Hierarchical mesoporous Pd/ZSM-5 for the selective catalytic hydrodeoxygenation of m-cresol to methylcyclohexane

Mesopore incorporation into ZSM-5 enhances the dispersion of Pd nanoparticles throughout the hierarchical framework, significantly accelerating m-cresol conversion relative to a conventional microporous ZSM-5, and dramatically increasing selectivity towards the desired methylcyclohexane deoxygenated product. Increasing the acid site density further promotes m-cresol conversion and methylcyclohexane selectivity through efficient dehydration of the intermediate methylcyclohexanol.

Fast pyrolysis of cassava rhizome in the presence of catalysts

Cassava rhizome was catalytically pyrolysed at 500 °C using analytical pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) in order to investigate the effect of catalysts on bio-oil properties. The catalysts studied were zeolite ZSM-5, two aluminosilicate mesoporous materials Al-MCM-41 and Al-MSU-F, and a proprietary commercial catalyst alumina-stabilised ceria MI-575. The influence of catalysts on pyrolysis products was observed through the yields of aromatic hydrocarbons, phenols, lignin-derived compounds, carbonyls, methanol and acetic acid. Results showed that all the catalysts produced aromatic hydrocarbons and reduced oxygenated lignin derivatives, thus indicating an improvement of bio-oil heating value and viscosity. Among the catalysts, ZSM-5 was the most active to all the changes in pyrolysis products. In addition, all the catalysts with the exception of MI-575 enhanced the formation of acetic acid. This is clearly a disadvantage with respect to the level of pH in the liquid bio-fuel.

Evaluation of catalytic pyrolysis of cassava rhizome by principal component analysis

Rhizome of cassava plants (Manihot esculenta Crantz) was catalytically pyrolysed at 500 °C using analytical pyrolysis–gas chromatography/mass spectrometry (Py–GC/MS) method in order to investigate the relative effect of various catalysts on pyrolysis products. Selected catalysts expected to affect bio-oil properties were used in this study. These include zeolites and related materials (ZSM-5, Al-MCM-41 and Al-MSU-F type), metal oxides (zinc oxide, zirconium (IV) oxide, cerium (IV) oxide and copper chromite) catalysts, proprietary commercial catalysts (Criterion-534 and alumina-stabilised ceria-MI-575) and natural catalysts (slate, char and ashes derived from char and biomass). The pyrolysis product distributions were monitored using models in principal components analysis (PCA) technique. The results showed that the zeolites, proprietary commercial catalysts, copper chromite and biomass-derived ash were selective to the reduction of most oxygenated lignin derivatives. The use of ZSM-5, Criterion-534 and Al-MSU-F catalysts enhanced the formation of aromatic hydrocarbons and phenols. No single catalyst was found to selectively reduce all carbonyl products. Instead, most of the carbonyl compounds containing hydroxyl group were reduced by zeolite and related materials, proprietary catalysts and copper chromite. The PCA model for carboxylic acids showed that zeolite ZSM-5 and Al-MSU-F tend to produce significant amounts of acetic and formic acids.

Catalytic pyrolysis of agricultural residues for bio-oil production

Agricultural residues from Thailand, namely stalk and rhizome of cassava plants, were employed as raw materials for bio-oil production via fast pyrolysis technology. There were two main objectives of this project. The first one was to determine the optimum pyrolysis temperature for maximising the organics yield and to investigate the properties of the bio-oils produced. To achieve this objective, pyrolysis experiments were conducted using a bench-scale (150 g/h) reactor system, followed by bio-oil analysis. It was found that the reactor bed temperature that could give the highest organics yield for both materials was 490±15ºC. At all temperatures studied, the rhizome gave about 2-4% higher organics yields than the stalk. The bio-oil derived from the rhizome had lower oxygen content, higher calorific value and better stability, thus indicating better quality than that produced from the stalk. The second objective was to improve the bio-oil properties in terms of heating value, viscosity and storage stability by the incorporation of catalyst into the pyrolysis process. Catalytic pyrolysis was initially performed in a micro-scale reactor to screen a large number of catalysts. Subsequently, seven catalysts were selected for experiments with larger-scale (150 g/h) pyrolysis unit. The catalysts were zeolite and related materials (ZSM-5, Al-MCM-41 and Al-MSU-F), commercial catalysts (Criterion-534 and MI-575), copper chromite and ash. Additionally, the combination of two catalysts in series was investigated. These were Criterion-534/ZSM-5 and Al-MSU-F/ZSM-5. The results showed that all catalysts could improve the bio-oils properties as they enhanced cracking and deoxygenation reactions and in some cases such as ZSM-5, Criterion-534 and Criterion-534/ZSM-5, valuable chemicals like hydrocarbons and light phenols were produced. The highest concentration of these compounds was obtained with Criterion-534/ZSM-5.

