Professor Michael Stockenhuber

Natural clinoptilolite (coded as Escott), synthetic BEA, and mixed Escott-BEA zeolites supported nickel and iron catalysts were employed for catalytic hydropyrolysis of eucalyptus globulus leaves. Comparing non-catalytic pyrolysis and catalytic pyrolysis in N2, the use of catalysts along with H2 (30 bar) resulted in improved yields of liquid oil and gas products, with reduced production of biochar/coke. Moreover, the biochar from catalytic hydropyrolysis showed a higher mesopore surface area (97 m2/g) than non-catalytic biochar (74 m2/g). Incorporating a small amount of BEA into Escott weakens the metal-support interaction, enhances H2 adsorption activity and increases the catalyst acidity, leading to an improved aromatic monomers selectivity while preventing excessive cracking of liquid oil. Consequently, Ni-Fe/Escott-BEA catalyst shows the highest content of valuable liquid organic components. Ni-Fe/Escott, with the largest Ni particles and lowest acidity, exhibits higher selectivity to methane and naphthalenes products. In contrast, Ni-Fe/BEA with excessive acid sites exhibited significantly lower content of liquid organic products but higher yields of C2-C5 gas products and deposited carbon, primarily ascribed to its high acidity promoting coupling, cracking and deoxygenation reactions. The deactivation of Brønsted acid sites was more pronounced than Lewis acid sites, underscoring their crucial role in coupling reactions and leading to increased coke deposition.

The effect of desilication on the physic-chemical properties of ferrierite zeolite was investigated using spectroscopic and solid characterisation techniques including N2-adsorption, XRD, SEM, H2-TPR, NH3-TPD and in situ FTIR. Stability of active oxygen species formed from N2O over the Fe-FER catalysts and the catalytic activity for direct conversion of methane to value-added products at temperatures between 300 °C and 400 °C were studied. Ferrierite zeolites, pre-treated with 0.1 M, 0.2 M and 0.3 M NaOH solutions preserved the crystal structure of the ferrierite zeolite but their textural properties were significantly modified, leading to an increase in mesopore area and creating a greater concentration of terminal Si-OH groups, concomitant with increase in the amount of extra-framework Al and reduction in the number of bridging Si-OH-Al species. Batch-mode catalytic reaction studies of methane with N2O conducted in an in situ FTIR cell demonstrate that the methoxy groups formed on extraframework iron sites followed by the migration of these species to silicon defect sites, which resulted in a decline in the intensity of terminal Si-OH groups bands in the IR spectra. N2O-TPD experiments confirm that N2O is converted to N2, O2 and NO over Fe-FER catalysts at 350 °C. The decline in the desorption temperature of these products observed over Fe-FER catalysts treated with alkaline solution is consistent with a significant increase in the mesopore surface area from 28.3 m2/g to 102.4 m2/g. The peak areas of desorbed O2 and NO were estimated, and the different ratios of O2/NO observed on these catalysts appears to be related to the difference stabilities of surface oxygen species. Studies under continuous reaction conditions demonstrate that, at a similar level of methane conversion (ca. 2.8 %), Fe-FER catalysts prepared with the moderately alkaline solution (0.2 M NaOH) results the highest yield of methanol, dimethyl ether and formaldehyde. It is asserted that this enhanced selectivity is the result of the comparatively high concentrations of terminal silanol groups, Brønsted-acid sites, stability of active oxygen species and mesopore volume.

In the present study, a series of La-HZSM5 catalysts were prepared through wet impregnation and investigated for the production of premium quality diesel fuel via hydrodeoxygenation (HDO) of oleic acid (OA). Several parameters were evaluated, such as reaction temperature (360¿400 °C), H2 pressure (1¿5 MPa), La concentration (5¿20%), catalyst loading (1¿7 wt%), and reaction time (1¿4 h). At a reaction of 400 °C for 2 h under 5 MPa H2 pressure, the La(10)HZSM5(90) catalyst showed 97% hydrocarbon yield with 92% of diesel selectivity. The superior HDO activity by La(10)HZSM5(90) in producing high quality diesel is due to a sufficient number of weak + medium acid sites and its mesoporous structure. Vacuum distillation was complementary for producing high quality diesel fractions consisting of C17 fractions. The reusability of the La(10)HZSM5(90) catalyst was also demonstrated, though the catalyst still had coking activity.

