Plant oils as fuels for compression ignition engines: a technical review and life-cycle analysis

As an alternative fuel for compression ignition engines, plant oils are in principle renewable and carbon-neutral. However, their use raises technical, economic and environmental issues. A comprehensive and up-to-date technical review of using both edible and non-edible plant oils (either pure or as blends with fossil diesel) in CI engines, based on comparisons with standard diesel fuel, has been carried out. The properties of several plant oils, and the results of engine tests using them, are reviewed based on the literature. Findings regarding engine performance, exhaust emissions and engine durability are collated. The causes of technical problems arising from the use of various oils are discussed, as are the modifications to oil and engine employed to alleviate these problems. The review shows that a number of plant oils can be used satisfactorily in CI engines, without transesterification, by preheating the oil and/or modifying the engine parameters and the maintenance schedule. As regards life-cycle energy and greenhouse gas emission analyses, these reveal considerable advantages of raw plant oils over fossil diesel and biodiesel. Typical results show that the life-cycle output-to-input energy ratio of raw plant oil is around 6 times higher than fossil diesel. Depending on either primary energy or fossil energy requirements, the life-cycle energy ratio of raw plant oil is in the range of 2–6 times higher than corresponding biodiesel. Moreover, raw plant oil has the highest potential of reducing life-cycle GHG emissions as compared to biodiesel and fossil diesel.

A comparative study on the pyrolysis of metal- and ash-enriched wood and the combustion properties of the gained char

This study aims to investigate the pyrolysis behaviour of metal-contaminated wood and the combustion properties of char derived from wood pyrolysis. Seven metals (Na, Mg, Ca, Zn, Cd, Pb and Fe(III)) were introduced to willow in cation form by ion-exchange and the thermal behaviour of demineralised samples and samples with additional ash were also investigated. The results show that the char yield increased from 21% to 24-28% and levoglucosan yield in vapour phase decreased from 88% to 62-29% after the addition of inorganic compounds, even though the metal binding capacity of wood varied from one metal ion to another. While char yield seems to be effected mainly by the concentration of the metal ions, levoglucosan yield was more dependent on the ionic species especially when sodium ions were present. When combustion experiments were carried out with char made of the metal enriched wood, two consecutive steps were observed, both effected by the presence of inorganic compounds. The first step was identified as the release and combustion of volatiles, while the second peak of the burning profile is the actual combustion of the fixed carbon. The burnout temperatures, estimated ignition indices and the conversion indicate that the type and not the amount of metal ions were the determining factors during the second step of combustion. © 2012 Published by Elsevier B.V.

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.

Characterisation of waste derived intermediate pyrolysis oils for use as diesel engine fuels

This paper studies the characteristics of intermediate pyrolysis oils derived from sewage sludge and de-inking sludge (a paper industry residue), with a view to their use as fuels in a diesel engine. The feedstocks were dried and pelletised, then pyrolysed in the Pyroformer intermediate pyrolysis system. The organic fraction of the oils was separated from the aqueous phase and characterised. This included elemental and compositional analysis, heating value, cetane index, density, viscosity, surface tension, flash point, total acid number, lubricity, copper corrosion, water, carbon residue and ash content. Most of these results are compared with commercial diesel and biodiesel. Both pyrolysis oils have high carbon and hydrogen contents and their higher heating values compare well with biodiesel. The water content of the pyrolysis oils is reasonable and the flash point is found to be high. Both pyrolysis oils have good lubricity, but show some corrosiveness. Cetane index is reduced, which may influence ignition. Also viscosity is increased, which may influence atomisation quality. Carbon residue and ash content are both high, indicating potential deposition problems. Compared with de-inking sludge pyrolysis oil (DSPO), sewage sludge pyrolysis oil (SSPO) has a higher heating value, but higher corrosiveness and viscosity. The conclusions are that both intermediate pyrolysis oils will be able to provide sufficient heat when used in diesel engine; however poor combustion and carbon deposition may be encountered. Blending of these pyrolysis oils with diesel or biodiesel could overcome these problems and is recommended for further investigation.

