Sequential pyrolysis of willow SRC at low and high heating rates:implications for selective pyrolysis

The main aim of the work is to investigate sequential pyrolysis of willow SRC using two different heating rates (25 and 1500 °C/min) between 320 and 520 °C. Thermogravimetric analysis (TGA) and pyrolysis - gas chromatography - mass spectroscopy (Py-GC-MS) have been used for this analysis. In addition, laboratory scale processing has been undertaken to compare product distribution from fast and slow pyrolysis at 500 °C. Fast pyrolysis was carried out using a 1 kg/h continuous bubbling fluidized bed reactor, and slow pyrolysis using a 100 g batch reactor. Findings from this study show that heating rate and pyrolysis temperatures have a significant influence on the chemical content of decomposition products. From the analytical sequential pyrolysis, an inverse relationship was seen between the total yield of furfural (at high heating rates) and 2-furanmethanol (at low heating rates). The total yield of 1,2-dihydroxybenzene (catechol) was found to be significant higher at low heating rates. The intermediates of catechol, 2-methoxy-4-(2-propenyl)phenol (eugenol); 2-methoxyphenol (guaiacol); 4-Hydroxy-3,5-dimethoxybenzaldehyde (syringaldehyde) and 4-hydroxy-3-methoxybenzaldehyde (vanillin), were found to be highest at high heating rates. It was also found that laboratory scale processing alters the pyrolysis bio-oil chemical composition, and the proportions of pyrolysis product yields. The GC-MS/FID analysis of fast and slow pyrolysis bio-oils reveals significant differences. © 2011 Elsevier Ltd. All rights reserved.

Melting of polymers

The project set out to investigate the relative effectiveness of thermal conductive heating (from external resistance heaters) and viscous heating in the heating (and melting) of low density polyethylene. A model system was used in order to simplify the mathematical analysis. A theory was developed to describe both processes in the model apparatus. The results showed large differences between the experimental and predicted results at low melt temperatures (the predicted results were much greater than the experimental) . Analysis of the results indicated that the apparatus was probably not producing the required shear rates in the sample. The theory appeared to be satisfactory, in that it did not over estimate the viscous heating to any significant extent. The theoretical results could therefore be considered to be a reasonable estimate of the viscous heating.

Experiments on the generation of activated carbon from biomass

Activated carbon is generated from various waste biomass sources like rice straw, wheat straw, wheat straw pellets, olive stones, pistachios shells, walnut shells, beech wood and hardcoal. After drying the biomass is pyrolysed in the temperature range of 500-600 °C at low heating rates of 10 K/min. The activation of the chars is performed as steam activation at temperatures between 800 °C and 900 °C. Both the pyrolysis and activation experiments were run in lab-scale facilities. It is shown that nut shells provide high active surfaces of 1000-1300 m/g whereas the active surface of straw matters does hardly exceed 800 m/g which might be a result of the high ash content of the straws and the slightly higher carbon content of the nut shells. The active surface is detected by BET method. Besides the testing of a many types of biomass for the suitability as base material in the activated carbon production process, the experiments allow for the determination of production parameters like heating rate and pyrolysis temperature, activation time and temperature as well as steam flux which are necessary for the scale up of the process chain. © 2006 Elsevier B.V. All rights reserved.