Ion exchanged Ru/ZSM-5 and Ru/BEA catalysts, prepared by replacing the extra framework NH4+ cations in zeolites with Ru3+ ions, are employed for the hydrodeoxygenation of guaiacol. The performance results indicate ion-exchanged Ru zeolites, with extremely low Ru contents (~0.2 wt%), possess a high intrinsic HDO activity compared to the catalysts prepared by the incipient wetness impregnation method. On the basis of TEM, FTIR, XPS and TPD analysis, the NH4+ ions in zeolite were substituted by Ru species, with metal particles entered the zeolite cages and finely dispersed on the support. These ion-exchanged Ru particles exhibit a strong electronic interaction with oxygen atoms of zeolite framework with a mixed Ru(0)-Ru(III) species observed in the reduced samples. In contrast, only Ru0 was detected in the reduced impregnated Ru/ZSM-5. The partial-reduced Ru species over the ion-exchanged Ru/ZSM-5 catalyst shows a high H2 adsorption activity facilitating the hydrogenation of guaiacol to the saturated products (such as 2-methoxycyclohexanol). In addition, ion-exchanged Ru-ZSM-5 and Ru-BEA catalysts present a similar normalized cyclohexane formation rate (based on the concentration of acid sites), suggesting the acid sites play a pivotal role in the deoxygenation of 2-methoxycyclohexanol to cyclohexane.

In this study, various metal-modified zeolite beta-based catalysts such as La(10)zeo(90), Co(10)zeo(90), Fe(10)zeo(90), Mg(10)zeo(90), Mn(10)zeo(90) and Zn(10)zeo(90) were investigated in the hydrodeoxygenation (HDO) of oleic acid (OA) to produce renewable diesel. The La(10)zeo(90) catalyst showed a conversion of OA up to 99 % with 83 % C15 and C17 selectivity after the reaction at 350 °C for 2 h under 4 MPa H2 pressure. The superior activity of La(10)zeo(90) was attributed to the synergistic interaction between La-Si-Al, a sufficient amount of weak + medium acid sites and excellent textural properties (large pore diameter). Larger pore diameter of La(10)zeo(90) is highly desirable as it will generate greater diffusion of bulky molecules, thereby improving the accessibility of the reactant and hence excellent catalytic activity. The vacuum distillation was used to purify the crude liquid product (CLP), producing high-quality diesel fractions mainly comprising C14, C15, and C17 fractions.

Formation of silica-rich passivation layers formed on the periphery of reacting feed particles is one of the primary obstacles in obtaining high magnesite yields during direct aqueous mineral carbonation of peridotites and serpentinites. The disruption of the silica-rich layer around partially reacted grains as a result of concurrent grinding on the degree of carbonation (magnesite yield) was investigated in this work. Three types of naturally-occurring magnesium silicate feedstocks, dunite, olivine and lizardite, as well as three types of grinding media, were examined. Discrete size fractions of feed samples, with and without grinding media, were carbonated. SEM readily disclosed the formation of a silica-rich shell around a magnesium rich core during carbonation. EDS analysis was employed to study the elemental composition of reacted particles' shell and core. The method confirmed that during concurrent grinding these silica-rich layers were removed and continuously produced a fresh surface available for further reaction. The removal of the silica-rich layer was shown to significantly improve magnesite yields up to a 600 % increase in yield. Among the three different grinding media used in this work, zirconia and stainless steel media resulted in similar and highest magnesite yields, which is believed to be due to a combination of their high densities and hardness. The findings of this research showed that enhanced magnesite yields could be achieved for all feedstock without the need for energy intensive pre-treatment steps (e.g. ultrafine grinding and heat-activation). Moreover, concurrent grinding resulted in a magnesite yield when raw lizardite was carbonated.

