Bio-inspired carbon electro-catalysis for the oxygen reduction reaction

We report the synthesis, characterisation and catalytic performance of two nature-inspired biomass-derived electro-catalysts for the oxygen reduction reaction in fuel cells. The catalysts were prepared via pyrolysis of a real food waste (lobster shells) or by mimicking the composition of lobster shells using chitin and CaCO3 particles followed by acid washing. The simplified model of artificial lobster was prepared for better reproducibility. The calcium carbonate in both samples acts as a pore agent, creating increased surface area and pore volume, though considerably higher in artificial lobster samples due to the better homogeneity of the components. Various characterisation techniques revealed the presence of a considerable amount of hydroxyapatite left in the real lobster samples after acid washing and a low content of carbon (23%), nitrogen and sulphur (<1%), limiting the surface area to 23 m2/g, and consequently resulting in rather poor catalytic activity. However, artificial lobster samples, with a surface area of ≈200 m2/g and a nitrogen doping of 2%, showed a promising onset potential, very similar to a commercially available platinum catalyst, with better methanol tolerance, though with lower stability in long time testing over 10,000 s.

The potential use of bio-ultracarbofluids in a standard diesel engine

The replacement of diesel fuel by ultra-carbofluids was perceived to offer the potential to decrease the emissions of environmental pollutants such as carbon dioxide, carbon monoxide, hydrocarbons (HC's) and smoke. Such ultracarbofluids consist of a suspension of coal in fuel oil and water generally in the ratio of 5: 3: 2 plus a small amount of stabilising additive. The literature relating to the economies of coal and fuel oil production, and the production and properties of charcoal and vegetable oils has been critically reviewed. The potential use of charcoal and vegetable oils as replacements for coal and fuel oil are discussed. An experimental investigation was undertaken using novel bio-ultracarbofluid formulations. These differed from an ultracarbofluid by having bio-renewable charcoal and vegetable oil in place of coal and fuel oil. Tests were made with a Lister-Petter 600cc 2-cylinder, 4-stroke diesel engine fitted with a Heenan-Froude DPX 1 water brake dynamometer to measure brake power output, and Mexa-321E and Mexa-211E analysers to measure exhaust pollutants. Measurements were made of engine brake power output, carbon dioxide, carbon monoxide, hydrocarbons and smoke emissions over the speed range 1000 to 3000 rpm at 200 rpm intervals. The results were compared with those obtained with a standard diesel reference fuel. All the bio-ultracarbofluid formulations produced lower brake power outputs (i.e. 5.6% to 20.7% less brake power) but substantially improved exhaust emissions of CO2, CO, HC's and smoke. The major factor in the formulation was found to be the type and amount of charcoal; charcoal with a high volatile content (27.2%) and present at 30% by mass yielded the best results, i.e. only slightly lower brake power output and significantly lower exhaust pollutants.

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.

Characteristics of the upper phase of bio-oil obtained from co-pyrolysis of sewage sludge with wood, rapeseed and straw

Sewage sludge was pyrolysed with 40% mixed wood, 40% rapeseed and 40% straw. The reason for the mixture of different biomass is to investigate the impact of co-pyrolysis on the upper phase of bio-oil in terms of changes to composition, elemental analysis, viscosity, water content, pH, higher heating value and acid number that could impact on their applications. The biomass was pyrolysed in a laboratory at 450 °C and bio-oil was collected from two cooling traps. The bio-oil obtained from co-pyrolysis of sewage sludge with wood, rapeseed and straw was analysed for composition using the gas chromatography mass spectrometry. The upper phase from the co-pyrolysis process was also characterised for ultimate analysis, higher heating values, water content, viscosity, pH and acid number. There was an increase in the amount of upper phase produced with co-pyrolysis of 40% rapeseed. It was also found that the upper phase from sewage sludge with mixed wood has the highest viscosity, acid number and lowest pH. The bio-oil containing 40% straw was found to have a pH of 6.5 with a very low acid number while the 40% rapeseed was found to have no acid number. Sewage sludge with 40% rapeseed was found to have the highest energy content of 34.8 MJ/kg, 40% straw has 32.5 MJ/kg while the 40% mixed wood pyrolysis oil has the lowest energy content of 31.3 MJ/kg. The 40% rapeseed fraction was found to have the highest water content of 8.2% compared to other fractions.