Flow patterns, performance and scale-up of distillation trays

This work is concerned with the nature of liquid flow across industrial sieve trays operating in the spray, mixed, and the emulsified flow regimes. In order to overcome the practical difficulties of removing many samples from a commercial tray, the mass transfer process was investigated in an air water simulator column by heat transfer analogy. The temperature of the warm water was measured by many thermocouples as the water flowed across the single pass 1.2 m diameter sieve tray. The thermocouples were linked to a mini computer for the storage of the data. The temperature data were then transferred to a main frame computer to generate temperature profiles - analogous to concentration profiles. A comprehensive study of the existing tray efficiency models was carried out using computerised numerical solutions. The calculated results were compared with experimental results published by the Fractionation Research Incorporation (FRl) and the existing models did not show any agreement with the experimental results. Only the Porter and Lockett model showed a reasonable agreement with the experimental results for cenain tray efficiency values. A rectangular active section tray was constructed and tested to establish the channelling effect and the result of its effect on circular tray designs. The developed flow patterns showed predominantly flat profiles and some indication of significant liquid flow through the central region of the tray. This comfirms that the rectangular tray configuration might not be a satisfactory solution for liquid maldistribution on sieve trays. For a typical industrial tray the flow of liquid as it crosses the tray from the inlet to the outlet weir could be affected by the mixing of liquid by the eddy, momentum and the weir shape in the axial or the transverse direction or both. Conventional U-shape profiles were developed when the operating conditions were such that the froth dispersion was in the mixed regime, with good liquid temperature distribution while in the spray regime. For the 12.5 mm hole diameter tray the constant temperature profiles were found to be in the axial direction while in the spray regime and in the transverse direction for the 4.5 mm hole tray. It was observed that the extent of the liquid stagnant zones at the sides of the tray depended on the tray hole diameter and was larger for the 4.5 mm hole tray. The liquid hold-up results show a high liquid hold-up at the areas of the tray with low liquid temperatures, this supports the doubts about the assumptions of constant point efficiency across an operating tray. Liquid flow over the outlet weir showed more liquid flow at the centre of the tray at high liquid loading with low liquid flow at both ends of the weir. The calculated results of the point and tray efficiency model showed a general increase in the calculated point and tray efficiencies with an increase in the weir loading, as the flow regime changed from the spray to the mixed regime the point and the tray efficiencies increased from approximately 30 to 80%.Through the mixed flow regime the efficiencies were found to remain fairly constant, and as the operating conditions were changed to maintain an emulsified flow regime there was a decrease in the resulting efficiencies. The results of the estimated coefficient of mixing for the small and large hole diameter trays show that the extent of liquid mixing on an operating tray generally increased with increasing capacity factor, but decreased with increasing weir loads. This demonstrates that above certain weir loads, the effect of eddy diffusion mechanism on the process of liquid mixing on an operating tray to be negligible.

Pyrolysis and gasification of biomass and acid hydrolysis residues

This research was carried for an EC supported project that aimed to produce ethyl levulinate as a diesel miscible biofuel from biomass by acid hydrolysis. The objective of this research was to explore thermal conversion technologies to recover further diesel miscible biofuels and/or other valuable products from the remaining solid acid hydrolysis residues (AHR). AHR consists of mainly lignin and humins and contains up to 80% of the original energy in the biomass. Fast pyrolysis and pyrolytic gasification of this low volatile content AHR was unsuccessful. However, successful air gasification of AHR gave a low heating value gas for use in engines for power or heat with the aim of producing all the utility requirements in any commercial implementation of the ethyl levulinate production process. In addition, successful fast pyrolysis of the original biomass gave organic liquid yields of up to 63.9 wt.% (dry feed basis) comparable to results achieved using a standard hardwood. The fast pyrolysis liquid can be used as a fuel or upgraded to biofuels. A novel molybdenum carbide catalyst was tested in fast pyrolysis to explore the potential for upgrading. Although there was no deoxygenation, some bio-oil properties were improved including viscosity, pH and homogeneity through decreasing sugars and increasing furanics and phenolics. AHR gasification was explored in a batch gasifier with a comparison with the original biomass. Refractory and low volatile content AHR gave relatively low gas yields (74.21 wt.%), low tar yields (5.27 wt.%) and high solid yields (20.52 wt.%). Air gasification gave gas heating values of around 5MJ/NM3, which is a typical value, but limitations of the equipment available restricted the extent of process and product analysis. In order to improve robustness of AHR powder for screw feeding into gasifiers, a new densification technique was developed based on mixing powder with bio-oil and curing the mixture at 150°C to polymerise the bio-oil.