Hydrodeoxygenation (HDO) of guaiacol was investigated over BEA-supported bimetallic Ni-Fe, Ni-Mo, and Ni-W catalysts in a continuous-flow reactor. The electronic properties of Ni were significantly modified following the addition of W and Fe as analyzed by X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption (TPD), which is well in line with density functional theory (DFT) calculations, suggesting that the formation of Ni-Fe and Ni-W alloys is thermodynamically favorable while the generation of a Ni-Mo alloy is unfavored. The HDO over 9 wt % Ni/BEA catalyst was significantly improved following the incorporation of small quantities (<2.2 wt %) of Mo or Fe, while the incorporation of W decreased the HDO rate. The selectivity to hydrogenation products over the Ni-Fe/BEA catalyst was not altered compared to that of Ni/BEA during the hydrogenation of toluene, indicating that the observed increase in guaiacol conversion was engendered by the promotion of the direct hydrogenolysis of guaiacol to aromatics over Ni-Fe species. The hydrogenation and HDO rates of the Ni-Mo/BEA catalyst were both higher than those of Ni/BEA, which was attributed to the increased Ni dispersion promoted by Mo as indicated by similar nickel turnover frequency (TOFNi) values observed over Ni/BEA and Ni-Mo/BEA.

Kinetics of pyrolysis of the pollutant perfluorooctanesulfonic acid (PFOS) in inert bath gases have been studied in two flow reactors constructed of a-alumina and of stainless steel (SS) at temperatures between 400 and 615 °C. Results from the SS reactor give support to previous and our own quantum chemical calculations based on smaller perfluorinated sulfonates, according to which initiation of decomposition of PFOS first takes place by elimination of HF to form an unstable a-sultone with a rate constant, k1. The sultone then rapidly liberates SO2 and forms perfluorooctanoyl fluoride with a rate constant, k2 with k2 » k1 such that the overall rate constant k' ¿ k1. Products observed from both reactors in the above temperature range comprised HF, SO2, and perfluorooctanoyl fluoride. The value of the rate constant for the formation of HF and SO2 measured in the SS reactor was found to be k1 = (1.3 ± 0.5) × 1014 exp(-253 ± 5 kJ/mol/RT) s-1.

Natural and synthetic (BEA, MOR) zeolite-supported nickel (~5 wt%) catalysts were prepared and employed for the hydrogenation of toluene and hydrodeoxygenation of anisole in a continuous-flow reactor. Ni/BEA and Ni/MOR display a higher level of metal dispersion and stronger metal-support interaction compared to the Ni/NZ and Ni/Escott catalysts, resulting in a higher concentration of charge-compensating Ni species and a larger high-temperature reduction peak. The Ni/BEA and Ni/MOR also present a significant mass of low-temperature desorbed H2(centred at 150 °C) based on H2-TPD, suggesting the H species are weakly adsorbed on small Ni clusters. In contrast, the H species were strongly adsorbed by the bulk Ni crystal over Ni/Escott and Ni/NZ, which were desorbed at maxima between 211 and 222 °C. We propose that the strongly adsorbed H species play a crucial role in the hydrogenation of toluene, leading to a significantly higher yield of methylcyclohexane over Ni/Escott and Ni/NZ compared to Ni/BEA and Ni/MOR. Both metal and acid sites are required in the hydrodeoxygenation of anisole. The strong Brønsted acid sites and numerous smaller Ni species over Ni/BEA facilitated the transalkylation of anisole to phenol and methylanisole and subsequently hydrogenolysis of phenol to benzene, followed by the hydrogenation of benzene to cyclohexane.