Catalytic intermediate pyrolysis of Brunei rice husk for bio-oil production

Rice husks from Brunei were subjected via intermediate pyrolysis for bio-oil production. Two main objectives were set out for this study. The application of intermediate pyrolysis on Brunei rice husk for the production of bio-oil is the main objective of this experiment. Characterisation of the rice husks was inclusive as a pre-requisite step to assess the suitability as feedstock for production of liquid fuels. Following on from the characterisation results, a temperature of 450°C was established as the optimum temperature for the production of bio-oil. A homogenous bio-oil was obtained from the pyrolysis of dry rice husk, and the physicochemical properties and chemical compositions were analysed. The second objective is the introduction of catalysts into the pyrolysis process which aims to improve the bio-oil quality, and maximise the desired liquid bio-oil properties. The incorporation of the catalysts was done via a fixed tube reactor into the pyrolysis system. Ceramic monoliths were used as the catalyst support, with montmorillonite clay as a binder to attach the catalysts onto the catalyst support. ZSM-5, Al-MCM-41, Al-MSU-F and Brunei rice husk ash (BRHA) together with its combination were adopted as catalysts. Proposed criterions dictated the selection of the best catalysts, subsequently leading to the optimisation process for bio-oil production. ZSM-5/Al-MCM-41 proved the most desirable catalyst, which increases the production of aromatics and phenols, decreased the organic acids and improved the physicochemical properties such as the pH, viscosity, density and H:C molar ratios. Variation in the ratio and positioning of both catalysts were the significant key factor for the catalyst optimisation study.

Hydrogen production by steam reforming of DME in a large scale CFB reactor. Part I:computational model and predictions

This study presents a computational fluid dynamic (CFD) study of Dimethyl Ether steam reforming (DME-SR) in a large scale Circulating Fluidized Bed (CFB) reactor. The CFD model is based on Eulerian-Eulerian dispersed flow and solved using commercial software (ANSYS FLUENT). The DME-SR reactions scheme and kinetics in the presence of a bifunctional catalyst of CuO/ZnO/Al2O3+ZSM-5 were incorporated in the model using in-house developed user-defined function. The model was validated by comparing the predictions with experimental data from the literature. The results revealed for the first time detailed CFB reactor hydrodynamics, gas residence time, temperature distribution and product gas composition at a selected operating condition of 300 °C and steam to DME mass ratio of 3 (molar ratio of 7.62). The spatial variation in the gas species concentrations suggests the existence of three distinct reaction zones but limited temperature variations. The DME conversion and hydrogen yield were found to be 87% and 59% respectively, resulting in a product gas consisting of 72 mol% hydrogen. In part II of this study, the model presented here will be used to optimize the reactor design and study the effect of operating conditions on the reactor performance and products.

Catalytic pyrolysis of rice husk for bio-oil production

Catalytic pyrolysis experiments have been carried out on Brunei rice husk (BRH) to obtain bio-oil using a fixed-bed pyrolysis rig. ZSM-5, Al-MCM-41, Al-MSU-F and Brunei rice husk ash (BRHA) were used as the catalysts for the catalytic pyrolysis experiments and comparison was done to analyse the changes in the bio-oil properties and yield. Properties of the liquid catalytic and non-catalytic bio-oil were analysed in terms of water content, pH, acid number, viscosity, density and calorific value. The bio-oil chemical composition shows that ZSM-5 increases the production of aromatic hydrocarbons and light phenols, whilst Al-MCM-41 reduces the acetic acid production. The catalytic runs increased the calorific value and water content in the bio-oil, whilst viscosity, density and acid number is decreased. © 2012 Elsevier B.V. All rights reserved.