Fast pyrolysis and nitrogenolysis of biomass and biogenic residues:production of a sustainable slow release fertiliser

The production of agricultural and horticultural products requires the use of nitrogenous fertiliser that can cause pollution of surface and ground water and has a large carbon footprint as it is mainly produced from fossil fuels. The overall objective of this research project was to investigate fast pyrolysis and in-situ nitrogenolysis of biomass and biogenic residues as an alternative route to produce a sustainable solid slow release fertiliser mitigating the above stated problems. A variety of biomasses and biogenic residues were characterized by proximate analysis, ultimate analysis, thermogravimetric analysis (TGA) and Pyrolysis – Gas chromatography – Mass Spectroscopy (Py–GC–MS) for their potential use as feedstocks using beech wood as a reference material. Beech wood was virtually nitrogen free and therefore suitable as a reference material as added nitrogen can be identified as such while Dried Distillers Grains with Solubles (DDGS) and rape meal had a nitrogen content between 5.5wt.% and 6.1wt.% qualifying them as high nitrogen feedstocks. Fast pyrolysis and in-situ nitrogenolysis experiments were carried out in a continuously fed 1kg/h bubbling fluidized bed reactor at around 500°C quenching the pyrolysis vapours with isoparaffin. In-situ nitrogenolysis experiments were performed by adding ammonia gas to the fast pyrolysis reactor at nominal nitrogen addition rates between 5wt.%C and 20wt.%C based on the dry feedstock’s carbon content basis. Mass balances were established for the processing experiments. The fast pyrolysis and in-situ nitrogenolysis products were characterized by proximate analysis, ultimate analysis and GC– MS. High liquid yields and good mass balance closures of over 92% were obtained. The most suitable nitrogen addition rate for the in-situ nitrogenolysis experiments was determined to be 12wt.%C on dry feedstock carbon content basis. However, only a few nitrogen compounds that were formed during in-situ nitrogenolysis could be identified by GC–MS. A batch reactor process was developed to thermally solidify the fast pyrolysis and in-situ nitrogenolysis liquids of beech wood and Barley DDGS producing a brittle solid product. This was obtained at 150°C with an addition of 2.5wt% char (as catalyst) after a processing time of 1h. The batch reactor was also used for modifying and solidifying fast pyrolysis liquids derived from beech wood by adding urea or ammonium phosphate as post processing nitrogenolysis. The results showed that this type of combined approach was not suitable to produce a slow release fertiliser, because the solid product contained up to 65wt.% of highly water soluble nitrogen compounds that would be released instantly by rain. To complement the processing experiments a comparative study via Py–GC–MS with inert and reactive gas was performed with cellulose, hemicellulose, lignin and beech wood. This revealed that the presence of ammonia gas during analytical pyrolysis did not appear to have any direct impact on the decomposition products of the tested materials. The chromatograms obtained showed almost no differences between inert and ammonia gas experiments indicating that the reaction between ammonia and pyrolysis vapours does not occur instantly. A comparative study via Fourier Transformed Infrared Spectroscopy of solidified fast pyrolysis and in-situ nitrogenolysis products showed that there were some alterations in the spectra obtained. A shift in frequencies indicating C=O stretches typically related to the presence of carboxylic acids to C=O stretches related to amides was observed and no double or triple bonded nitrogen was detected. This indicates that organic acids reacted with ammonia and that no potentially harmful or non-biodegradable triple bonded nitrogen compounds were formed. The impact of solid slow release fertiliser (SRF) derived from pyrolysis and in-situ nitrogenolysis products from beech wood and Barley DDGS on microbial life in soils and plant growth was tested in cooperation with Rothamsted Research. The microbial incubation tests indicated that microbes can thrive on the SRFs produced, although some microbial species seem to have a reduced activity at very high concentrations of beech wood and Barley DDGS derived SRF. The plant tests (pot trials) showed that the application of SRF derived from beech wood and barley DDGS had no negative impact on germination or plant growth of rye grass. The fertilizing effect was proven by the dry matter yields in three harvests after 47 days, 89 days and 131 days. The findings of this research indicate that in general a slow release fertiliser can be produced from biomass and biogenic residues by in-situ nitrogenolysis. Nevertheless the findings also show that additional research is necessary to identify which compounds are formed during this process.

