Activity and coke formation of nickel and nickel carbide in dry reforming: A deactivation scheme from density functional theory

Dry reforming is a promising reaction to utilise the greenhouse gases CO2 and CH4. Nickel-based catalysts are the most popular catalysts for the reaction, and the coke formation on the catalysts is the main obstacle to the commercialisation of dry reforming. In this study, the whole reaction network of dry reformation on both flat and stepped nickel catalysts (Ni(111) and Ni(211)) as well as nickel carbide (flat: Ni3C(001); stepped: Ni3C(111)) is investigated using density functional theory calculations. The overall reaction energy profiles in the free energy landscape are obtained, and kinetic analyses are utilised to evaluate the activity of the four surfaces. By careful examination of our results, we find the following regarding the activity: (i) flat surfaces are more active than stepped surfaces for the dry reforming and (ii) metallic nickel catalysts are more active than those of nickel carbide, and therefore, the phase transformation from nickel to nickel carbide will reduce the activity. With respect to the coke formation, the following is found: (i) the coke formation probability can be measured by the rate ratio of CH oxidation pathway to C oxidation pathway (r(CH)/r(C)) and the barrier of CO dissociation, (ii) on Ni(111), the coke is unlikely to form, and (iii) the coke formations on the stepped surfaces of both nickel and nickel carbide can readily occur. A deactivation scheme, using which experimental results can be rationalised, is proposed. 

Co-tape casting fabrication, field assistant sintering and evaluation of a coke resistant La0.2Sr0.7TiO3-Ni/YSZ functional gradient anode supported solid oxide fuel cell

The ability to directly utilize hydrocarbons and other renewable liquid fuels is one of the most important issues affecting the large scale deployment of solid oxide fuel cells (SOFCs). Herein we designed La_0.2Sr_0.7TiO₃-Ni/YSZ functional gradient anode (FGA) supported SOFCs, prepared with a co-tape casting method and sintered using the field assisted sintering technique (FAST). Through SEM observations, it was confirmed that the FGA structure was achieved and well maintained after the FAST process. Distortion and delamination which usually results after conventional sintering was successfully avoided. The La_0.2Sr_0.7TiO₃-Ni/YSZ FGA supported SOFCs showed a maximum power density of 600mWcm^-2 at 750°C, and was stable for 70h in CH₄. No carbon deposition was detected using Raman spectroscopy. These results confirm the potential coke resistance of La_0.2Sr_0.7TiO₃-Ni/YSZ FGA supported SOFCs.

Simulation of Oil Shale Semi-Coke Particle Cold Transportation in a Spouted Bed Using CPFD Method

The spouted bed was widely used due to its good mixing of particles and effective phase transferability between the gas and solid phase. In this paper, the transportation process of particles in a 3D spouted bed was studied using the Computational Particle Fluid Dynamics (CPFD) numerical method. Experiments were conducted to verify the validity of the simulation results. Distributions of the pressure, velocities and particle concentration of transportation devices were investigated. The motion state and characteristics of multiphase flows in the transportation device were demonstrated under various operating conditions. The results showed that a good consistency was obtained between the simulated results and the experimental results. The motion characteristics of the gas-solid two-phase flow in the device was effectively predicted, which could assist the optimal operating condition estimation for the spouted transportation process.

Influence of preparation conditions on the characteristics of activated carbons produced in laboratory and pilot scale systems

The central theme of this investigation is to evaluate the feasibility of using bituminous coal as a precursor material for the production of chars and activated carbons using physical and chemical activation processes. The chemical activation process was accomplished by impregnating the raw materials with different dehydrating agents in different ratios and concentrations, prior to heat treatment (ZnCl2, KCl, KOH, NaOH and Fe2(SO4)3·xH2O). Steam activation of the precursor material was adopted for the preparation of activated carbon using physical activation technology. Different types of bituminous coal; namely, contaminated Columbian (contaminated with pet. coke), pure Columbian, Venezuelan and New Zealand bituminous coal were used in the production processes. BET surface area, micropore area, pore size distribution and total pore volume of the chars and activated carbons were determined from N2 adsorption/desorption isotherm, measured at 77 K. Charring conditions, charring temperature of 800 °C and charring time of 4 h, proved to be the optimum conditions for preparing chars. Contaminated Columbian were found to be the best precursor material for the production of char with reasonable physical characteristics (surface area = 138.1 m2 g-1 and total pore volume of 8.656 × 10-0.2 cm3 g-1). An improvement in the physical characteristics of the activated carbons was obtained upon the treatment of coal with dehydrating agents. Contaminated Columbian treated with 10 wt% ZnCl2 displayed the highest surface area and total pore volume (surface area = 231.5 m2 g-1 and total pore volume = 0.1227 cm3 g-1) with well-developed microporisity (micropore area = 92.3 m2 g-1). Venezuelan bituminous coal using the steam activation process was successful in producing activated carbon with superior physical characteristics (surface area = 863.50 m2 g-1, total pore volume = 0.469 cm3 g-1 and micropore surface area = 783.58 m2 g-1).

