Temperature-programmed Oxidation Research Articles

Proposal of a new mechanism of ammonia on the coking inhibition of n-decane under supercritical conditions

The coking problem of hydrocarbon fuel pyrolysis is the key factor affecting the application of active cooling technology for high-speed aircraft. The purpose of this work is to investigate the coking inhibition performance and coking mechanism of using ammonia as an additive during the thermal cracking. In this study, the pyrolysis and coking characteristics of supercritical n-decane were experimentally studied using an electrically heated tube. ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometer), GC–MS (Gas Chromatograph Mass Spectrometer), SEM (Scanning Electron Microscope), EDS (Energy Dispersive Spectroscopy), TPO (Temperature Programmed Oxidation), and Raman spectroscopy are applied to characterize the anti-coking performance of the additives. The results show that the additive hardly affects the cracking of the fuel under high-temperature conditions, but the coke mass deposited on the inner surface of the tube is significantly reduced, and the coking inhibition rate can reach 80% at 750 °C. The addition of additives reduced the graphitization degree and oxidative activity of the coke. The maximum oxidation temperature of the coke obtained at 750 °C was reduced by 145 °C, and the ID/IG value of the Raman spectroscopy peak-fitting was 3.29. The new mechanism of the effect of additives on the formation of coking precursors and the deposition of coke on the surface of the tube wall is proposed. Ammonia can react with Ni of the inner metal tube and radicals generated by fuel cracking to form a carbonized film, achieving the effect of inhibiting metal catalytic coking. Meanwhile, the amino radicals generated by ammonia dehydrogenation can regulate the coking reaction path by forming a stable p-π conjugate structure with unsaturated radicals. Therefore, the research will contribute to a deeper comprehension of the coking inhibition mechanism and the development of more effective coking inhibitors, providing new technical support for active cooling technologies.

New strategy for coking pathway regulation during n-decane cracking with the additives containing hydroxyl groups

Coking during the endothermic hydrocarbon fuel pyrolysis is a key issue that needs to be solved in the development of regenerative cooling technology for high-speed aircrafts. The compounds containing hydroxyl groups are developed to inhibit coking by regulating coking pathway during the thermal cracking of hydrocarbon fuels. Pyrolytic deposition experiments of n-decane with additives were performed using the method of electrical heating. The anti-coking performance of the additives was characterized by means of gas chromatograph–mass spectrometer (GC–MS), scanning electron microscopy (SEM), temperature programmed oxidation (TPO) and Raman spectroscopy. The results showed that the degree of cracking is reduced at low fuel temperature due to the dilution of the additives, and the additives do not affect the fuel cracking as the fuel temperature increased. With the function of additives, the masses of filamentous and amorphous coke were decreased. A possible mechanism for the additives inhibiting coking has been proposed. The additives containing hydroxyl groups can block the initial coking reaction path to inhibit coking at the source. In general, the hydroxyl radicals released by the additives oxidize the coking precursors to prevent its further growth, and react with the substrate to form particulate matters serving as passivation coating, inhibiting the bulk phase coking and metal catalytic coking simultaneously. This work provides significant ideas for inhibiting coking by regulating coking reaction pathways.

Stable and highly efficient HMDS terminated m-Cresol inhibitor for inhibiting coal spontaneous combustion

A stable and highly efficient 1, 1, 3, 3, 3-hexamethyldisilazane (HMDS) terminated m-Cresol inhibitor was synthesized based on the protection-deprotection strategy. The inhibitory effect of HMDS terminated m-Cresol inhibitor on spontaneous combustion of lignite was explored through temperature-programmed oxidation tests, in-situ infrared analysis and thermogravimetric analysis. Results show that, the oxidation of active phenolic hydroxyl groups in the m-Cresol inhibitor can be hindered by the protection of HMDS. After encountering coal, the HMDS terminated inhibitor can be gradually deprotected to regenerate the m-Cresol inhibitor that contains massive active phenolic hydroxyl groups, thus improving the chemical inhibition efficiency of coal spontaneous combustion. For the coal sample inhibited with HMDS terminated m-Cresol inhibitor, the initial contents of the active functional groups are lower and more stable during heating, and the inhibition rate reaches 70% at 130 °C. Moreover, the crossing-point temperature rises by 32.4 °C–181.2 °C. The activation energy increases by 11 kJ/mol and 18 kJ/mol at below and above 130 °C respectively. The peak temperature at maximum weight loss rate rises by 65 °C–431.2 °C, and the corresponding residual carbon rate increased by 31.3%–61.6%. The inhibition mechanism of the HMDS terminated m-Cresol inhibitor on coal spontaneous combustion was deduced.