This study investigated the hydrodeoxygenation (HDO) of oleic acid (OA) that is abundantly found in palm oil for the production of renewable diesel. The effectiveness of mesoporous catalysts, HZSM-5 and zeolite beta, in favoring diesel hydrocarbons was determined. The catalysts were activated by calcination at 550¿°C for 5¿h and their physicochemical properties were determined using X-ray diffraction (XRD), scanning electron microscopy (SEM), temperature-programmed desorption using ammonia probe molecules (TPD-NH3), and Brunauer¿Emmett¿Teller analysis (BET). XRD analysis of both zeolite beta and HZSM5 showed high crystalline size of 24 and 84¿nm, respectively. BET analysis found that the zeolite beta catalyst had a greater surface area (648 m2¿g-1) than HZSM5 (465¿m¿g-1) without significant differences in pore size and volume. According to the TPD-NH3 study, zeolite beta had the most weak + medium acid sites when compared to HZSM5. It should be noted that HZSM5 also demonstrated the presence of strong acid sites. The optimal conditions for both catalysts were 350¿°C, 4¿MPa hydrogen pressure, and 5% catalyst load over a 2¿h reaction period. From the results, the zeolite beta exhibited superior HDO reaction activity than HZSM5 with diesel selectivity ~ 77%.

The in situ X-ray absorption fine structure (XAFS) was measured in the titanium-peroxo system supported by titanium silicalite-1 (TS-1). After this, the complex was heated, in line with previous in situ FTIR studies, in order to reproduce the catalytic conditions in those studies which demonstrate a reaction pathway to reaction products other than epoxides, namely, carbonyls, which have not been reported previously on this type of catalyst.

BEA supported Ni-Fe catalysts, prepared by various impregnation techniques, were characterised and examined for their activity for the hydrodeoxygenation (HDO) of guaiacol and hydrogenation of toluene. The aim of the study was to explore the factors affecting the formation of Ni-Fe active species and explore the relationship between the concentration of surface Ni, Ni-Fe species and HDO activity. Catalysts prepared initially with Fe, or co-currently with Fe and Ni exhibited a higher level of HDO rate compared to catalyst that was prepared with Ni initially. When a catalyst was impregnated initially with Fe, metal-supported interaction was relatively weak, thus the formation of Ni-Fe species was promoted. In contrast, a reduced number of Ni sites was involved in the formation of Ni-Fe species when the catalyst was initially impregnated with Ni, resulting in a low HDO rate. The rate of cyclohexane formation is proportional to the concentration of surface Ni-Fe over the catalysts with similar Ni and Fe loadings but prepared by different impregnation sequences. The enhanced HDO rate is attributed to the hydrogenolysis activity of Ni-Fe species. The effect of Ni/Fe ratio on HDO activity was also investigated under differential conditions and the catalyst with a Ni/Fe mass ratio of 3.3 exhibited the highest rate of cyclohexane formation.

To overcome diffusional limitations associated with the catalytic cracking of large hydrocarbons, a novel core-shell hierarchical zeolite has been developed and evaluated. Large, branched hydrocarbons encounter diffusional limitations in micropores of zeolites for cracking reactions, a limitation overcome by improved textural properties of hierarchical zeolites, leading to enhanced cracking activity. This will result in an improvement in deactivation rate, cracking activity, and enhanced product selectivity towards light hydrocarbon products. The impact of chain length involving a long chain paraffin (hexadecane) and a highly branched aromatic (1,3,5-TIPB) was also investigated to study the influence of the presence of the micro-mesopore network in overcoming diffusion limitations. This paper investigates the use of hierarchical core-shell BEA@NanoZSM-5 in the catalytic cracking of 1,3,5 triisopropylbenzene (1,3,5-TIPB), and n-hexadecane (C16). The novel hierarchical composite was synthesized by preliminary seeding of the core BEA crystals and subsequent growth under hydrothermal conditions leading to the formation of an intergrown and distinctive nanocrystalline ZSM-5 shell zeolite. Evidence of the existence of a hierarchical structure was probed by Ar sorption utilising non-local density functional theory (NLDFT) pore size distribution analysis.