The deoxidation of steel with simple and complex deoxidisers

The deoxidation of steel with complex deoxidisers was studied at 1550°C and compared with silicon, aluminium and silicon/aluminium alloys as standards. The deoxidation alloy systems, Ca/Si/Al, Mg/Si/Al and Mn/Si/Al, were chosen for the low liquidus temperatures of many of their oxide mixtures and the potential deoxidising power of their constituent elements. Product separation rates and compositional relationships following deoxidation were examined. Silicon/aluminium alloy deoxidation resulted in the product compositions and residual oxygen contents expected from equilibrium and stoichiometric considerations, but with the Ca/Si/Al and Mg/Si/Al alloys the volatility of calcium and magnesium prevented them participating in the final solute equilibrium, despite their reported solubility in liquid iron. Electron-probe microanalysis of the products showed various concentrations of lime and magnesia, possibly resulting from reaction between the metal vapours and dissolved oxygen.The consequent reduction of silica activity in the products due to the presence of CaO and hgO produced an indirect effect of calcium and magnesium on the residual oxygen content. Product separation rates, indicated by vacuum fusion analyses, were not significantly influenced by calcium and magnesium but the rapid separation of products having a high Al2O3Si02 ratio was confirmed. Manganese participated in deoxidation, when present either as an alloying element in the steel or as a deoxidation alloy constituent. The compositions of initial oxide products were related to deoxidation alloy compositions. Separated products which were not alumina saturated, dissolved crucible material to achieve saturation. The melt equilibrated with this slag and crucible by diffusion to determine the residual oxygen content. MnO and SiO2 activities were calculated, and the approximate values of MnO deduced for the compositions obtained. Separation rates were greater for products of high interfacial tension. The rates calculated from a model based on Stoke's Law, showed qualitative agreement with experimental data when corrected for coalescence effects.

Residual stress effects during near-threshold fatigue crack growth

The fatigue crack propagation behaviour of a low alloy, boron-containing steel has been examined after austenitizing at 900°C or 1250°C and tempering at a range of temperatures up to 400°C. Fatigue threshold values were found to vary with austenitizing and tempering treatment in a range between 3.3 to 6 MPa √m when tested at a stress ratio (R) of 0.2. Crack propagation rates in the Paris regime were insensitive to heat treatment variations. The crack propagation path was essentially transgranular in all conditions with small regions of intergranular facets appearing at growth rates around the knee of the da/dN vs ΔK curve. The crack front shape showed marked retardation in the centre of the specimen at low tempering temperatures. Experimental determinations and computer predictions of residual stress levels in the specimens indicated that this was due to a central residual compressive stress resulting from differential cooling rates and the volume change associated with the martensite transformation. The results are discussed in terms of microstructural and residual stress effects on fatigue behaviour. © 1987.

Aspects of 350 ºC (500 ºF) embrittlement in a CrMoV steel

A study has been made of the fracture modes associated with toughness minima, observed in notched impact tests at 173K, for a weldable CrMoV steel, quenched from different austenitising temperatures, and tempered in the range 300-900K. The fracture mode at 623K varied from 100% transgranular cleavage for an austenitising temperature of 1523K. The results are discussed in terms of mechanisms for 350 ºC embrittlement, such mechanisms require modification to allow for the difficulty of dissolving alloy carbides at low austenitising temperatures.

Thermal processing of miscanthus, sugarcane bagasse, sugarcane trash and their acid hydrolysis residues