Preparation and inhibition performance of dry water materials for preventing spontaneous combustion of coal

This work aimed to effectively prevent the spontaneous combustion of coal in goafs by preparing a type of dry water material with a solid-in-liquid structure through the mechanical stirring method, with nano-aluminum hydroxide aqueous solution as the core material and hydrophobic nano-silicon dioxide as the wall material. The effects of solid-to-liquid ratio, stirring time, and mass concentration of nano-aluminum hydroxide on the particle size and microstructure of dry water were studied. Results showed that the prepared dry water powder was the most uniform and fine when nano-silica, nano-aluminum hydroxide, and water were mixed at a mass ratio of 5:0.75:49.25 and stirred at a speed of 23,000 r/min for 25 s. The samples were characterized by using a temperature-programmed oxidation device, a thermogravimetric analyzer, and a Fourier-transform infrared spectrometer, and the inhibition performance of dry water was evaluated. Results revealed that dry water effectively slowed the oxidation rate of coal and inhibited the release of CO in the low-temperature environment, and the cross-point temperature increased from 125.1 °C to 155.4 °C for raw coal. In a high-temperature environment, dry water delayed the process of spontaneous combustion of coal, the temperature leading to the maximum mass increased from 308.6 °C to 369.4 °C, and the ignition temperature rose from 458.2 °C to 484.7 °C. In addition, the dry water material can inhibit the oxidative decomposition of aliphatic hydrocarbons and the transformation of oxygen-containing functional groups in coal samples, thus indicating, from a microscopic level, that it has good inhibition performance.

Fabrication of the coke-resistant and easily reducible Ni/SiC catalyst for CO2 methanation

The catalytic methanation of carbon dioxide, which is a promising process for CO2 to fuels, has been extensively investigated using Ni-based catalysts due to their high CH4 selectivity, high CO2 conversion, and affordability. However, owing to its highly exothermic nature, CO2 methanation can cause severe carbon deposition and sintering effects, resulting in catalyst deactivation. This is where high thermal conductivity SiC presents itself as a viable alternative support to enhance the performance of Ni-based catalysts. In this work, Ni catalysts supported on a cheap commercial SiC were prepared by wet impregnation method with different Ni loadings and calcination temperatures. The as-prepared and spent catalysts were characterized using N2 physisorption, X-ray diffraction, H2 temperature-programmed reduction (H2-TPR), temperature-programmed oxidation (TPO) and transmission electron microscopy. H2-TPR analysis revealed that reduction at 400 °C for 15 min is enough to convert most of NiO to active Ni0 to archive the highest activity toward CO2 methanation. The catalytic performance and long-term stability of the as-prepared Ni/SiC catalysts were evaluated for CO2 methanation at stoichiometric CO2/H2 ratio of 1/4, different gas hourly space velocities, reaction temperatures, and reduction conditions. Among the synthesized catalysts, the 10%Ni/SiC-500 exhibited highest CO2 conversion (70%) and CH4 selectivity (98%) as well as stable catalytic performance for 30 h on stream at a GHSV of 20,000 h−1 and reaction temperature of 400 °C.