Chlorpyrifos (CPF) is a widely used pesticide; however, limited experimental work has been completed on its thermal decomposition. CPF is known to decompose into 3,5,6-trichloro-2-pyridinol (TCpyol) together with ethylene and HOPOS. Under oxidative conditions TCpyol can decompose into the dioxin-like 2,3,7,8-tetrachloro-[1,4]-dioxinodipyridine (TCDDPy). With CPF on the cusp of being banned in several jurisdictions worldwide, the question might arise as to how to safely eliminate large stockpiles of this pesticide. Thermal methods such as incineration or thermal desorption of pesticide-contaminated soils are often employed. To assess the safety of thermal methods, information about the toxicants arising from thermal treatment is essential. The present flow reactor study reports the products detected under inert and oxidative conditions from the decomposition of CPF representative of thermal treatments and of wildfires in CPF-contaminated vegetation. Ethylene and TCpyol are the initial products formed at temperatures between 550 and 650 °C, although the detection of HOPOS as a reaction product has proven to be elusive. During pyrolysis of CPF in an inert gas, the dominant sulfur-containing product detected from CPF is carbon disulfide. Quantum chemical analysis reveals that ethylene and HOPOS undergo a facile reaction to form thiirane (c-C2H4S) which subsequently undergoes ring opening reactions to form precursors of CS2. At elevated temperatures (>650 °C), TCpyol undergoes both decarbonylation and dehydroxylation reactions together with decomposition of its primary product, TCpyol. A substantial number of toxicants is observed, including HCN and several nitriles, including cyanogen. No CS2 is observed under oxidative conditions-sulfur dioxide is the fate of S in oxidation of CPF, and quantum chemical studies show that SO2 formation is initiated by the reaction between HOPOS and O2. The range of toxicants produced in thermal decomposition of CPF is summarised.

This paper presents the results of dichloromethane (DCM) decomposition to polymers utilising dielectric barrier discharge under non-oxidative reaction conditions. The conversion levels, mass balance, reaction mechanism and polymer characterisation in relation to DCM reaction are presented in this paper. Reaction pathways describing the decomposition of DCM and subsequent formation of the major products are outlined. Speculation of the mechanism of formation of CHCl3 and C2HCl3 are supported by quantum chemical calculations. In addition, the effect of introducing methane in the reaction feed on the conversion level of DCM and the polymer structure is also examined in this paper.

This work has used high range imaging mass spectrometry to study a coal sample that has undergone heating with a temperature gradient. A custom made hotplate was heated to 1000°C and the coal was allowed to heat naturally through conduction to produce a large thermal gradient typical of conditions in a coke oven. The sample was quenched, sectioned and analysed using laser desorption time of flight imaging mass spectrometry (LDI-TOF-IMS) to study the molecular changes that occur within the plastic layer and in the semi-coke. The raw coal was observed to have a molecular weight range between 500 and 20,000 Da with a peak occurring at 2000 Da. The plastic layer was observed to have a prevalence for increasing 500-1000 Da structures though this formed part of the larger molecular weight range. Resolidification of the plastic layer coincided with a rise in 4000 Da structures. The semi-coke spectrum had a series of repeating peaks separated by 24 Da extending from 1000 Da to 3000 Da. This was considered evidence of broad molecular ordering. A second phenomenon was observed in the semi-coke associated with low range molecular weights (50-300 Da). This appeared as high intensity signals in a molecular range typically considered as ion fragments (being too low in size to remain in the high vacuum environment). It was speculated that these low range structures may be associated with the coking of volatile tars exiting the hot-side of the plastic layer through high temperature semi-coke. Overall, this preliminary work provides a novel methodology to study the heating impacts during coking on a molecular level.

A novel Pd supported on TS-1 combustion catalyst was synthesized and tested in methane combustion under very lean and under highly humid conditions (<1%). A notable increase in hydrothermal stability was observed over 1900 h time-on-stream experiments, where an almost constant, steady state activity obtaining 90% methane conversion was achieved below 500 °C. Surface oxygen mobility and coverage plays a major role in the activity and stability of the lean methane combustion in the presence of large excess of water vapour. We identified water adsorption and in turn the hydrophobicity of the catalyst support as the major factor influencing the long term stability of combustion catalysts. While Pd/Al2O3 catalyst shows a higher turn-over frequency than that of Pd/TS-1 catalyst, the situation reversed after ca. 1900 h on stream. Two linear regions, with different activation energies in the Arrhenius plot for the equilibrium Pd/TS-1 catalyst, were observed. The conclusions were supported by catalyst characterization using H2-chemisorption, TPD, XPS analyses as well as N2-adsorption-desorption, XRD, SEM, TEM. The hydrophobicity and competitive adsorption of water with oxygen is suggested to influence oxygen surface coverage and in turn the apparent activation energy for the oxidation reaction.

