MoS2, thereby enhancing the hydrogenation activity of the catalyst and its ability to suppress coke formation. This work validates the efficient bimetallic synergistic catalytic effect of presulfided oil-soluble NiMo catalysts in the slurry bed hydrocracking process.

Decoupling Aromatic Yield and Coke Formation in Methanol‐to‐Aromatic Reaction on Zn(II) Exchanged H‐ZSM‐5 Zeolite

AbstractMethanol to aromatic reaction is an alternative pathway to produce aromatics from non‐petroleum resources. Zn‐modified ZSM‐5 zeolite is the widespread catalyst for MTA due to its high activity and selectivity to aromatics. However, a desired high yield of aromatics is usually accompanied with undesired coke formation and fast deactivation of catalyst, because aromatic molecules also serve as the precursor for coke formation. To decouple the aromatic yield and coke formation rate, in this work we use Zn‐ZSM‐5 to investigate coke formation and catalyst deactivation. The coke distribution along the catalyst bed was analyzed and its correlation with the concentration gradient of methanol, olefins and aromatics along the bed was deciphered. Coke was found to form very fast at catalyst bed in the copresence of methanol and aromatics. On the contrary, much less coke was observed at the later layers of the catalyst bed where methanol had been fully converted and aromatics were present in the highest concentration. Based on this finding, we adjusted the reaction conditions to successfully improve the yield of aromatics without reducing catalyst lifetime in compromise, by applying a higher methanol partial pressure that enables a faster consumption of methanol and reduces the period of copresence of methanol and aromatics.

Fine-tuning Pt nanoparticle and coordination for enhanced catalytic efficiency in microwave-assisted methylcyclohexane dehydrogenation over Pt/Al2O3 catalysts

The advancement of microwave-assisted catalysis technology will play a crucial role in the realms of energy conversion and catalysis. In this study, we developed a series of Pt/Al2O3-H catalysts by varying the reduction temperature and duration to control the Pt particle size, aiming to optimize the catalytic performance for microwave-assisted methylcyclohexane (MCH) dehydrogenation. Among the synthesized catalysts, Pt/Al2O3-H-400–15 emerged as the most effective, characterized by Pt particles of 1.5 nm and a Pt-Pt coordination number of 2.8. This particular catalyst demonstrated a high metal-support interaction, which significantly enhanced its activity and stability during the dehydrogenation process. Notably, it showed superior performance in MCH dehydrogenation under microwave irradiation, maintaining high stability and minimal methane formation over 626 h. The enhanced catalytic behavior under microwave irradiation is attributed to the elimination of low-temperature dead zones, which are commonly observed in traditional thermal catalysis, resulting in higher efficiency, greater activity, and reduced by-product and coke formation. This study underscores the potential of microwave-assisted catalysis as a more effective alternative to conventional thermal methods for the dehydrogenation of MCH.

Single feed droplet–catalyst particle collision in a liquid containing gas–solid fluidized bed to convert fructose to value-added chemicals

Carbohydrates, comprising C6 sugars, dehydrate to form furfural (FUR) and 5- hydroxymethyl furfural (HMF). HMF is an intermediate for value-added specialty chemicals like 2,5-diformyl furan (DFF) and 2,5-furandi carboxylic acid, a monomer for polyethylene furaonate. Atomizing sugar solutions into catalytic fluidized beds operating beyond the caramelization temperature, Tcarm, accelerates reaction rates while avoiding humins, which are color forming agents characteristic of liquid phase processes. However, droplets partially coat particles in the spray zone and agglomerate due to liquid cohesive forces, which reduces heat transfer rates at the micro-scale and degrades reaction rates at the macro-scale. Here, we developed a CFD model to study the collision between a single feed droplet and a catalytic particle above Tcarm. We focused on evaluating the evaporation rate and heat transfer between the droplet and particle to promote vaporization the liquid feed, and assessing the impact of bed temperature, liquid feed rate, and superficial gas velocity. The highest DFF and furfural selectivity obtained are 17% and 24%, respectively, and these values are correlated to the maximum coke formation and agglomeration of 0.6% and 12g. However, the corresponding heat transfer and mass transfer are among the lowest values of 40% and 0.5W.