The research presented in this thesis was developed as part of DIBANET, an EC funded project aiming to develop an energetically self-sustainable process for the production of diesel miscible biofuels (i.e. ethyl levulinate) via acid hydrolysis of selected biomass feedstocks. Three thermal conversion technologies, pyrolysis, gasification and combustion, were evaluated in the present work with the aim of recovering the energy stored in the acid hydrolysis solid residue (AHR). Mainly consisting of lignin and humins, the AHR can contain up to 80% of the energy in the original feedstock. Pyrolysis of AHR proved unsatisfactory, so attention focussed on gasification and combustion with the aim of producing heat and/or power to supply the energy demanded by the ethyl levulinate production process. A thermal processing rig consisting on a Laminar Entrained Flow Reactor (LEFR) equipped with solid and liquid collection and online gas analysis systems was designed and built to explore pyrolysis, gasification and air-blown combustion of AHR. Maximum liquid yield for pyrolysis of AHR was 30wt% with volatile conversion of 80%. Gas yield for AHR gasification was 78wt%, with 8wt% tar yields and conversion of volatiles close to 100%. 90wt% of the AHR was transformed into gas by combustion, with volatile conversions above 90%. 5volO2%-95vol%N2 gasification resulted in a nitrogen diluted, low heating value gas (2MJ/m3). Steam and oxygen-blown gasification of AHR were additionally investigated in a batch gasifier at KTH in Sweden. Steam promoted the formation of hydrogen (25vol%) and methane (14vol%) improving the gas heating value to 10MJ/m3, below the typical for steam gasification due to equipment limitations. Arrhenius kinetic parameters were calculated using data collected with the LEFR to provide reaction rate information for process design and optimisation. Activation energy (EA) and pre-exponential factor (ko in s-1) for pyrolysis (EA=80kJ/mol, lnko=14), gasification (EA=69kJ/mol, lnko=13) and combustion (EA=42kJ/mol, lnko=8) were calculated after linearly fitting the data using the random pore model. Kinetic parameters for pyrolysis and combustion were also determined by dynamic thermogravimetric analysis (TGA), including studies of the original biomass feedstocks for comparison. Results obtained by differential and integral isoconversional methods for activation energy determination were compared. Activation energy calculated by the Vyazovkin method was 103-204kJ/mol for pyrolysis of untreated feedstocks and 185-387kJ/mol for AHRs. Combustion activation energy was 138-163kJ/mol for biomass and 119-158 for AHRs. The non-linear least squares method was used to determine reaction model and pre-exponential factor. Pyrolysis and combustion of biomass were best modelled by a combination of third order reaction and 3 dimensional diffusion models, while AHR decomposed following the third order reaction for pyrolysis and the 3 dimensional diffusion for combustion.

Element characteristic tolerance for semi-batch fixed bed biomass pyrolysis

Biomass pyrolysis to bio-oil is one of the promising sustainable fuels. In this work, relation between biomass feedstock element characteristic and crude bio-oil production yield and lower heating value was explored. The element characteristics considered in this study include moisture, ash, fix carbon, volatile matter, C, H, N, O, S, cellulose, hemicellulose, and lignin content. A semi-batch fixed bed reactor was used for biomass pyrolysis with heating rate of 30 °C/min from room temperature to 600 °C and the reactor was held at 600 °C for 1 h before cooling down. Constant nitrogen flow (1bar) was provided for anaerobic condition. Sago and Napier glass were used in the study to create different element characteristic of feedstock by altering mixing ratio. Comparison between each element characteristic to crude bio-oil yield and low heating value was conducted. The result suggested potential key element characteristic for pyrolysis and provide a platform to access the feedstock element acceptance range.

A study in the application of domestic solar assisted heat pumps for heating and cooling

In the present work, the more important parameters of the heat pump system and of solar assisted heat pump systems were analysed in a quantitative way. Ideal and real Rankine cycles applied to the heat pump, with and without subcooling and superheating were studied using practical recommended values for their thermodynamics parameters. Comparative characteristics of refrigerants here analysed looking for their applicability in heat pumps for domestic heating and their effect in the performance of the system. Curves for the variation of the coefficient of performance as a function of condensing and evaporating temperatures were prepared for R12. Air, water and earth as low-grade heat sources and basic heat pump design factors for integrated heat pumps and thermal stores and for solar assisted heat pump-series, parallel and dual-systems were studied. The analysis of the relative performance of these systems demonstrated that the dual system presents advantages in domestic applications. An account of energy requirements for space and hater heating in the domestic sector in the O.K. is presented. The expected primary energy savings by using heat pumps to provide for the heating demand of the domestic sector was found to be of the order of 7%. The availability of solar energy in the U.K. climatic conditions and the characteristics of the solar radiation here studied. Tables and graphical representations in order to calculate the incident solar radiation over a tilted roof were prepared and are given in this study in section IV. In order to analyse and calculate the heating load for the system, new mathematical and graphical relations were developed in section V. A domestic space and water heating system is described and studied. It comprises three main components: a solar radiation absorber, the normal roof of a house, a split heat pump and a thermal store. A mathematical study of the heat exchange characteristics in the roof structure was done. This permits to evaluate the energy collected by the roof acting as a radiation absorber and its efficiency. An indication of the relative contributions from the three low-grade sources: ambient air, solar boost and heat loss from the house to the roof space during operation is given in section VI, together with the average seasonal performance and the energy saving for a prototype system tested at the University of Aston. The seasonal performance as found to be 2.6 and the energy savings by using the system studied 61%. A new store configuration to reduce wasted heat losses is also discussed in section VI.