In this contribution, the development of a process for the synthesis of potentially highly valuable polymeric products from the reaction of waste glycerol with ammonia is reported for the first time. The polymers were the result of a single step, continuous gas phase process, catalysed by an alumina-supported iron catalyst, operating under relatively mild reaction conditions. The solid product was characterised using 1D and 2D NMR spectroscopy, FTIR spectroscopy, qualitative chemical tests and elemental analysis. Characterisation revealed building blocks with unsaturated, amido and ester functionalities shaping a mixture of polymers. Nitrogen atoms were present in the main chain of the resultant polymers. NMR analyses of the polymer denotes the formation of structural defects such as unsaturation and branching; whilst the partial solubility of the polymer in solvents such as CDCl3 and THF is indicative of the formation of cross-linked structures. Insights into the mechanism of formation of these functional groups were based on the liquid and gas phase product distribution. Polymers with chain structures similar to those synthesised in this work are currently manufactured from fossil fuels and are widely used in biomedical applications not only because of their architecture but also due to their response to changes in pH and temperature.

An increased interest in using hydrocarbons in solid oxide fuel cells for the production of power has led to research into operation on synthesis (syn) gas, a mixture of hydrogen and carbon monoxide. Hydrocarbons are typically reformed, either internally or in an external reformer prior to the fuel cell, producing syngas with various H2:CO ratios depending on the hydrocarbon used. This paper examines the effect of varying the H2:CO ratio with respect to C1 to C4 steam reforming reactions and additionally a mixture containing a higher ratio of carbon monoxide. It was found that there was no significant relationship between cell performance and H2:CO ratio when a high feed rate was employed. For low flow rates, however, the high carbon monoxide concentration resulted in a significant decrease in cell performance. It was determined that this was caused by reversible carbon deposition as opposed to a decrease in carbon monoxide reactivity.

© 2014 Elsevier B.V. All rights reserved. Reagents from a base catalysed condensation reaction (Knoevenagel condensation reaction between ethyl cyanoacetate and benzaldehyde), were adsorbed on ZnO and Al < inf > 2 < /inf > O < inf > 3 < /inf > catalyst surfaces and subject to temperature programmed desorption experiments, monitored using mass spectrometry. Ethyl formate, ketenimine species, carbon dioxide and carbon monoxide were desorption products from ethyl cyanoacetate, while benzene, carbon dioxide and carbon monoxide were desorbed from the catalysts loaded with benzaldehyde. The formation of the ketenimine species was confirmed by in situ FTIR experiments. The observation of the decomposition species further substantiates a proposed reaction mechanism for the Knoevenagel condensation reaction on the catalyst surface of some oxide catalysts.

Reaction of phenol with hydrogen peroxide over H-MFI, Fe-MFI, H-BEA, Fe-BEA and TS-1 zeolite catalysts was investigated. Over H-BEA, biphenyl product was observed. It is suggested, that the larger pore size of H-BEA facilitates coupling of two phenol molecules. Two distinct reaction mechanisms are proposed for acid and redox catalysts. © 2013 Springer Science+Business Media New York.

In this paper we focus on the development of a methodology for treatment of carbon tetrachloride utilising a non-equilibrium plasma operating at atmospheric pressure, which is not singularly aimed at destroying carbon tetrachloride but rather at converting it to a non-hazardous, potentially valuable commodity. This method encompasses the reaction of carbon tetrachloride and methane, with argon as a carrier gas, in a quartz dielectric barrier discharge reactor. The reaction is performed under non-oxidative conditions. Possible pathways for formation of major products based on experimental results and supported by quantum chemical calculations are outlined in the paper. We elucidate important parameters such as carbon tetrachloride conversion, product distribution, mass balance and characterise the chlorinated polymer formed in the process. © 2014 Elsevier B.V.