Catalytic properties of beta zeolite exchanged with Pd and Fe for toluene total oxidation

Dealuminated beta zeolites exchanged with Pd and Fe were prepared to investigate the influence of iron and dealumination on the activity and selectivity of Pd/BEA zeolite for toluene total oxidation. The specific areas determined by BET method and EPR studies allowed to know that the palladium would be more easily agglomerated on the BEA than on the DBEA. Moreover, a quantification of the palladium saturation on the BEA zeolite was deduced by EPR. Effects of dynamic and static oxidation and weak and strong reduction treatments were studied by EPR. Several isolated and interacted Pd+ species and hole centers were detected. The Pd was much reduced after the catalytic test in dealuminated and Fe doped samples. This result could be directly correlated to the catalytic deactivation. The deactivation could be also explain by the type of coke deposed on the catalyst and by the hydroscopic behavior of the samples. Addition of Fe or dealumination could prevent the deactivation and then lead to better catalysts for VOCs oxidation.

Activity and deactivation studies for direct dimethyl ether synthesis using CuO-ZnO-Al2O3 with NH(4)ZSM-5, HZSM-5 or gamma-Al2O3

Herein we investigate the use of CuO-ZnO-Al2O3 (CZA) with different solid acid catalysts (NH(4)ZSM-5. HZSM-5 or gamma-Al2O3) for the production of dimethyl ether from syngas. It was found that of the solid acids, which are necessary for the dehydration function of the admixed system, the CZA/HZSM-5 bifunctional catalyst with a 0.25 acid fraction showed high stability over a continuous period of 212 h.

As this particular system was observed to loose around 16.2% of its initial activity over this operating period this study further investigates the CZA/HZSM-5 bifunctional catalyst in terms of its deactivation mechanisms. TPO investigations showed that the catalyst deactivation was related to coke deposited on the metallic sites: interface between the metallic sites and the support near the metal-support: and on the support itself. 

Hierarchical zeolites prepared by organosilane templating: A study of the synthesis mechanism and catalytic activity

The crystallization of hierarchical ZSM-5 in the presence of the organosilane octadecyl-dimethyl-(3-trimethoxysilyl-propyl)-ammonium chloride as the mesoporogen was investigated as a function of time and temperature. The synthesis by this method proceeds in two steps. The rapid formation of a predominantly amorphous disordered mesoporous aluminosilicate precursor phase is followed by the formation of globular highly mesoporous zeolite particles involving dissolution of the precursor phase. It is difficult to completely convert the initial phase into the final hierarchical zeolite. This limits the amount of aluminium built into the MFI network and the resulting Bronsted acidity. In the presence of iron, more crystalline hierarchical zeolite is obtained. These Fe-containing zeolites are excellent catalysts for the selective oxidation of benzene to phenol. Their hierarchical pore structure leads to higher reaction rates due to increased mass transfer and increased catalyst longevity despite more substantial coke formation. (C) 2011 Elsevier B.V. All rights reserved.

Microwave-assisted Cu-catalyzed Ullmann ether synthesis in a continuous-flow milli-plant