Impact of various metal promoters on the propane dehydrogenation performance of cobalt-based catalysts

Large-scale exploitation of natural gas and shale gas has spurred the development of the propane dehydrogenation technology. While cobalt-based catalysts, known for their low cost and low toxicity, effectively activate C–H bonds, they are often deactivated because of coke formation. In this study, we prepared SBA-15 molecular sieves using a hydrothermal synthesis method and developed a series of Co-based catalysts supported on SBA-15 with various metal promoters (denoted Co-X/SBA-15, where X = Mn, Fe, Mg, Zn, or La) via an incipient wetness impregnation method. Characterization techniques and activity evaluation results revealed that the Co–O–Mg structure in the Co-Mg/SBA-15 catalyst stabilizes the primary Co2+ active site and hinders the reduction of the CoOx species. The incorporation of Mg enhances the total alkalinity of the catalyst, facilitating propane adsorption and propylene desorption, leading to superior activity and stability. Although the addition of La improved propylene selectivity, it did not significantly enhance propane conversion. Conversely, the introduction of Mn, Fe, and Zn into the catalyst inhibited the reaction.

Insights into the Phases Transformation of Copper and Nickel Catalysts during Partial Oxidation and Steam Reforming of Methane

AbstractThe paper shows the structural changes of copper and nickel catalysts in the presence of strong (O2) and weak (H2O) oxidizing agents and their influence on the course of methane conversion. The changes in oxidation states of investigated catalysts were studied during partial oxidation and steam reforming of methane using an X‐ray reactor chamber (XRD) coupled with an online mass spectrometer. Also, the susceptibility of these catalysts to oxidation and reduction by individual reaction components was investigated using TPR, TPO, and in situ XPS techniques. The obtained results indicated the distinct catalytic behavior of copper and nickel catalysts depending on their oxidation state and the importance of coke formation in the activation of the partial oxidation process. The mechanism of re‐reduction of catalysts under reaction conditions and a method to increase the activity of nickel catalysts are proposed.

Value-added bioproducts by bioethanol dehydrogenation to acetaldehyde through Cu and Zn modified biochar catalysts

ABSTRACT In this study, the efficiency of a series of biochar-supported Cu catalysts, biochar-supported Zn catalysts, and biochar-supported Cu-Zn catalysts was determined through bioethanol dehydrogenation to the high-value chemical, acetaldehyde. Each metal, with weight percentages of 10, 20, and 30, and the combination of Cu-Zn, including 10 wt% of Cu and Zn, 15 wt% of Cu – 5 wt% of Zn, and 15 wt% of Cu and Zn, were fully loaded onto biochar using an incipient wetness impregnation technique. Subsequently, all biocatalysts were subjected to bioethanol dehydrogenation reactions in a temperature range of 200–400 °C. The optimum metal loading for the catalyst was found to be the combination of 15 wt% Cu and 15 wt% Zn. This catalyst resulted in a reasonable acetaldehyde yield of 56.2%, an initial bioethanol conversion of 57.3%, and a very high acetaldehyde selectivity of 98.1% at a mild reaction temperature of 300 °C and ambient pressure. These results were attributed to the optimal concentration of weak-medium acid and medium base sites. Active acid and base sites were identified through temperature-programmed desorption of ammonia (NH3-TPD) and temperature-programmed desorption of carbon dioxide (CO2-TPD), respectively. Furthermore, the reaction stability test of the best biocatalyst (15Cu-15Zn/BB) was proven by maintaining this reaction at the same temperature (300 °C) for 10 h. However, the catalytic performance slightly decreased due to the coke formation of Cu species.

Coke formation and mineral accumulation on HZSM-5/Al2O3 catalysts during in-situ catalytic fast pyrolysis of microalgae over multiple regeneration cycles