Preparation and characterization of Na4Mn9O18 whiskers on channel surface of cordierite honeycomb ceramics for soot catalytic combustion

Na4Mn9O18 whiskers were prepared on the wall of cordierite honeycomb ceramics using the molten salt synthesis, and Na4Mn9O18 whiskers were grew on channel surface of cordierite honeycomb ceramics to form hierarchical microstructure for catalytic combustion of soot. Scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and X-ray diffraction (XRD) were used to characterize the structural morphology and phase compositions. Na4Mn9O18 whiskers with aspect ratio of 24.4 measured by statistics. It was found that the loading rate of the monolithic catalyst reaches 3.588% while the binding rate after sonication almost no change. Whiskers are tightly combined with the cordierite ceramic substrate by the binding strength experiments and EDS analysis. The oxygen temperature-programmed desorption (O2-TPD) measurements were performed to investigate the O2 adsorption property. The catalytic performance of the samples were examined by semi-quantitative thermal gravimetric analysis (TG-DTG) and temperature-programmed oxidation (TPO). The catalyst performance study demonstrates that Na4Mn9O18 whiskers decrease the soot combustion temperature apparently. Experiments show the characteristic temperature could be reduced by increasing the catalyst loading. The Na4Mn9O18 decreased the ignition temperature of soot particles oxidation, and the cycle stability experiment confirmed that the sample (0h-m-k) has good structural stability and stable catalytic performance. The coarseness of the interface increased because Na4Mn9O18 whiskers grew on the cordierite substrate, and the trapping ability improved. Na4Mn9O18 is an important type of catalyst which is rarely studied in catalytic oxidation of soot. This catalyst displays good activity and stability in the soot catalytic oxidation. This unique microstructure has potential application in the DPF field.

Sintering behavior of platinum and modification effect of ceria on silica-alumina supports for diesel soot oxidation

In this work, silica-alumina mixed oxides with different SiO2 contents (5% and 30%) were adopted as acidic supports for platinum catalysts for soot oxidation. The obtained catalysts were thermally aged in air at 550, 650 and 750 °C for 2 h, respectively. The catalysts were characterized by transmission electron microscopy (TEM), CO chemisorption, inductively coupled plasma (ICP), N2 adsorption/desorption, NH3 temperature-programmed desorption (TPD), H2 temperature-programmed reduction (TPR), infrared (IR) spectroscopy of CO and NH3 adsorption, and NO temperature-programmed oxidation (TPO). The acidic support Pt catalysts had higher catalytic activities for NO oxidation and soot oxidation. After aging at 750 ℃, severer sintering of Pt occurred on the acidic supports, and some Pt particles larger than 50 nm formed, resulting in serious deactivation. It was ascribed to metallic state of Pt on the acidic supports with weakened metal-support interactions (SMI). Thus, CeO2 was added to the silica-alumina support by ball milling to strengthen the SMI via forming Pt-O-Ce bonds. In this way, Pt nanoparticles were anchored to the modified support to inhibit sintering at high temperatures, and the obtained Pt/CeO2/SiO2-Al2O3 catalyst exhibited both high soot oxidation activity and superior thermal stability.

Study on the Catalytic Characteristics of Precious Metal Catalysts with Different Pt/Pd Ratios for Soot Combustion.

Soot particles in engine exhaust seriously pollute the atmosphere and endanger human health. For soot oxidation, Pt and Pd precious metal catalysts are widely used and are effective. In this paper, the catalytic characteristics of catalysts with different Pt/Pd mass ratios for soot combustion were studied through X-ray diffraction, X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller analysis, scanning electron microscopy, transmission electron microscopy, the temperature-programmed oxidation reaction, and thermogravimetry. Besides, the adsorption characteristics of soot and O2 on the catalyst surface were explored by density functional theory (DFT) calculations. The research results showed that the activity of catalysts for soot oxidation from strong to weak is Pt/Pd = 10:1, Pt/Pd = 5:1, Pt/Pd = 1:0, and Pt/Pd = 1:1. XPS results showed that the concentration of oxygen vacancies in the catalyst is the highest when the Pt/Pd ratio is 10:1. The specific surface area of the catalyst increases first and then decreases with the increase of Pd content. When the Pt/Pd ratio is 10:1, the specific surface area and pore volume of the catalyst reach the maximum. The following are the DFT calculation results. With the increase of Pd content, the adsorption energy of particles on the catalyst surface decreases first and then increases. When the Pt/Pd ratio is 10:1, the adsorption of C on the catalyst surface is the strongest, and the adsorption of O2 is also strong. In addition, this surface has a strong ability to donate electrons. The theoretical simulation results are consistent with the activity test results. The research results have a guiding significance for optimizing the Pt/Pd ratio and improving the soot oxidation performance of the catalyst.