Sequential pyrolysis and catalytic low temperature reforming of wheat straw

Aim of the work is the implementation of a low temperature reforming (LT reforming) unit downstream the Haloclean pyrolyser in order to enhance the heating value of the pyrolysis gas. Outside the focus of this work was to gain a synthesis gas quality for further use. Temperatures between 400 °C and 500 °C were applied. A commercial pre-reforming catalyst on a nickel basis from Südchemie was chosen for LT reforming. As biogenic feedstock wheat straw has been used. Pyrolysis of wheat straw at 450 °C by means of Haloclean pyrolysis leads to 28% of char, 50% of condensate and 22% of gas. The condensate separates in a water phase and an organic phase. The organic phase is liquid, but contains viscous compounds. These compounds could underlay aging and could lead to solid tars which can cause post processing problems. Therefore, the implementation of a catalytic reformer is not only of interest from an energetic point of view, it is generally interesting for tar conversion purposes after pyrolysis applications. By using a fixed bed reforming unit at 450–490 °C and space velocities about 3000 l/h the pyrolysis gas volume flow could be increased to about 58%. This corresponds to a decrease of the yields of condensates by means of catalysis up to 17%, the yield of char remains unchanged, since pyrolysis conditions are the same. The heating value in the pyrolysis gas could be increased by the factor of 1.64. Hydrogen concentrations up to 14% could be realised.

Low-temperature isothermal Rankine cycle for desalination

In brackish groundwater desalination, high recovery ratio (of fresh water from saline feed) is desired to minimise concentrate reject. To this effect, previous studies have developed a batch reverse osmosis (RO) desalination system, DesaLink, which proposed to expand steam in a reciprocating piston cylinder and transmit the driving force through a linkage crank mechanism to pressurise batches of saline water (recirculating) in a water piston cylinder unto RO membranes. However, steam is largely disadvantaged at operation from low temperature (< 150oC) thermal sources; and organic working fluids are more viable, though, the obtainable thermal cycle efficiencies are generally low with low temperatures. Consequently, this thesis proposed to investigate the use of organic working fluid Rankine cycle (ORC) with isothermal expansion, to drive the DesaLink machine, at improved thermal efficiency from low temperature thermal sources. Following a review of the methods of achieving isothermal expansion, ‘liquid flooded expansion’ and ‘expansion chamber surface heating’ were identified as potential alternative methods. Preliminary experimental comparative analysis of variants of the heated expansion chamber technique of effecting isothermal expansion favoured a heated plain wall technique, and as such was adopted for further optimisation and development. Further, an optimised isothermal ORC engine was built and tested at < 95oC heat source temperature, with R245fa working fluid – which was selected from 16 working fluids that were analysed for isothermal operation. Upon satisfactory performance of the test engine, a larger (10 times) version was built and coupled to drive the DesaLink system. Operating the integrated ORC-RO DesaLink system, gave freshwater (approximately 500 ppm) production of about 12 litres per hour (from 4000 ppm feed water) at a recovery ratio of about 0.7 and specific energy consumption of 0.34 kWh/m3; and at a thermal efficiency of 7.7%. Theoretical models characterising the operation and performance of the integrated system was developed and utilised to access the potential field performance of the system, when powered by two different thermal energy sources – solar and industrial bakery waste heat – as case studies.