The combination of milli-scale processing and microwave heating has been investigated for the Cu-catalyzed Ullmann etherification in fine-chemical synthesis, providing improved catalytic activity and selective catalyst heating. Wall-coated and fixed-bed milli-reactors were designed and applied in the Cu-catalyzed Ullmann-type CO coupling of phenol and 4-chloropyridine. In a batch reactor the results show clearly increased yields for the microwave heated process at low microwave powers, whereas high powers and catalyst loadings reduced the benefits of microwave heating. Slightly higher yields were found in the Cu/ZnO wall-coated as compared to the Cu/TiO fixed-bed flow-reactor. The benefit here is that the reaction occurs at the surface of the metal nanoparticles confined within a support film making the nano-copper equally accessible. Catalyst deactivation was mainly caused by Cu oxidation and coke formation; however, at longer process times leaching played a significant role. Catalyst activity could partially be recovered by removal of deposited by-product by means of calcination. After 6h on-stream the reactor productivities were 28.3 and 55.1kgprod/(mR3h) for the fresh Cu/ZnO wall-coated and Cu/TiO fixed-bed reactor, respectively. Comparison of single- and multimode microwaves showed a threefold yield increase for single-mode microwaves. Control of nanoparticles size and loading allows to avoid high temperatures in a single-mode microwave field and provides a novel solution to a major problem for combining metal catalysis and microwave heating. Catalyst stability appeared to be more important and provided twofold yield increase for the CuZn/TiO catalyst as compared to the Cu/TiO catalyst due to stabilized copper by preferential oxidation of the zinc. For this catalyst a threefold yield increase was observed in single-mode microwaves which, to the best of our knowledge, led to a not yet reported productivity of 172kgprod/(mR3h) for the microwave and flow Ullmann CO coupling. © 2012 Elsevier B.V.

Mesoporous SSZ-13 zeolite prepared by a dual-template method with improved performance in the methanol-to-olefins reaction

Hierarchical SSZ-13 zeolites were synthesized by combining N,N,N-trimethyl-1-adamantanammonium hydroxide (TMAdOH) as the structure-directing agent for chabazite formation with mono- and diquaternary ammonium-type and organosilane mesoporogens and extensively characterized for their structural, textural, and catalytic properties. Mesoporous SSZ-13 zeolites can be synthesized in one step by combining TMAdOH and the diquaternary ammonium-type surfactant C22-4-4Br2. The mesopore volume increases with the mesoporogen/SDA ratio. The hierarchical zeolites are highly crystalline and exhibit similar Brønsted acidity as SSZ-13. Hierarchical SSZ-13 zeolites display increased lifetime in packed-bed MTO experiments than conventional SSZ-13 at similar light olefins yield. The increased lifetime is due to better utilization of the micropore space. With increasing mesoporosity, the micropore space is used more efficiently, but also the rate of coke formation at the crystal periphery increases. Accordingly, the most stable zeolite is obtained at a relatively low C22-4-4Br2/SDA ratio. These zeolite catalysts can be regenerated without substantial loss of activity.

Catalytic performance of sheet-like Fe/ZSM-5 zeolites for the selective oxidation of benzene with nitrous oxide

Hierarchical Fe/ZSM-5 zeolites were synthesized with a diquaternary ammonium surfactant containing a hydrophobic tail and extensively characterized by XRD, Ar porosimetry, TEM, DRUV-Vis, and UV-Raman spectroscopy. Their catalytic activities in catalytic decomposition of NO and the oxidation of benzene to phenol with NO as the oxidant were also determined. The hierarchical zeolites consist of thin sheets limited in growth in the b-direction (along the straight channels of the MFI network) and exhibit similar high hydrothermal stability as a reference Fe/ZSM-5 zeolite. Spectroscopic and catalytic investigations point to subtle differences in the extent of Fe agglomeration with the sheet-like zeolites having a higher proportion of isolated Fe centers than the reference zeolite. As a consequence, these zeolites have a somewhat lower activity in catalytic NO decomposition (catalyzed by oligomeric Fe), but display higher activity in benzene oxidation (catalyzed by monomeric Fe). The sheet-like zeolites deactivate much slower than bulk Fe/ZSM-5, which is attributed to the much lower probability of secondary reactions of phenol in the short straight channels of the sheets. The deactivation rate decreases with decreasing Fe content of the Fe/ZSM-5 nanosheets. It is found that carbonaceous materials are mainly deposited in the mesopores between the nanosheets and much less so in the micropores. This contrasts the strong decrease in the micropore volume of bulk Fe/ZSM-5 due to rapid clogging of the continuous micropore network. The formation of coke deposits is limited in the nanosheet zeolites because of the short molecular trafficking distances. It is argued that at high Si/Fe content, coke deposits mainly form on the external surface of the nanosheets. © 2012 Elsevier Inc. All rights reserved.