Morphological and Compositional Analysis on Thermal Deposition of Supercritical Aviation Kerosene in Micro Channels.

The integration of active cooling systems in super or hypersonic aircraft using endothermic hydrocarbon fuels is considered an effective way to relieve the thermal management issues caused by overheating. When the temperature of aviation kerosene exceeds 150 °C, the oxidation reaction of fuel is accelerated, forming insoluble deposits that could cause safety hazards. This work investigates the deposition characteristic as well as the morphology of the deposits formed by thermal-stressed Chinese RP-3 aviation kerosene. A microchannel heat transfer simulation device is used to simulate the heat transfer process of aviation kerosene under various conditions. The temperature distribution of the reaction tube was monitored by an infrared thermal camera. The properties and morphology of the deposition were analyzed by scanning electron microscopy and Raman spectroscopy. The mass of the deposits was measured using the temperature-programmed oxidation method. It is observed that the deposition of RP-3 is highly related to dissolved oxygen content (DOC) and temperature. When the outlet temperature increased to 527 °C, the fuel underwent violent cracking reactions, and the structure and morphology of deposition were significantly different from those caused by oxidation. Specifically, this study reveals that the structure of the deposits caused by short-to-medium term oxidation are dense, which is different from long-term oxidative deposits.

Combined steam and dry reforming of methanol over Ni-M/Ce–Al2O3 (M=Fe, Cu, and Zn) catalysts to syngas formation

In the present work, the influences of different transition metals (Fe, Cu, and Zn) addition to Ni/Ce–Al2O3 catalyst on combined steam and dry reforming of methanol (CSDRM) reaction were evaluated in the temperature range of 500 ºC-900 °C, to achieve the higher conversion and H2 yield following by minimum coke formation on the catalyst surface. The fresh and spent catalysts were characterized via X-ray diffraction (XRD), thermal gravimetric analysis (TGA), inductively coupled plasma atomic emission spectrometer (ICP-AES), temperature programmed oxidation (TPO), N2 adsorption/desorption and temperature programmed reduction (TPR). Their results presented that the addition of these transition metals had a little effect on the crystallinity, surface area, pore volume and mean pore size. However, thermal stability, coke deposition coke amount, reducibility and catalytic activity were improved. The methanol conversion was approximately fixed up to 50 h initial on stream with no obvious deactivation for Ni/Ce–Al2O3 catalyst, while this time was 55 h for the modified catalyst with transition metals (Cu, Fe, and Zn). The maximum methanol and CO2 conversions and anti-coke deposition ability were obtained from Ni–Zn/Ce–Al2O3 which was remarkably related to synergism between Ni and Zn, also the larger reducibility. However, the maximum value of H2 yield was 85.2% at 900 °C over Ni–Cu/Ce–Al2O3 catalyst. Ni–Zn/Ce–Al2O3 catalyst in the CSDRM reaction produced syngas with an H2/CO ratio of 2.06, suggesting to a suitable feed for Fischer-Tropsch synthesis.

Neodymium promoted ceria and alumina supported nickel catalysts for CO2 methanation reaction

Two series of catalysts containing 20 wt.% nickel, promoted with different amounts of neodymium from 1 to 10 wt.% were prepared by the impregnation method, using nano-CeO2 and γ-Al2O3 as supports. Ceria supported nickel catalysts showed high activity in CO2 methanation reaction and weak activity changes were observed with an increase in Nd content. X-ray diffraction, hydrogen chemisorption and transmission electron microscopy studies evidenced a decrease in the average size of nickel crystallites and an increase in the active surface area of catalysts. The temperature-programmed reduction, oxidation and CO2 desorption, XPS, Raman and in-situ FTIR spectroscopy indicated complex changes in the nature of their redox and base centres. Non-promoted alumina supported nickel catalyst despite higher surface area showed lower activity than similar catalyst with ceria as support. However, an introduction of Nd-promoter led to strong increase in their activity. Such effect was mainly ascribed to the increase in their basicity, facilitation of CO2 activation and subsequent transformation of the intermediate surface species to methane with participation of hydrogen atoms activated on metallic nickel crystallites.