Results of the IEA round robin on viscosity and stability of fast pyrolysis bio-oils

An international round robin study of the stability of fast pyrolysis bio-oil was undertaken. Fifteen laboratories in five different countries contributed. Two bio-oil samples were distributed to the laboratories for stability testing and further analysis. The stability test was defined in a method provided with the bio-oil samples. Viscosity measurement was a key input. The change in viscosity of a sealed sample of bio-oil held for 24 h at 80 °C was the defining element of stability. Subsequent analyses included ultimate analysis, density, moisture, ash, filterable solids, and TAN/pH determination, and gel permeation chromatography. The results showed that kinematic viscosity measurement was more generally conducted and more reproducibly performed versus dynamic viscosity measurement. The variation in the results of the stability test was great and a number of reasons for the variation were identified. The subsequent analyses proved to be at the level of reproducibility, as found in earlier round robins on bio-oil analysis. Clearly, the analyses were more straightforward and reproducible with a bio-oil sample low in filterable solids (0.2%), compared to one with a higher (2%) solids loading. These results can be helpful in setting standards for use of bio-oil, which is just coming into the marketplace. © 2012 American Chemical Society.

The development of a novel Bio-MEMS filtration chip for the separation of specific cells in fluid suspension

In the clinical/microbiological laboratory there are currently several ways of separating specific cells from a fluid suspension. Conventionally cells can be separated based on size, density, electrical charge, light-scattering properties, and antigenic surface properties. Separating cells using these parameters can require complex technologies and specialist equipment. This paper proposes new Bio-MEMS (microelectromechanical systems) filtration chips manufactured using deep reactive ion etching (DRIE) technology that, when used in conjunction with an optical microscope and a syringe, can filter and grade cells for size without the requirement for additional expensive equipment. These chips also offer great versatility in terms of design and their low cost allows them to be disposable, eliminating sample contamination. The pumping mechanism, unlike many other current filtration techniques, leaves samples mechanically and chemically undamaged. In this paper the principles behind harnessing passive pumping are explored, modelled, and validated against empirical data, and their integration into a microfluidic device to separate cells from a mixed population suspension is described. The design, means of manufacture, and results from preliminary tests are also presented. © IMechE 2007.

Ash control methods to limit biomass inorganic content and its effect on fast pyrolysis bio-oil stability

This research investigates specific ash control methods to limit inorganic content within biomass prior to fast pyrolysis and effect of specific ash components on fast pyrolysis processing, mass balance yields and bio-oil quality and stability. Inorganic content in miscanthus was naturally reduced over the winter period from June (7.36 wt. %) to February (2.80 wt. %) due to a combination of senescence and natural leaching from rain water. September harvest produced similar mass balance yields, bio-oil quality and stability compared to February harvest (conventional harvest), but nitrogen content in above ground crop was to high (208 kg ha.-1) to maintain sustainable crop production. Deionised water, 1.00% HCl and 0.10% Triton X-100 washes were used to reduce inorganic content of miscanthus. Miscanthus washed with 0.10% Triton X-100 resulted in the highest total liquid yield (76.21 wt. %) and lowest char and reaction water yields (9.77 wt. % and 8.25 wt. % respectively). Concentrations of Triton X-100 were varied to study further effects on mass balance yields and bio-oil stability. All concentrations of Triton X-100 increased total liquid yield and decreased char and reaction water yields compared to untreated miscanthus. In terms of bio-oil stability 1.00% Triton X-100 produced the most stable bio-oil with lowest viscosity index (2.43) and lowest water content index (1.01). Beech wood was impregnated with potassium and phosphorus resulting in lower liquid yields and increased char and gas yields due to their catalytic effect on fast pyrolysis product distribution. Increased potassium and phosphorus concentrations produced less stable bio-oils with viscosity and water content indexes increasing. Fast pyrolysis processing of phosphorus impregnated beech wood was problematic as the reactor bed material agglomerated into large clumps due to char formation within the reactor, affecting fluidisation and heat transfer.