Size-controlled TiO2 nanoparticles on porous hosts for enhanced photocatalytic hydrogen production

Nanocystalline TiO2 particles were successfully synthesized on porous hosts (SBA-15 and ZSM-15) via a sol-gel impregnation method. Resulting nanocomposites were characterized by XRD, TEM, BET surface analysis, Raman and UV-vis diffuse reflectance spectroscopy, and their photocatalytic activity for H2 production evaluated. XRD evidences the formation of anatase nanoparticles over both ZSM-5 and SBA-15 porous supports, with TEM highlighting a strong particle size dependence on titania precursor concentration. Photocatalytic activities of TiO2/ZSM-5 and TiO2/SBA-15 composites were significantly enhanced compared to pure TiO2, owing to the smaller TiO2 particle size and higher surface area of the former. TiO2 loadings over the porous supports and concomitant photocatalytic hydrogen production were optimized with respect to light absorption, available surface reaction sites and particle size. 10%TiO2/ZSM-5 and 20%TiO2/SBA-15 proved the most active photocatalysts, exhibiting extraordinary hydrogen evolution rates of 10,000 and 8800μmolgTiO2 -1 h-1 under full arc, associated with high external quantum efficiencies of 12.6% and 5.4% respectively under 365nm irradiation.

Studies on the deactivation and reactivation of spent hydroprocessing catalyst

A study is reported on the deactivation of hydroprocessing catalysts and their reactivation by the removal of coke and metal foulants. The literature on hydrotreating catalyst deactivation by coke and metals deposition, the environmental problems associated with spent catalyst disposal, and its reactivation/rejuvenation process were reviewed. Experimental studies on catalyst deactivation involved problem analysis in industrial hydroprocessing operations, through characterization of the spent catalyst, and laboratory coking studies. A comparison was made between the characteristics of spent catalysts from fixed bed and ebullating bed residue hydroprocessing reactor units and the catalyst deactivation pattern in both types of reactor systems was examined. In the laboratory the nature of initial coke deposited on the catalyst surface and its role on catalyst deactivation were studied. The influence of initial coke on catalyst surface area and porosity was significant. Both catalyst acidity and feedstock quality had a remarkable influence on the amount and the nature of the initial coke. The hydroenitrogenation function (HDN) of the catalyst was found to be deactivated more rapidly by the initial coke than the hydrodesulphurization function (HDS). In decoking experiments, special attention was paid to the initial conditions of coke combustion, since the early stages of contact between the coke on the spent catalyst surface and the oxygen are crucial in the decoking process. An increase in initial combustion temperature above 440oC and the oxygen content of the regeneration gas above 5% vanadium led to considerable sintering of the catalyst. At temperatures above 700oC there was a substantial loss of molybdenum from the catalyst, and phase transformations in the alumina support. The preferred leaching route (coked vs decoked form of spent catalyst) and a comparison of different reagents (i.e., oxalic acid and tartaric acid) and promoters (i.e., Hydrogen Peroxide and Ferric Nitrate) for better selectivity in removing the major foulant (vanadium), characterization and performance evaluation of the treated catalysts and modelling of the leaching process were addressed in spent catalyst rejuvenation studies. The surface area and pore volume increased substantially with increasing vanadium extraction from the spent catalyst; the HDS activity showed a parallel increase. The selectivity for leaching of vanadium deposits was better, and activity recovery was higher, for catalyst rejuvenated by metal leaching prior to decoking.

Three-dimensional nitrogen-doped graphene supported molybdenum disulfide nanoparticles as an advanced catalyst for hydrogen evolution reaction

An efficient three-dimensional (3D) hybrid material of nitrogen-doped graphene sheets (N-RGO) supporting molybdenum disulfide (MoS2) nanoparticles with high-performance electrocatalytic activity for hydrogen evolution reaction (HER) is fabricated by using a facile hydrothermal route. Comprehensive microscopic and spectroscopic characterizations confirm the resulting hybrid material possesses a 3D crumpled few-layered graphene network structure decorated with MoS2 nanoparticles. Electrochemical characterization analysis reveals that the resulting hybrid material exhibits efficient electrocatalytic activity toward HER under acidic conditions with a low onset potential of 112 mV and a small Tafel slope of 44 mV per decade. The enhanced mechanism of electrocatalytic activity has been investigated in detail by controlling the elemental composition, electrical conductance and surface morphology of the 3D hybrid as well as Density Functional Theory (DFT) calculations. This demonstrates that the abundance of exposed active sulfur edge sites in the MoS2 and nitrogen active functional moieties in N-RGO are synergistically responsible for the catalytic activity, whilst the distinguished and coherent interface in MoS 2 /N-RGO facilitates the electron transfer during electrocatalysis. Our study gives insights into the physical/chemical mechanism of enhanced HER performance in MoS2/N-RGO hybrids and illustrates how to design and construct a 3D hybrid to maximize the catalytic efficiency.

