Tuning solid acid catalysts for glucose conversion to platform chemicals

Worldwide concern over dwindling fossil fuel reserves and impact of CO2 emissions on climate change means there is an urgent need to reduce our dependence on oil based sources of fuels and chemicals. The direct conversion of lignocellulosic derived glucose to 5-Hydroxymethylfurfural (5-HMF) is an attractive process for the production of chemicals and fuels but requires a bi-functional catalyst with acid-base or Lewis-Brönsted sites which can operate efficiently in the aqueous phase. While conventionally viewed as a superacid, the potential for tuning the acid strength in SO4/ZrO2 and potential for coupling bi-functional ZrO2-SO4/ZrO2 sites at low sulfate contents have been overlooked. Our previous work has shown effective tuning of the acid strength in SO4/ZrO2 can be used to direct selectivity in terpene isomerisation thus we rationalised control over HMF selectivity could achieved in a similar fashion. Here we report on a systematic study of the impact of acid properties of SO4/ZrO2 catalysts on the conversion of C6 sugars to 5-HMF in aqueous media and correlate the surface acid-base properties with glucose isomerisation and dehydration capabilities.

Designing heterogeneous catalysts for biodiesel synthesis

Concerns over dwindling oil reserves, carbon dioxide emissions from fossil fuel sources and associated climate change is driving the urgent need for clean, renewable energy supplies. The conversion of triglycerides to biodiesel via catalytic transesterification remains an energetically efficient and attractive means to generate transportation fuel1. However, current biodiesel manufacturing routes employing soluble alkali based catalysts are very energy inefficient producing copious amounts of contaminated water waste during fuel purification. Technical advances in catalyst and reactor design and introduction of non-food based feedstocks are thus required to ensure that biodiesel remains a key player in the renewable energy sector for the 21st century. This presentation will give an overview of some recent developments in the design of solid acid and base catalysts for biodiesel synthesis. A particular focus will be on the benefits of designing materials with interconnected hierarchical macro-mesoporous networks to enhance mass-transport of viscous plant oils during reaction.

Hierarchical porous catalysts tailored for biodiesel production

There is a pressing need for sustainable transportation fuels to combat both climate change and dwindling fossil fuel reserves. Biodiesel, synthesised from non-food plant (e.g., Jatropha curcas) or algal crops is one possible solution, but its energy efficient production requires design of new solid catalysts optimized for the bulky triglyceride and fatty acid feedstocks. Here we report on the synthesis of hierarchical macroporous-mesoporous silica and alumina architectures, and their subsequent functionalization by propylsulfonic acid groups or alkaline earth oxides to generate novel solid acid and base catalysts. These materials possess high surface areas and well-defined, interconnected macro-mesopore networks with respective narrow pore size distributions tuneable around 300 nm and 5 nm. Their high conductivity and improved mass transport characteristics enhance activity towards transesterification of bulky tricaprylin and palmitic acid esterification, over mesoporous analogues. This opens the way to the wider application of hierarchical catalysts in biofuel synthesis and biomass conversion.

Simulation process of biodiesel production over heterogeneous catalysts

Biodiesel production is a very promising area due to the relevance that it is an environmental-friendly diesel fuel alternative to fossil fuel derived diesel fuels. Nowadays, most industrial applications of biodiesel production are performed by the transesterification of renewable biological sources based on homogeneous acid catalysts, which requires downstream neutralization and separation leading to a series of technical and environmental problems. However, heterogeneous catalyst can solve these issues, and be used as a better alternative for biodiesel production. Thus, a heuristic diffusion-reaction kinetic model has been established to simulate the transesterification of alkyl ester with methanol over a series of heterogeneous Cs-doped heteropolyacid catalysts. The novelty of this framework lies in detailed modeling of surface reacting kinetic phenomena and integrating that with particle-level transport phenomena all the way through to process design and optimisation, which has been done for biodiesel production process for the first time. This multi-disciplinary research combining chemistry, chemical engineering and process integration offers better insights into catalyst design and process intensification for the industrial application of Cs-doped heteropolyacid catalysts for biodiesel production. A case study of the transesterification of tributyrin with methanol has been demonstrated to establish the effectiveness of this methodology.