Catalyst deactivation caused by coke formation and mineral accumulation occurs simultaneously and intensively during the catalytic pyrolysis of biomass. A comprehensive understanding of their distinction and interactions during the deactivation and regeneration process of shaped catalysts are essential for catalyst advancement and longevity in industrial application. In this study, we report the reversible and non-reversible catalyst deactivation caused by coke formation, mineral accumulation and the interactions thereof by a multi-technique characterization of a HZSM-5/Al2O3 catalyst (crushed extrudates; particle size 1–3 mm) in fast pyrolysis. A total of 5 cycles of catalyst reaction/regeneration were performed in a bench scale reactor (60 g/h feedstock feeding rate; pyrolysis temperature of 500°C) using both raw microalgae (Scenedesmus almeriensis, or SA) and citric acid treated microalgae (CA-SA). The measured properties of the fresh and used catalysts (SA-R5, 5th recycled and reacted catalyst mixed with SA) disclosed the anticorrelation of the metal contents (increased by a factor of 2.5 times) with surface area (-4.4 %) and Brønsted acid (-70.4 %). The presence of minerals in the feedstock might catalytically alter the pyrolysis chemistry, interfere with the shape selectivity and acidity of the catalysts, thus reduced the formation of coke. Additionally, metal species from the microalgae ash that ended up on the catalyst could promote coke combustion during the regeneration process. This work revealed the demineralization of the microalgae prior to fast pyrolysis minimized the rate of irreversible catalyst deactivation. Whereas, the trade-off between promoted coke formation after the ash removal of microalgae and accelerated minerals accumulation without microalgae demineralization should be evaluated.

Dry reforming of model-biogas over ceria-supported nickel catalyst: the effect of charge enhanced dry impregnation on the catalytic performance and coke resistance

In this study, we investigated the effectiveness of charge charge-enhanced dry impregnation (CEDI) method on a ceria-supported nickel-based catalyst (10Ni/CeO2) used to produce synthesis (syngas) under biogas dry reforming conditions. The CEDI method was used to enhance the electrostatic adsorption of nickel precursor onto the ceria support during dry impregnation (DI), hence charge-enhanced dry impregnation. The other ceria-supported nickel-based catalyst (labelled 10Ni/CeO2-DI) was prepared by the commonly used DI method and used as the reference catalyst. The catalysts were then tested for stability and catalytic performance (biogas conversion and syngas yield) under biogas reforming conditions using CatLab-QGA equipment supplied by Hidden Analytical. The characterisation studies: X-ray diffraction (XRD), N2 adsorption/desorption, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), oxygen temperature programmed oxidation (O2-TPO), temperature programmed reduction (TPR), and H2-chemisorption were performed on the fresh and spent catalysts to gain insight into the influence of the CEDI method on dispersion, nanoparticles size of the active phase, metal-support interaction, bulk composition, and phase composition. The results showed that enhancing electrostatic attraction during the DI method produced 10Ni/CeO2-CEDI with smaller nanoparticles (3.33 nm), improved nickel dispersion from 1.40 to 5.04% and improved metal-support interaction inferred from TPR values increased from 290 to 340 °C. These favourable physicochemical properties had a positive correlation with the improvement in the conversion of model biogas feed and the least coke formation.

Facile synthesis of highly basic, nanocrystalline Fe2O3-NiO composites as promising and durable catalysts for selective dehydrogenation of 2-butanol.

Nanocrystalline Fe2O3-NiO composite catalysts were prepared using a sonication-assisted green preparation method. The prepared catalysts were characterized using different techniques, including thermal analyses (TGA/DTA), X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, surface area measurements (SBET), and scanning electron microscopy (SEM). The surface basicity of the prepared catalysts was measured using the temperature-programmed desorption of CO2 (CO2-TPD) as a highly acidic probe molecule. The catalytic activity of all the prepared catalysts was tested at a temperature range of 250-325 °C towards the dehydrogenation of 2-butanol to methyl-ethyl ketone (MEK), which is considered a promising fossil fuel alternative and has several industrial applications. The composite catalysts showed better catalytic activity compared to the pure oxides (i.e., Fe2O3 and NiO) due to the strong synergetic effect between the two oxides. Fe2O3 prevented the coke formation over the surface of NiO by the oxygen-scavenging effect of Fe, which promotes the oxidation of the carbonaceous species and increases the catalyst's resistance to deactivation. The effect of weight hourly space velocity (WHSV) on the catalytic activity was tested over a selected catalyst. In addition, the stability and durability of the catalyst were tested across four successive reaction cycles, demonstrating remarkable performance throughout all the reaction cycles.