On the Application of an In Situ Catalyst Characterization System (ICCS) and a Mass Spectrometer Detector as Powerful Techniques for the Characterization of Catalysts

The in situ characterization of catalysts provides important information on the catalyst and the understanding of its catalytic performance and selectivity for a specific reaction. Temperature programmed analyses (TPX) techniques for catalyst characterization reveal the role of the support on the stabilization and dispersion of the active sites. However, these can be altered at high temperatures since sintering of active species can occur as well as possible carbon deposition which hinders the active species and deactivates the catalyst. The in situ characterization of the spent catalyst, however, may expose the causes of catalyst deactivation. For example, a simple temperature programmed oxidation (TPO) analysis on the spent catalyst may produce CO and CO2 via a reaction with O2 at high temperatures and this is a strong indication that deactivation may be due to the deposition of carbon. Other TPX techniques such as temperature programmed reduction (TPR) and pulse chemisorption are also valuable techniques when they are applied in situ to the fresh catalyst and then to the catalyst upon deactivation. In this work, two Ni supported catalysts were considered as examples to elucidate the importance of these techniques in the characterization study of catalysts applied to the reaction of hydrogenation of CO2.

Synergy of Oxygen Vacancies and Ni0 Species to Promote the Stability of a Ni/ZrO2 Catalyst for Dry Reforming of Methane at Low Temperatures

Low-temperature dry reforming of methane (DRM) can avoid the sintering of nickel and reduce the cost of the process. However, inefficient activation of CO2 and oxidization of Ni0 hamper the catalytic performance of Ni-based catalysts at low temperatures. Herein, a Ni/ZrO2 catalyst was prepared and used in the DRM reaction, which exhibited stable activity at low temperatures (400, 320 and 300 °C) for 10 h, with CH4 and CO2 turnover frequencies of 0.26 and 0.18 s–1 at 320 °C, respectively. The presence of Ni0 species and oxygen vacancies promotes the activation of CO2 at 300 °C, proved by CO2 temperature-programmed oxidation (CO2-TPO). Combined with O2 temperature-programmed decomposition (O2-TPD), C18O2-DRM, in situ X-ray photoelectron spectroscopy (XPS), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) results, after CH4 decomposition on the Ni0 site, the resultant C would react with nearby surface oxygen species and lattice oxygen species of ZrO2, forming CO and an oxygen vacancy. The oxygen vacancy nearby Ni0 species with more electron transfer would promote the activation of CO2. This work highlights the importance of CO2 activation and emphasizes the key role of the synergistic effect between Ni0 species and the oxygen vacancy in enhancing the stability of catalysts over low-temperature DRM reactions.

Effect of CaO, Al2O3, and MgO Supports of Ni Catalysts on the Formation of Graphite-like Carbon Species during the Boudouard Reaction and Methane Cracking.

The investigation of the course of the Boudouard reaction and methane cracking was performed over nickel catalysts based on oxides of calcium, aluminum, and magnesium. The catalytic samples were synthesized by the impregnation method. The physicochemical characteristics of the catalysts were determined using atomic adsorption spectroscopy (AAS), Brunauer-Emmett-Teller method analysis (BET), temperature-programmed desorption of ammonia and carbon dioxide (NH3- and CO2-TPD), and temperature-programmed reduction (TPR). Qualitative and quantitative identification of formed carbon deposits after the processes were carried out using total organic carbon analysis (TOC), temperature-programmed oxidation (TPO), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The selected temperatures for the Boudouard reaction and methane cracking (450 and 700 °C, respectively) were found to be optimal for the successful formation of graphite-like carbon species over these catalysts. It was revealed that the activity of catalytic systems during each reaction is directly related to the number of weakly interacted nickel particles with catalyst support. Results of the given research provide insight into the mechanism of carbon deposit formation and the role of the catalyst support in this process, as well as the mechanism of the Boudouard reaction.