Pyrolysis liquids and gases as alternative fuels in internal combustion engines:a review

Liquids and gases produced through biomass pyrolysis have potential as renewable fuels to replace fossil fuels in conventional internal combustion engines. This review compares the properties of pyrolysis fuels, produced from a variety of feedstocks and using different pyrolysis techniques, against those of fossil fuels. High acidity, the presence of solid particles, high water content, high viscosity, storage and thermal instability, and low energy content are typical characteristics of pyrolysis liquids. A survey of combustion, performance and exhaust emission results from the use of pyrolysis liquids (both crude and up-graded) in compression ignition engines is presented. With only a few exceptions, most authors have reported difficulties associated with the adverse properties of pyrolysis liquids, including: corrosion and clogging of the injectors, long ignition delay and short combustion duration, difficulty in engine start-up, unstable operation, coking of the piston and cylinders and subsequent engine seizure. Pyrolysis gas can be used more readily, either in spark ignition or compression ignition engines; however, NO reduction techniques are desirable. Various approaches to improve the properties of pyrolysis liquids are discussed and a comparison of the properties of up-graded vs. crude pyrolysis liquid is included. Further developments in up-gradation techniques, such as hydrocracking and bio-refinery approaches, could lead to the production of green diesel and green gasoline. Modifications required to engines for use with pyrolysis liquids, for example in the fuel supply and injection systems, are discussed. Storage stability and economic issues are also reviewed. Our study presents recent progress and important R&D areas for successful future use of pyrolysis fuels in internal combustion engines.

Omnigen:providing electricity, food preparation, cold storage and pure water using a variety of local fuels

We describe a polygeneration system that can run on neat plant oils, such as Jatropha and Pongamia, or standard diesel fuel. A prototype has been constructed using a compression ignition engine of 9.9 kW shaft output. It consumes 3 L/h of fuel and will produce 40 kg/h of ice by means of an adsorption refrigerator powered from the engine jacket heat. Steaming of rice, deep and shallow frying, and other types of food preparation heated by the exhaust gas have been demonstrated. In addition, the feasibility of producing distilled water by means of multiple-effect distillation powered by the engine waste heat is shown. Overall plant efficiency and potential savings in greenhouse gas emissions are discussed. © 2012 Elsevier Ltd.

Low severity Fischer-Tropsch synthesis for the production of synthetic hydrocarbon fuels