Highly dispersed Ni nanoparticles confined in mesoporous SBA-15 for methane dry reforming with improved coke resistance and stability

Methane dry reforming (DRM) is a promising route for sustainable syngas production, in which Ni-based catalysts face challenges of metal sintering and coke formation. In this work, highly dispersed Ni nanoparticles (NPs) embedded in the mesopores of SBA-15 were prepared using a simple solid-state impregnation (SSI) method. TEM and cross-section HRTEM results clearly indicated that ultra-small Ni NPs (3–4 nm) were orderly dispersed within the mesopores of the SBA-15 support. Compared with the conventional wetness impregnation (WI) method, the Ni/SBA-15 catalyst prepared by solid-state impregnation method possessed much better catalytic activity, stability, and coke resistance in DRM. In-situ DRIFTS and semi-in-situ XRD were used to elucidate the dispersion and encapsulation mechanism of Ni within the mesopores of SBA-15 during the sample preparation process. Specifically, WI formed large NiO particles, while SSI formed smaller NiO NPs with stronger interaction between metal and support (SIMS) via forming Ni-O-Si species which is beneficial for the DRM reactivity. This work establishes relationships among catalyst preparation, structure, and DRM performance, paving the way for general template-assisted methods to prepare nanometallic catalysts for various applications.

Coke evolution study in a liquid atomization into gas-solid fluidized bed to convert fructose to value-added chemicals

Glucose and fructose are valuable compounds, which have the potential to displace fossil fuels as a feedstock for highly valued products. One of the promising reactions is the oxi-dehydration of fructose to produce Hydroxymethylfurfural, 2,5-diformylfuran, and furfural. Current processes to produce platform chemicals like Hydroxymethylfurfural, furfural, and 2,5-diformylfuran operate in liquid phase with homogeneous heterogeneous catalyst, but commercialization is limited by scale and environmental impact of the large volume solvent required. Here we developed a gas-phase process to convert fructose in a fluidized bed reactor over Mo − V − WO3/TiO2. However, in the catalytic oxi-dehydration of fructose, coke forms on active sites and decreases conversion but increases selectivity. Coke and reactor performance depends on fructose concentration and O2/fructose ratio. In the first 2 h, acidic amorphous coke accumulates (based on TPO, FTIR, and UV–vis). Feeding excess O2 maintains coke in an amorphous structure and liberates oxide sites. Whereas coke promotes, water block active site reducing yield. In this work, we optimized the operating parameters of fructose concentration (%) and O2/fructose ratio, while simultaneously mitigating the issues associated with coke formation and its detrimental effects.

Spectroscopic Elucidation of Phase Evolution in NiO/YSZ Under Oxidative and Reductive Gas Environments