Effect of water and methanol concentration in the feed on the deactivation of In2O3-ZrO2/SAPO-34 catalyst in the conversion of CO2/CO to olefins by hydrogenation

On account of the superior performance of In2O3-ZrO2/SAPO-34 tandem catalyst in the direct synthesis of olefins from CO, CO2 and CO/CO2 mixture by hydrogenation, it is interesting to establish the conditions to avoid its deactivation due to the rapid coke deposition on SAPO-34. The co-feeding of H2O and/or methanol together with H2 + CO2/CO was studied in a packed bed reactor at: 400 °C, 30 bar; CO2/COx in the feed, 0–1; H2/COx in the feed, 1–3; and space time of 5 gcat h molC−1, quantifying the evolution with time on stream (up to 16 h) of CO2 and COx conversions and olefin, paraffin and CH4 yields. The effects of the co-feeding on coke content and its nature were determined by temperature programmed oxidation (TPO) analyses of the spent catalyst. The results highlighted the complex effect of the concentration of H2O and oxygenates (methanol/dimethyl ether (DME)) on the deactivation of SAPO-34 and on the products yields in the pseudo-steady state of the catalyst. Co-feeding H2O lessens coke deactivation, however, high H2O concentration leads to attenuate the acidity of SAPO-34, limiting the performance of the tandem catalyst (mainly in the CO2 conversion). Oxygenates co-feeding concentration limit value lies on its favoring effect for coke formation. In addition to this effect, the favorable attenuation of coke deactivation by the high H2 concentration (studied in runs with H2/COx ratio in the feed in the 1–3 range) plays a key role in the viability of the process, leading to a pseudo-steady catalyst state in which the activity is constant. The proven effect of H2O and methanol concentrations will be useful for establishing new catalysts and reaction conditions at which their presence in the reactor will attenuate deactivation.

Strategies for regeneration of Pt-alloy catalysts supported on silica for propane dehydrogenation

Catalyst stability, resistance to deactivation, and regeneration remain a challenge for high temperature reaction processes. For Pt alloys used in propane dehydrogenation (PDH), the primary pathways of catalyst deactivation include coke formation and metal nanoparticle sintering over time. Recent work shows that silica-supported catalysts provide excellent selectivity for this reaction, but the regenerability of silica-supported catalysts has not been established. In this work, we study a series of Pt alloys, including PtMn, PtZn, and PtSn, for the PDH reaction at 550 °C and 600 °C, and we subject the catalysts to regeneration over multiple cycles. While oxidation in air restores the reactivity completely with minimal catalyst sintering, it is surprising to find that these catalysts can also be regenerated in pure hydrogen. Here we explore the types of coke formed on these catalysts using in situ temperature programmed oxidation (TPO). Two types of coke are found: one on the metallic NP surface, and a second on the silica support. Our work shows that treatment in hydrogen causes redistribution of the coke between the metal and support, which can restore most catalytic activity lost during a reaction run. Periodic introduction of H2 during a reaction cycle may constitute an unexplored strategy for extending the lifetime of PDH catalysts.

Oxidative ethanol dry reforming for production of syngas over Co-based catalyst: Effect of reaction temperature

Till date, oxidative ethanol steam reforming use Ni-based catalysts to produce syngas. However, Ni catalysts suffer from easy deactivation due to the coke formation at low temperatures. Therefore, oxidative ethanol dry reforming is a promising method and was investigated over 10 %Co/Al2O3 catalyst due to their high activity and stability to produce high-quality syngas. More importantly, the syngas can be upgraded to produce liquid biofuels and chemicals. The catalyst was evaluated in a quartz fixed-bed reactor under atmospheric pressure at PCO2 =PO2= 5 kPa, PC2H5OH = 15 kPa, with reaction temperature ranging between 773 and 973 K. The γ-Al2O3 support and 10 %Co/Al2O3 catalyst had BET surface areas of 175.2 m2 g−1 and 143.1 m2 g−1, respectively. Co3O4 and spinel CoAl2O4 phases were detected through X-ray diffraction measurements on the 10 %Co/Al2O3 catalyst surface. H2-TPR measurements indicate that the 10 %Co/Al2O3 catalyst was completely reduced at a temperature beyond 1000 K. NH3-TPD measurements indicated the presence of the weak, medium, and strong acid sites on the γ-Al2O3 support and 10 %Co/Al2O3 catalyst. Due to increased reaction temperature from 773 to 973 K, C2H5OH and CO2 conversions improved from 22.5 % to 93.6 % and 16.9–52.8 %, respectively. Additionally, the optimal yield of H2 and CO obtained at 68.1 % and 58.3 %, respectively. Temperature-programmed oxidation experiments indicated that the amount of carbon deposition was the lowest (28,92 %) at 973 K and increased by 41.48 % at 773 K.