Conversion of glycerol to allyl alcohol was carried out over an iron on alumina catalyst. With the aim of enhancing selectivity towards the desired product and to reduce acrolein formation (a detrimental impurity in the subsequent epoxidation of allyl alcohol) the supported iron catalyst was modified using alkali metals. It was found that lithium, sodium, potassium, rubidium and caesium deposition on the catalyst surface increased allyl alcohol yield and reduced the rate of catalyst deactivation. Coincidently, acrolein selectivity decreased by up to 75% following treatment with the alkali salt.Changes in the product distribution were determined to be associated with altering the acid/base properties of the catalyst, as confirmed by isopropanol dehydration/dehydrogenation, ammonia and carbon dioxide temperature programmed desorption. The treatment was also found to influence the physical properties of the catalyst surface. A correlation between acid to basic site concentration and allyl alcohol selectivity was established. A reduction in the former value results in an enhancement in the rate of allyl alcohol formation. A reaction mechanism was developed based on the effect of iron and alkali metals catalysing the conversion of glycerol into allyl alcohol. The proposed catalyst modification technique is a straightforward method, readily applicable at a larger scale due to the simplicity of the alkali inclusion and its striking influence on the reaction selectivity. © 2014.

In this paper, we report new insights into the deactivation phenomenon of palladium based catalysts for catalytic combustion of ventilation air methane (VAM). It was found that the primary factor responsible for low temperature catalyst deactivation is the water vapour present in the feed stream. The influence of water vapour on VAM was examined by comparing the properties of fresh catalysts with catalysts following over 1000 h reaction time-on-stream. The techniques applied to characterize the catalysts included TPD, XRD, N 2-isotherm adsorption, H2-chemisorption and XPS analyses. Alternating between dry and water vapour-saturated VAM feed disclosed ca. 50% reversible drop in activity. XPS analysis suggests an absence of a palladium hydroxide phase during the initial 2 h on stream, although prolonged exposure to the reactant leads to the formation of palladium hydroxide, which appears to match the progressive deactivation of the Pd/Al2O3 catalyst. Introduction of VAM dust (a mixture of fine coal, CaCO3 and aluminosilicate particles) causes a variation in catalytic activity originating from coal-dust ignition and the effect of chloride on the surface of the catalyst. In the presence of these inhibiting agents, an average methane conversion of higher than 75% over 1100 h was achieved at reaction temperatures below 600°C. This journal is © the Partner Organisations 2014.

A continuous process for the conversion of glycerol to allyl alcohol, where ammonia or organic acids are added to the feed as sacrificial reductants, was investigated. Significant enhancement on the rate of formation and yield of the allyl alcohol is observed with some of the reducing agents examined over an alumina-supported iron catalyst. Optimising the molar ratio of the reductant relative to feed glycerol results in an increase in the yield of allyl alcohol from 9% (in the absence of additives) to 11.3% with ammonia, 15.1% with ammonium hydroxide, 17.8% with oxalic acid and 19.5% with formic acid. Moreover, the addition of other organic acids, which are produced in a typical glycerol conversion experiment, was studied. However, acetic and propanoic acids had little effect on the rate of formation of allyl alcohol. Analysis of the product distribution in the liquid and gas phases when oxalic and formic acids were added suggests a two-step process for the formation of allyl alcohol under the operating conditions of the reaction; the initial step involves the dehydration of glycerol while the second comprises the reduction of the species produced in step one. © the Partner Organisations 2014.

The adsorption complex of hydrogen chloride on copper-modified ZSM-5 was studied by FTIR and theoretical calculations. The results indicate that the Cl atom of hydrogen chloride is bound to the Cu cations when adsorbed at low pressures (<1 µbar). At higher pressures, HCl adsorbs on the zeolite Brønsted acid sites as well as is hydrogen bonded to the Cu in a larger cluster. Using in situ infrared spectroscopy, we observed a sharp decrease in stretching vibrational frequency of HCl of about 700 cm-1 compared with the H-Cl stretching vibration of gaseous hydrochloric acid. The findings were supported by density functional theory cluster quantum chemical calculations. © 2013 American Chemical Society.