High temperature co-electrolysis of CO2 and H2O serves a viable, energy efficient, and scalable route to produce syngas (CO+ H2), which can be used to generate a variety of utility hydrocarbons. Solid oxide electrolysis cell (SOEC) has proven to be a promising technology for CO2 utilization and a carbon neutral route to curb CO2 emissions. The design of cathode catalyst is critical as it must facilitate the activation of CO2 and H2O and also exhibit high electronic and oxygen ion conductivity. The state-of-the-art cathode material used in SOECs is Ni/YSZ (8 mol% Yttria Stabilized Zirconia) ceramic composite (known as cermet), whose performance is dependent on various operating factors including temperature, composition of feed gas stream, presence of contaminants like SOx/NOx etc. There is a very limited number of studies on the evolution of the cathode materials under process level conditions. To begin with, effect of different oxidative and reductive gas environments and temperature over Ni/YSZ is studied using in situ Raman spectroscopy.Typical flue gas composition is chosen as the basis for the concentration of different components like 15% CO2, 10% H2O, 5% O2 with argon. Under oxidative conditions (O2, CO2, H2O) with temperature variation range of RT-800 0C, NiO/YSZ vibrational modes revealed that it is composed of NiO and YSZ phases. It is seen that there is thermal broadening in the bands of NiO and YSZ, thermal effects reversible upon cooling down and red shift in the NiO bands exemplified the lattice expansion. Exposing the NiO/YSZ to 5% H2 at high temperature resulted in the formation of metallic Ni, which is corroborated by the absence of the Ni-O vibrational modes in Raman spectrum at 400 0C. YSZ phase is quite stable in H2 at elevated temperature.After reduction of NiO/YSZ to get Ni/YSZ, exposure to oxidative environments (i.e., O2, CO2, H2O) aided in the formation of defect laden NiOx phase on YSZ. Specifically, NiOx formation starts at 350 0C under oxygen and at 450 0C under CO2 and H2O. Under 15% CO2, there is an overlap between the bands associated to the carbonate like species and the NiO phase but there is no formation of coke at these conditions as D and G bands were not observed (Fig. 1). It could be due to the oxidation of Ni that obliterated coke formation. The blue shift at 1046 cm-1 (2P mode of NiO) signifies the shortening of bond length in Ni-O with gradual conversion of Ni to NiOx. Compared to the NiOx phase formed under 5% O2 and 15% CO2 which has a sharp feature in Raman spectra, there is a broad band of NiOx phase formed under 10 % H2O in the region 480-580 cm-1 . This observation demonstrates the variation in the microcrystalline size of the defect laden NiOx phase formed under exposure to different oxidizers.Another set of experiments were done with the dry hydrogen (5 % H2) and humidified hydrogen (5% H2 + 10 % H2O) to study the role of presence of water on the reduction of NiO/YSZ with temperature variation between 120 – 800 0C. It was found that reduction of NiO to Ni is not affected by the presence of water. Under both conditions this transformation occurs between 400-600 0C. The results from the current study provide the key information on the effects of temperature and gas compositions over Ni/YSZ which serves as a guide for the process level design and operation of SOECs. References Juliana Carneiro et al, Industrial & Engineering Chemistry Research 2020 59(36), 15884-15893.John Kirtley et al, The Journal of Physical Chemistry C2013, 117 (49), 25908-25916.A. Naumenko et al, Phys Chem Solid State 2008, 9, 121–125. Figure 1

Presence of oxygen in catalytic pyrolysis of lignin impacts evolution of both coke and aromatic hydrocarbons

Coking is a major issue in catalytic pyrolysis of biomass over zeolite catalysts. Using oxidative gas might mitigate formation of carbonaceous deposits. This was verified herein by catalytic pyrolysis of lignin with different oxygen concentrations (0 %, 3 %, 6 %, 9 % and 12 %) in carrier gas using ZSM-5 as the catalyst at 600 °C. The results indicated that the O2 introduced oxidized both volatiles and biochar, reducing bio-oil yield from 29.2 to 20.7 % and biochar yield from 56.8 to 53.7 % with increasing O2 concentration from 0 to 12 %. Oxidation of intermediates in “hydrocarbon pool” on surface of catalyst decreased the yield of BTX from 11.5 % in inert gas to 6.1–8.0 % and also other aromatics with 1 or 2 benzene rings. The aromatics with rigid polycyclic aromatic structures were more resistant towards oxidation. However, toluene, xylene, and other aromatic hydrocarbons or phenolics with side chains were more prone to be oxidized, abundance of which decreased more significantly at high O2 concentrations. Such results were also observed in catalytic pyrolysis of guaiacol or vanillin. The benefit of using O2 was diminished formation of coke and/or precursors of coke over ZSM-5. Characterization of reaction intermediates in catalytic pyrolysis of lignin with in-situ IR showed that O2 presence remarkably decreased the abundance of aliphatic intermediates containing –OH, -C-H and C=O through oxidation reactions and also interrupted aromatization organics in both coke and biochar.

Synergistic Ni-Ce-SSZ-13 catalysts for enhanced dry reforming of methane

The dry reforming of methane (DRM) serves as a pivotal reaction for hydrogen generation and the simultaneous conversion of methane and carbon dioxide, two major greenhouse gases, into syngas that can further be converted into high-value fuels and chemicals. However, catalyst deactivation imposes a major challenge that prohibits the market penetration of DRM. Here we reported a series of bifunctional Ni-Ce catalysts supported on SSZ-13 (Ni-Ce-SSZ-13) and discovered that a small amount of Ce could significantly enhance the activity, selectivity, and stability for DRM. Optimal ratio of Ni to Ce has been identified to yield peak catalytic performance. The optimal performance is correlated with the maximum Ce3+/Ce4+ ratio as revealed by XPS analysis, which implies an increased presence of oxygen vacancies in the catalysts. It played a crucial role in facilitating the oxidation of activated CH4 species at Ni sites, thereby enhancing DRM activity and diminishing the detrimental coke formation. It is also disclosed that integrating proper amount of Ce fosters its interactions with Ni, effectively preventing the agglomeration of Ni sites. This work presents great implications for the rational design and catalytic synergy of bi-/multi-functional zeolite catalysts for other technological applications.