Syngas production from CO2 reforming of glycerol by mesoporous Ni/CeO2 catalysts

In this paper, the mesoporous Ni/CeO2 catalyst with high specific surface area was prepared by the colloidal solution combustion method and used for the production of syngas by glycerol dry reforming (GDR). The thermodynamic analysis was conducted by using a non-stoichiometric methodology based on the minimization of Gibbs's free energy. The characterization results show that the higher the Ni content, the weaker the interaction between Ni and the CeO2 support. 5Ni/CeO2 shows the most consistent Ni dispersion and uniform particle size, and it has the best catalytic activity in the GDR and the conversion of glycerol can reach 84.1 % at 750 °C. Besides, all catalysts exhibited excellent stability during the 10 h catalytic process. The temperature-programmed oxidation (TPO) results show that Ni loading ratio of 5 can reduce the production of filamentous carbon. Based on a kinetic model assuming a power law as a first-order reaction, the activation energy of the Ni-based catalyst for glycerol dry reforming was calculated.

Coke evolution during the air- and oxy-firing regeneration of a spent Ni/ZnO sulfur adsorbent

Reactive adsorption desulfurization (RADS) is an effective desulfurization technology in refineries to reduce the sulfur contents in oil products. To ameliorate the desulfurization technology, the evolution of coke was first studied in the air-firing regeneration of a typical spent Ni/ZnO sulfur adsorbent used in RADS. Efforts were made to elaborate the conversion of carbon and sulfur during the oxy-firing regeneration of the spent adsorbent to test the possibility of applying that carbon capture technology – oxy-fuel combustion to the sulfur adsorbent regeneration. A lab-scale drop-tube furnace was employed to conduct the combustion experiments; and the speciation of carbon and sulfur in the regenerated adsorbents was characterized by advanced techniques including near-edge X-ray absorption fine structure (NEXAFS), Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD). The catalytic role of metals (Ni/Zn) in the coke combustion was also verified by acid leaching and temperature-programmed oxidation (TPO) experiments. It has been founded that the carbonaceous materials deposited on the adsorbent comprise five groups, including polyaromatic and graphitic carbon with a fraction of around 27 mol% of the entire carbon, and the other groups which are mostly light aliphatic compounds and oxygen-containing functional groups. During the air-firing regeneration process, most of the light coke species were oxidized into oxygenated intermediates and then desorbed as CO and CO2, with a small portion being polymerized into heavy molecules. Oxy-firing regeneration was verified to improve the efficiency of coke combustion due to the metal-catalyzed CO2 gasification reaction and improved the sulfur conversion under the oxygen-lean condition such as 3 vol% O2 in CO2. The carbon conversion increased from 23% in 3%O2/N2 to 31% in 3%O2/CO2 at 510 ℃. In the meantime, the sulfur conversion was also increased from 50% to 57% at 750 ℃, which is probably due to that the CO2 gasification of coke alleviated the competition of oxygen between carbon and sulfur.

Performance of Modified Alumina-Supported Ruthenium Catalysts in the Reforming of Methane with CO2

Ruthenium (1 wt%) catalysts supported on alumina doped with alkaline (Na and K) and alkaline earth metals (Ba, Ca, and Mg) of different concentrations (1, 5, and 10 wt%) were tested in the dry reforming of methane. All catalysts were prepared by the successive impregnation method. Supports were characterized by X-ray diffraction, BET surface area, temperature-programmed desorption of CO2, and 2-propanol dehydration. Additionally, catalysts were characterized by temperature-programmed reduction (TPR), temperature-programmed oxidation (TPO), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). Stability tests to study coke deposition were performed using long-time dry reforming reactions. All the catalysts showed good catalytic activity, and activity falls were never detected. Ru metallic phase seemed to be resistant to coke formation even though its particles are sintered during a long-term reaction.