Currently, the main source for the production of liquid transportation fuels is petroleum, the continued use of which faces many challenges including depleting oil reserves, significant oil price rises, and environmental concerns over global warming which is widely believed to be due to fossil fuel derived CO2 emissions and other greenhouse gases. In this respect, lignocellulosic or plant biomass is a particularly interesting resource as it is the only renewable source of organic carbon that can be converted into liquid transportation fuels. The gasification of biomass produces syngas which can then be converted into synthetic liquid hydrocarbon fuels by means of the Fischer-Tropsch (FT) synthesis. This process has been widely considered as an attractive option for producing clean liquid hydrocarbon fuels from biomass that have been identified as promising alternatives to conventional fossil fuels like diesel and kerosene. The resulting product composition in FT synthesis is influenced by the type of catalyst and the reaction conditions that are used in the process. One of the issues facing this conversion process is the development of a technology that can be scaled down to match the scattered nature of biomass resources, including lower operating pressures, without compromising liquid composition. The primary aims of this work were to experimentally explore FT synthesis at low pressures for the purpose of process down-scaling and cost reduction, and to investigate the potential for obtaining an intermediate FT synthetic crude liquid product that can be integrated into existing refineries under the range of process conditions employed. Two different fixed-bed micro-reactors were used for FT synthesis; a 2cm3 reactor at the University of Rio de Janeiro (UFRJ) and a 20cm3 reactor at Aston University. The experimental work firstly involved the selection of a suitable catalyst from three that were available. Secondly, a parameter study was carried out on the 20cm3 reactor using the selected catalyst to investigate the influence of reactor temperature, reactor pressure, space velocity, the H2/CO molar ratio in the feed syngas and catalyst loading on the reaction performance measured as CO conversion, catalyst stability, product distribution, product yields and liquid hydrocarbon product composition. From this parameter study a set of preferred operating conditions was identified for low pressure FT synthesis. The three catalysts were characterized using BET, XRD, TPR and SEM. The catalyst selected was an unpromoted Co/Al2O3 catalyst. FT synthesis runs on the 20cm3 reactor at Aston were conducted for 48 hours. Permanent gases and light hydrocarbons (C1-C5) were analysed in an online GC-TCD/FID at hourly intervals. The liquid hydrocarbons collected were analyzed offline using GC-MS for determination of fuel composition. The parameter study showed that CO conversion and liquid hydrocarbon yields increase with increasing reactor pressure up to around 8 bar, above which the effect of pressure is small. The parameters that had the most significant influence on CO conversion, product selectivity and liquid hydrocarbon yields were reactor temperature and catalyst loading. The preferred reaction conditions identified for this research were: T = 230ºC, P = 10 bar, H2/CO = 2.0, WHSV = 2.2 h-1, and catalyst loading = 2.0g. Operation in the low range of pressures studied resulted in low CO conversions and liquid hydrocarbon yields, indicating that low pressure BTL-FT operation may not be industrially viable as the trade off in lower CO conversions and once-through liquid hydrocarbon product yields has to be carefully weighed against the potential cost savings resulting from process operation at lower pressures.

Techno-economic assessment and uncertainty analysis of thermochemical processes for second generation biofuels

Biomass-To-Liquid (BTL) is one of the most promising low carbon processes available to support the expanding transportation sector. This multi-step process produces hydrocarbon fuels from biomass, the so-called “second generation biofuels” that, unlike first generation biofuels, have the ability to make use of a wider range of biomass feedstock than just plant oils and sugar/starch components. A BTL process based on gasification has yet to be commercialized. This work focuses on the techno-economic feasibility of nine BTL plants. The scope was limited to hydrocarbon products as these can be readily incorporated and integrated into conventional markets and supply chains. The evaluated BTL systems were based on pressurised oxygen gasification of wood biomass or bio-oil and they were characterised by different fuel synthesis processes including: Fischer-Tropsch synthesis, the Methanol to Gasoline (MTG) process and the Topsoe Integrated Gasoline (TIGAS) synthesis. This was the first time that these three fuel synthesis technologies were compared in a single, consistent evaluation. The selected process concepts were modelled using the process simulation software IPSEpro to determine mass balances, energy balances and product distributions. For each BTL concept, a cost model was developed in MS Excel to estimate capital, operating and production costs. An uncertainty analysis based on the Monte Carlo statistical method, was also carried out to examine how the uncertainty in the input parameters of the cost model could affect the output (i.e. production cost) of the model. This was the first time that an uncertainty analysis was included in a published techno-economic assessment study of BTL systems. It was found that bio-oil gasification cannot currently compete with solid biomass gasification due to the lower efficiencies and higher costs associated with the additional thermal conversion step of fast pyrolysis. Fischer-Tropsch synthesis was the most promising fuel synthesis technology for commercial production of liquid hydrocarbon fuels since it achieved higher efficiencies and lower costs than TIGAS and MTG. None of the BTL systems were competitive with conventional fossil fuel plants. However, if government tax take was reduced by approximately 33% or a subsidy of £55/t dry biomass was available, transport biofuels could be competitive with conventional fuels. Large scale biofuel production may be possible in the long term through subsidies, fuels price rises and legislation.