Enhanced selective aerobic alcohol oxidation through nanoengineered catalyst supports

The selective conversion of alcohols to their carbonyl derivatives is a critical step towards a sustainable chemical industry. Heterogeneous Pd catalysts represent some of the most active systems known, even so further studies into the active species and role of support are required. Through controlling support mesostructure, using non-interconnected SBA-15 and interlinked SBA-16 and KIT-6, we have evaluated the role of pore architecture on supported Pd nanoparticles and their subsequent activity for liquid phase aerobic allylic alcohol selective oxidation.[1,2] These synthesised silica supports exhibit high surface areas (>800 m2g-1), and similar mesopore diameters (3.5 to 5 nm), but differ in their pore connectivity and arrangement; p6mm (SBA-15), I3mm (SBA-16) and I3ad (KIT-6). When evaluated alongside commercial non-mesoporous silica (200 m2 g-1) they promote enhanced Pd dispersion with interpenetrating assemblies providing further elevation. Macropore introduction into SBA-15, producing a hierarchical macro-mesoporous silica (MM-SBA-15), allows control over mesopore length and accessibility which escalates Pd distribution to levels akin to KIT-6 and SBA-16. Controlling dispersion, and likewise nanoparticle size, is thus facilitated through the choice of support and additionally Pd loading, with cluster sizes spanning 3.2 to 0.8 nm. X-ray spectroscopies indicate nanoparticles are PdO terminated with the oxide content a function of dispersion. Kinetic studies allude to surface PdO being the active site responsible, with a constant TOF observed, independent of loading and support. This confirms activity is governed by PdO density, whilst also overruling internal mass diffusion constraints. MM-SBA-15 facilitates superior activity and TOFs for long chain acyclic terpene alcohols due to reduced internal mass transport constraints.

Hierarchically ordered nanoporous Pd/SBA-15 catalyst for the aerobic selective oxidation of sterically challenging allylic alcohols

The utility of a hierarchically ordered nanoporous SBA-15 architecture, comprising 270 nm macropores and 5 nm mesopores (MM-SBA-15), for the catalytic aerobic selective oxidation of sterically challenging allylic alcohols is shown. Detailed bulk and surface characterization reveals that incorporation of complementary macropores into mesoporous SBA-15 enhances the dispersion of sub 2 nm Pd nanoparticles and thus their degree of surface oxidation. Kinetic profiling reveals a relationship between nanoparticle dispersion and oxidation rate, identifying surface PdO as the catalytically active phase. Hierarchical nanoporous Pd/MM-SBA-15 outperforms mesoporous analogues in allylic alcohol selective oxidation by (i) stabilizing PdO nanoparticles and (ii) dramatically improving in-pore diffusion and access to active sites by sesquiterpenoid substrates such as farnesol and phytol. © 2013 American Chemical Society.

A polyoxometallate-tethered Ru complex as a catalyst in solventless phenyl acetylene oligomerisation

A novel compound comprising a Ru–tethered polyoxometallate Keggin anion of formula [HNEt3]+[(Ru{η5-C5H5}{PPh3}2)2(PW12O40)]− has been synthesised that shows high activity and selectivity in alkyne oligomerisation. In situ IR binding studies using CO confirmed the accessibility of the Ru centre for catalysis. Phenyl acetylene was successfully dimerised under a heterogeneous catalytic regime. Selectivity towards the (E)-enyne, not found in the homogeneous Ru(η5-C5H5)(PPh3)2Cl analogue, was achieved while retaining high a turnover frequency of 225 h−1.

Propene combustion over a model Pt/Al2O3/NiAl{110} catalyst

The genesis of a catalytically active model Pt/Al2O3/NiAl{110} oxidation catalyst is described. An ultrathin, crystalline γ-Al2O3 film was prepared via direct oxidation of a NiAl{110} single-crystal substrate. The room-temperature deposition of Pt clusters over the γ-Al2O3 film was characterised by LEED, AES and CO titration and follows a Stranski–Krastanov growth mode. Surface sulfation was attempted via SO2/O2 adsorption and thermal processing over bare and Pt promoted Al2O3/NiAl{110}. Platinum greatly enhances the saturation SOx coverage over that of bare alumina. Over clean Pt/γ-Al2O3 surfaces some adsorbed propene desorbs molecularly [similar]250 K while the remainder decomposes liberating hydrogen. Coadsorbed oxygen or sulfate promote propene combustion, with adsorbed sulfoxy species the most efficient oxidant. The chemistry of these alumina-supported Pt clusters shows a general evolution from small polycrystalline clusters to larger clusters with properties akin to low-index, Pt single-crystal surfaces.