Acidic properties of nanolayered ZSM-5 zeolites

The acidic properties of nanolayered ZSM-5 zeolites synthesized with the aid of multiquaternary ammonium surfactants were investigated in detail. A substantial fraction of Al is present in highly dispersed form at extraframework positions indicative of the defective nature of the calcined nanolayered zeolites. Acidity characterization reveals that the Brønsted acid sites are similar in strength to those in bulk HZSM-5. Nanolayered zeolites contain a higher amount of Brønsted acid sites (BAS) at their external (mesopore) surface. Unilamellar zeolites have a higher concentration of external BA and silanol sites than multilamellar ones. The number of BAS in the nanolayered zeolites is considerably lower than the tetrahedral Al content, the difference increasing with nanolayer thickness. Except for one particular sample (nanolayered ZSM-5 synthesized from COH template), the total turnover of methanol normalized per BAS trends inversely with the concentration of BAS. There is no correlation with the concentration of external BAS. Catalyst deactivation due to coke mainly depends on the BAS concentration. A unilamellar ZSM-5 zeolite prepared using COH displayed substantially improved performance in terms of a much lower rate of coke deactivation in line with earlier data Choi et al. [10]. Since the acidic and textural properties of this zeolite did not differ significantly from the others, it remains to be determined why this zeolite performs so much better. © 2013 Elsevier Ltd. All rights reserved.

Potassium-doped Ni-MgO-ZrO catalysts for dry reforming of methane to synthesis gas

Ni/K-MgO-ZrO catalysts for dry reforming of methane, with a range of Mg/Zr ratios and each containing about 10 wt% Ni, were prepared via Ni nitrate impregnation on MgO-ZrO supports synthesized by co-precipitation using KCO. It was found that a proportion of the potassium of the precipitant remained in the samples and improved the stability of the catalysts in the reaction. It was also shown that reduction of the catalysts at 1,023 K without calcination in air is necessary for stable and high activity; calcination in air at 1,073 K gives a deterioration of the catalytic properties, leading to rapid deactivation during the reaction. The order of the CH conversions of the reduced catalysts after 14 h on stream was as follows: Ni/K-MgZr ~ Ni/K-Mg ≥ Ni/K-MgZr Ni/K-Zr. A catalyst with 0.95 wt% K on MgO-ZrO with a Mg:Zr mole ratio of 5:2 showed the best resistance to deactivation. Experiments in a microbalance system showed that there was only negligible coke deposition on the surface of this sample. This behaviour was attributed to the presence of Ni nanoparticles with a diameter of less than 10 nm located on a MgO/NiO solid solution shell doped by K ions; this in turn covers a core of tetragonal ZrO and/or a MgO/ZrO solid solution. This conclusion was supported by EDS/TEM, XPS, XRD and H chemisorption measurements. © 2013 Springer Science+Business Media New York.

Self-cleaning perovskite type catalysts for the dry reforming of methane

Gas-to-liquid processes are generally used to convert natural gas or other gaseous hydrocarbons into liquid fuels via an intermediate syngas stream. This includes the production of liquid fuels from biomass-derived sources such as biogas. For example, the dry reforming of methane is done by reacting CH4 and CO2, the two main components of natural biogas, into more valuable products, i.e., CO and H2. Nickel containing perovskite type catalysts can promote this reaction, yielding good conversions and selectivities; however, they are prone to coke laydown under certain operating conditions. We investigated the addition of high oxygen mobility dopants such as CeO2, ZrO2, or YSZ to reduce carbon laydown, particularly using reaction conditions that normally result in rapid coking. While doping with YSZ, YDC, GDC, and SDC did not result in any improvement, we show that a Ni perovskite catalyst (Na0.5La0.5Ni0.3Al0.7O2.5) doped with 80.9 ZrO2 15.2 CeO2 gave the lowest amount of carbon formation at 800 °C and activity was maintained over the operating time.

Self‐cleaning perovskite type catalysts for the dry reforming of methane

Gas-to-liquid processes are generally used to convert natural gas or other gaseous hydrocarbons into liquid fuels via an intermediate syngas stream. This includes the production of liquid fuels from biomass-derived sources such as biogas. For example, the dry reforming of methane is done by reacting CH4 and CO2, the two main components of natural biogas, into more valuable products, i.e., CO and H2. Nickel containing perovskite type catalysts can promote this reaction, yielding good conversions and selectivities; however, they are prone to coke laydown under certain operating conditions. We investigated the addition of high oxygen mobility dopants such as CeO2, ZrO2, or YSZ to reduce carbon laydown, particularly using reaction conditions that normally result in rapid coking. While doping with YSZ, YDC, GDC, and SDC did not result in any improvement, we show that a Ni perovskite catalyst (Na0.5La0.5Ni0.3Al0.7O2.5) doped with 80.9 ZrO2 15.2 CeO2 gave the lowest amount of carbon formation at 800 °C and activity was maintained over the operating time.