A comprehensive thermodynamic analysis of hydrogen and synthesis gas production from steam reforming of propionic acid: Effect of O2 addition and CaO as CO2 sorbent

A thermodynamic analysis was performed for the production of synthesis gas and hydrogen gas from steam reforming of propionic acid, one of the constituents of the bio-oil, using ASPEN Plus v8.8. The aim of the study was to perform a global analysis on steam reforming of propionic acid focusing on several parameters such as steam-to-propionic acid ratio, reaction temperature, addition of O2 in the feed stream and presence of CaO as a CO2 sorbent in the reaction environment. The results showed that higher amounts of steam/propionic acid ratio resulted in higher H2 and CO2 yields. It was also observed that high H2O/PA molar ratios led to reduced coke production as WGS reaction was favored with excess steam, causing CO in the reaction mixture to be consumed through the WGS reaction rather than the Boudouard reaction. Addition of O2 in the reaction environment was observed to negatively affect yield of H2. Yet, coke formation was deprived and increasing the O2 amount in the feed stream decreased the energy required for the process. Furthermore, the presence of CaO enhanced H2 yield and energy requirements of the process compared to conventional steam reforming process. 100 % yield of H2 production with a heat generation of −83.4 MJ/kmol of PA and almost zero formation of CO2, CO, CH4 and coke is achieved at 600 °C for sorption enhanced steam reforming of propionic acid.

Deactivation mechanism of NiWS/SAPO-11 catalyst in hydroisomerization of n-hexadecane: Insights into coke deposition behavior and active phase migration

The application of non-noble metal supported catalysts in the hydroisomerization of long-chain n-alkanes is a novel field, and there is currently not any research available on the deactivation process of these catalysts. We investigated into the deactivation mechanism of NiWS/SAPO-11 catalyst in the hydroisomerization of n-hexadecane in this work for the first time. Specifically, coke deposition behavior and active phase migration were investigated. The reduction of catalytic efficiency of the catalyst was partially aided by the decrease in specific surface area, pore volume, and acid density. From the perspective of the active phase, the clusters of NiWS active phase migrated as the reaction time increased, mostly resulting in an increase in both the stacking number and the length of active phase slabs. The migration of active phase increased the distance between active phase clusters and metal sites, and decreased the utilization ratio of active metal atoms. From the perspective of coke deposition, the coke formed on the catalyst includes soft coke and hard coke. The formation and evolution of coke on the catalyst were investigated. The soft coke (aliphatic compounds) progressively transformed into hard coke (polycyclic aromatic hydrocarbons and graphite-like), and the coke gradually migrated from the external surface of the catalyst to the pore channels as the reaction time increased. It is expected to provide theoretical basis and reference value for the deactivation research and design of non-noble metal supported hydroisomerization catalyst.

The impact of surface-impregnated versus support-dispersed Fe in Fe–Ni/γ-Al2O3 catalysts for partial oxidation of methane: Insights into the effect of Fe incorporation method on coking and on the reaction mechanism

Two sets of Fe-modified Ni/γ-Al2O3 catalysts were prepared and tested in partial oxidation of methane. In one set, Fe was co-impregnated on the surface (NiFe) and in the other set Fe was incorporated in the support bulk (Ni/Fe). The two types showed significantly different coking resistance and performance. While Fe well dispersed in the support bulk significantly enhanced coking resistance, Fe co-impregnated with Ni on the surface enhanced the rate of coke deposition on the catalysts’ surfaces. The impact of Fe in the Ni/Fe catalysts is referred to its partially reduced ions (Fe2+) in redox reactions, and to the Ni-support strong interaction retarding the coke formation pathways. On the contrary, carbon formation on the NiFe catalysts is referred to the formation of Ni–Fe alloy particles which may block Ni active sites and can promote cracking of methane as well as CO molecules resulting in higher rates of coking.