Simulation process of biodiesel production over heterogeneous catalysts

Biodiesel production is a very promising area due to the relevance that it is an environmental-friendly diesel fuel alternative to fossil fuel derived diesel fuels. Nowadays, most industrial applications of biodiesel production are performed by the transesterification of renewable biological sources based on homogeneous acid catalysts, which requires downstream neutralization and separation leading to a series of technical and environmental problems. However, heterogeneous catalyst can solve these issues, and be used as a better alternative for biodiesel production. Thus, a heuristic diffusion-reaction kinetic model has been established to simulate the transesterification of alkyl ester with methanol over a series of heterogeneous Cs-doped heteropolyacid catalysts. The novelty of this framework lies in detailed modeling of surface reacting kinetic phenomena and integrating that with particle-level transport phenomena all the way through to process design and optimisation, which has been done for biodiesel production process for the first time. This multi-disciplinary research combining chemistry, chemical engineering and process integration offers better insights into catalyst design and process intensification for the industrial application of Cs-doped heteropolyacid catalysts for biodiesel production. A case study of the transesterification of tributyrin with methanol has been demonstrated to establish the effectiveness of this methodology.

Thermochemical conversion of Brewers Spent Grain combined with catalytic reforming of pyrolysis vapours

The brewing process is an energy intensive process that uses large quantities of heat and electricity. To produce this energy requires a high, mainly fossil fuel consumption and the cost of this is increasing each year due to rising fuel costs. One of the main by-products from the brewing process is Brewers Spent Grain (BSG), an organic residue with very high moisture content. It is widely available each year and is often given away as cattle feed or disposed of to landfill as waste. Currently these methods of disposal are also costly to the brewing process. The focus of this work was to investigate the energy potential of BSG via pyrolysis, gasification and catalytic steam reforming, in order to produce a tar-free useable fuel gas that can be combusted in a CHP plant to develop heat and electricity. The heat and electricity can either be used on site or exported. The first stage of this work was the drying and pre-treatment of BSG followed by characterisation to determine its basic composition and structure so it can be evaluated for its usefulness as a fuel. A thorough analysis of the characterisation results helps to better understand the thermal behaviour of BSG feedstock so it can be evaluated as a fuel when subjected to thermal conversion processes either by pyrolysis or gasification. The second stage was thermochemical conversion of the feedstock. Gasification of BSG was explored in a fixed bed downdraft gasifier unit. The study investigated whether BSG can be successfully converted by fixed bed downdraft gasification operation and whether it can produce a product gas that can potentially run an engine for heat and power. In addition the pyrolysis of BSG was explored using a novel “Pyroformer” intermediate pyrolysis reactor to investigate the behaviour of BSG under these processing conditions. The physicochemical properties and compositions of the pyrolysis fractions obtained (bio-oil, char and permanent gases) were investigated for their applicability in a combined heat power (CHP) application.

On the role of surface roughness in the aerodynamic performance and energy conversion of horizontal wind turbine blades:a review

Summary: Renewable energy is one of the main pillars of sustainable development, especially in developing economies. Increasing energy demand and the limitation of fossil fuel reserves make the use of renewable energy essential for sustainable development. Wind energy is considered to be one of the most important resources of renewable energy. In North African countries, such as Egypt, wind energy has an enormous potential; however, it faces quite a number of technical challenges related to the performance of wind turbines in the Saharan environment. Seasonal sand storms affect the performance of wind turbines in many ways, one of which is increasing the wind turbine aerodynamic resistance through the increase of blade surface roughness. The power loss because of blade surface deterioration is significant in wind turbines. The surface roughness of wind turbine blades deteriorates because of several environmental conditions such as ice or sand. This paper is the first review on the topic of surface roughness effects on the performance of horizontal-axis wind turbines. The review covers the numerical simulation and experimental studies as well as discussing the present research trends to develop a roadmap for better understanding and improvement of wind turbine performance in deleterious environments.