Optical fibre gratings with response to 2μm and their sensing capabilities

Recently, we have extended fibre grating devices in to mid-IR range. Fibre Bragg gratings (FBGs) and long-period gratings (LPGs) with spectral responses from near-IR (800nm) to mid-IR ( ∼ 2μm) have been demonstrated with transmission loss as strong as 10-20dB. 2μm FBG and LPG showed temperature and refractive index (RI) sensitivities of ∼ 91pm/°C and 357nm/RIU respectively. Finally, we have performed a bio sensing experiment by monitoring the degradation of foetal bovine serum at room temperature. The results encouragingly show that the mid-IR LPGs can be an ideal biosensor platform as they have high RI sensitivity and can be used to detect concentration change of bio-samples. © 2012 SPIE.

Viscosity of aged bio-oils from fast pyrolysis of beech wood and miscanthus:shear rate and temperature dependence

The viscosity of four aged bio-oil samples was measured experimentally at various shear rates and temperatures using a rotational viscometer. The experimental bio-oils were derived from fast pyrolysis of beech wood at 450, 500, and 550 °C and Miscanthus at 500 °C (in this work, they were named as BW1, BW2, BW3, and MXG) in a bubbling fluidized bed reactor. The viscosity of all bio-oils was kept constant at various shear rates at the same temperature, which indicated that they were Newtonian fluids. The viscosity of bio-oils was strongly dependent upon the temperature, and with the increase of the temperature from 30 to 80 °C, the viscosity of BW1, BW2, BW3, and MXG decreased by 90.7, 93.3, 92.6, and 90.2%, respectively. The Arrhenius viscosity model, which has been commonly used to represent the temperature dependence of the viscosity of many fluids, did not fit the viscosity-temperature experimental data of all bio-oils very well, especially in the low- and high-temperature regions. For comparison, the Williams-Landel-Ferry (WLF) model was also used. The results showed that the WLF model gave a very good description of the viscosity-temperature relationship of each bio-oil with very small residuals and the BW3 bio-oil had the strongest viscosity-temperature dependence.

Impact of potassium and phosphorus in biomass on the properties of fast Pyrolysis bio-oil

This study investigates fast pyrolysis bio-oils produced from alkali-metal-impregnated biomass (beech wood). The impregnation aim is to study the catalytic cracking of the pyrolysis vapors as a result of potassium or phosphorus. It is recognized that potassium and phosphorus in biomass can have a major impact on the thermal conversion processes. When biomass is pyrolyzed in the presence of alkali metal cations, catalytic cracking of the pyrolysis liquids occurs in the vapor phase, reducing the organic liquids produced and increasing yields of water, char, and gas, resulting in a bio-oil that has a lower calorific value and an increased chance of phase separation. Beech wood was impregnated with potassium or phosphorus (K impregnation and P impregnation, respectively) in the range of 0.10-2.00 wt %. Analytical pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) was used to examine the pyrolysis products during thermal degradation, and thermogravimetric analysis (TGA) was used to examine the distribution of char and volatiles. Both potassium and phosphorus are seen to catalyze the pyrolytic decomposition of biomass and modify the yields of products. 3-Furaldehyde and levoglucosenone become more dominant products upon P impregnation, pointing to rearrangement and dehydration routes during the pyrolysis process. Potassium has a significant influence on cellulose and hemicellulose decomposition, not just on the formation of levoglucosan but also other species, such as 2(5H)-furanone or hydroxymethyl-cyclopentene derivatives. Fast pyrolysis processing has also been undertaken using a laboratory-scale continuously fed bubbling fluidized-bed reactor with a nominal capacity of 1 kg h-1 at the reaction temperature of 525 °C. An increase in the viscosity of the bio-oil during the stability assessment tests was observed with an increasing percentage of impregnation for both additives. This is because bio-oil undergoes polymerization while placed in storage as a result of the inorganic content. The majority of inorganics are concentrated in the char, but small amounts are entrained in the pyrolysis vapors and, therefore, end up in the bio-oil.