Heterogeneously catalyzed lignin depolymerization

Biomass offers a unique resource for the sustainable production of bio-derived chemical and fuels as drop-in replacements for the current fossil fuel products. Lignin represents a major component of lignocellulosic biomass, but is particularly recalcitrant for valorization by existing chemical technologies due to its complex cross-linking polymeric network. Here, we highlight a range of catalytic approaches to lignin depolymerisation for the production of aromatic bio-oil and monomeric oxygenates.

Combustion of fuel blends containing digestate pyrolysis oil in a multi-cylinder compression ignition engine

Digestate from the anaerobic digestion conversion process is widely used as a farm land fertiliser. This study proposes an alternative use as a source of energy. Dried digestate was pyrolysed and the resulting oil was blended with waste cooking oil and butanol (10, 20 and 30 vol.%). The physical and chemical properties of the pyrolysis oil blends were measured and compared with pure fossil diesel and waste cooking oil. The blends were tested in a multi-cylinder indirect injection compression ignition engine.Engine combustion, exhaust gas emissions and performance parameters were measured and compared with pure fossil diesel operation. The ASTM copper corrosion values for 20% and 30% pyrolysis blends were 2c, compared to 1b for fossil diesel. The kinematic viscosities of the blends at 40 C were 5–7 times higher than that of fossil diesel. Digested pyrolysis oil blends produced lower in-cylinder peak pressures than fossil diesel and waste cooking oil operation. The maximum heat release rates of the blends were approximately 8% higher than with fossil diesel. The ignition delay periods of the blends were higher; pyrolysis oil blends started to combust late and once combustion started burnt quicker than fossil diesel. The total burning duration of the 20% and 30% blends were decreased by 12% and 3% compared to fossil diesel. At full engine load, the brake thermal efficiencies of the blends were decreased by about 3–7% when compared to fossil diesel. The pyrolysis blends gave lower smoke levels; at full engine load, smoke level of the 20% blend was 44% lower than fossil diesel. In comparison to fossil diesel and at full load, the brake specific fuel consumption (wt.) of the 30% and 20% blends were approximately 32% and 15% higher. At full engine load, the CO emission of the 20% and 30% blends were decreased by 39% and 66% with respect to the fossil diesel. Blends CO2 emissions were similar to that of fossil diesel; at full engine load, 30% blend produced approximately 5% higher CO2 emission than fossil diesel. The study concludes that on the basis of short term engine experiment up to 30% blend of pyrolysis oil from digestate of arable crops can be used in a compression ignition engine.

Experimental investigation of the fuel properties of glidfuel, palm oil mill effluent biodiesel and blends

Biofuels derived from industry waste have potential to substitute fossil fuels (Diesel and Gasoline) in internal combustion (IC) engines. Use of waste streams as fuels would help to reduce considerably life-cycle greenhouse gas emissions and minimise waste processing costs. In this study an investigation into the fuel properties of two waste derived biofuels were carried out, they are: (i) Glidfuel (GF) biofuel - a waste stream from paper industry, and (ii) Palm Oil Mill Effluent (POME) biodiesel - biodiesel produced from palm oil industry effluent through various treatment and transesterification process. GF and POME was mixed together at various proportions and separately with fossil diesel (FD) to assess the miscibility and various physical and chemical properties of the blends. Fuel properties such as kinematic viscosity, higher heating value, water content, acid number, density, flash point temperature, CHNO content, sulphur content, ash content, oxidation stability, cetane number and copper corrosion ratings of all the fuels were measured. The properties of GF, POME and various blends were compared with the corresponding properties of the standard FD. Significance of the fuel properties and their expected effects on combustion and exhaust emission characteristics of the IC engine were discussed. Results showed that most properties of both GF and POME biodiesel were comparable to FD. Both GF and POME were miscible with each other, and also separately with the FD. Flash point temperatures of GF and POME biodiesel were 40.7°C and 158.7°C respectively. The flash point temperature of GF was about 36% lower than corresponding FD. The water content in GF and FD were 0.74 (% wt) and 0.01 (% wt) respectively. Acidity values and corrosion ratings of both GF and POME biodiesel were low compared to corresponding value for FD. The study concluded that optimum GF-POME biofuel blends can substitute fossil diesel use in IC engines.