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.

Breakdown of plant cell biomass by filamentous fungi

Three species of filamentous fungi, Botrytis cinerea, Sporotrichum thermophile and Trichoderma viride, have been selected to assess the potential of utilizing filamentous fungi to degrade plant cell biomass produced by mass cell culture techniques. All three fungal species grew comparatively well on plant cell biomass with no requirement for supplementary nutrients. Of the three species assessed B. cinerea demonstrated the most growth. This species also produced the greatest yield of D-glucose. However, when culture conditions were modified, yields of D-glucose were markedly reduced indicating that the combination of species and culture conditions must be thoroughly investigated to ensure maximum product yield. The growth of filamentous fungi on plant cells also markedly affected the nature of the resulting fungal-plant cell residue, increasing the levels of soluble carbohydrates and essential amino acids with the largest increase in these materials being promoted by B. cinerea.

The breakdown of plant cell biomass by fungi

Three species of fungi Sporotrichum thermophile, Botrytis cinerea and Trichoderma viride were assessed for their ability to utilize a variety of plant cell substrates (methanol extracted), Catharanthus roseus, Daucus carota, re-autoclaved C. roseus, re-autoclaved D. carota) which preliminary studies had indicated contained the necessary nutrients for fungal growth. Incubated in a suitable manner all three fungal species were able to grow on C. roseus and D. carota plant cell biomass in addition to material which had undergone methanol extraction or a re-autoclaving process to remove soluble components. Fungal biomass yields were markedly influenced by substrate, with each fungal species demonstrating a preference for particular plant cell material. Incubation conditions i.e. static or shaken and temperature also proved important. Release of glucose (i.e. values higher than Day 0) promoted by fungal breakdown of plant cell biomass was only noted with methanol extracted, re-autoclaved C. roseus and re-autoclaved D. carota material. A re-autoclaved substrate was also generally associated with high fungal C1, Cx, B-glucosidase and endo-polygalacturonase activity. In addition for each enzyme highest values were usually obtained from a particular fungal species. Buffering cultures at pH 3 or 5 further influenced enzyme activity, however in a majority of cases when flasks were unbuffered and the pH rose naturally to alkaline values higher enzyme activity was recorded. Likewise Tween 80 addition had only a limited beneficial effect. Finally filtrates containing glucose produced both from the re-autoclaving process and through fungal activity on plant cell biomass were utilized for Fusarium oxysporum, Saccharomyces cerevisiae and C. roseus plant cell culture. Although reasonable fungal biomass was obtained the use of such filtrates proved unsuitable for plant cell growth.

Analysis of transport costs for energy crops for use in biomass pyrolysis plant networks

Fast pyrolysis of biomass produces a liquid bio-oil that can be used for electricity generation. Bio-oil can be stored and transported so it is possible to decouple the pyrolysis process from the generation process. This allows each process to be separately optimised. It is necessary to have an understanding of the transport costs involved in order to carry out techno-economic assessments of combinations of remote pyrolysis plants and generation plants. Published fixed and variable costs for freight haulage have been used to calculate the transport cost for trucks running between field stores and a pyrolysis plant. It was found that the key parameter for estimating these costs was the number of round trips a day a truck could make rather than the distance covered. This zone costing approach was used to estimate the transport costs for a range of pyrolysis plants size for willow woodchips and baled miscanthus. The possibility of saving transport costs by producing bio-oil near to the field stores and transporting the bio-oil to a central plant was investigated and it was found that this would only be cost effective for large generation plants.

An interdisciplinary approach to designing and evaluating a hybrid solar-biomass power plant

Purpose: Energy security is a major concern for India and many rural areas remain un-electrified. Thus, innovations in sustainable technologies to provide energy services are required. Biomass and solar energy in particular are resources that are widely available and underutilised in India. This paper aims to provide an overview of a methodology that was developed for designing and assessing the feasibility of a hybrid solar-biomass power plant in Gujarat. Design/methodology/approach: The methodology described is a combination of engineering and business management studies used to evaluate and design solar thermal collectors for specific applications and locations. For the scenario of a hybrid plant, the methodology involved: the analytical hierarchy process, for solar thermal technology selection; a cost-exergy approach, for design optimisation; quality function deployment, for designing and evaluating a novel collector - termed the elevation linear Fresnel reflector (ELFR); and case study simulations, for analysing alternative hybrid plant configurations. Findings: The paper recommended that for a hybrid plant in Gujarat, a linear Fresnel reflector of 14,000 m2 aperture is integrated with a 3 tonne per hour biomass boiler, generating 815 MWh per annum of electricity for nearby villages and 12,450 tonnes of ice per annum for local fisheries and food industries. However, at the expense of a 0.3 ¢/kWh increase in levelised energy costs, the ELFR can increase savings of biomass (100 t/a) and land (9 ha/a). Research limitations/implications: The research reviewed in this paper is primarily theoretical and further work will need to be undertaken to specify plant details such as piping layout, pump sizing and structure, and assess plant performance during real operational conditions. Originality/value: The paper considers the methodology adopted proved to be a powerful tool for integrating technology selection, optimisation, design and evaluation and promotes interdisciplinary methods for improving sustainable engineering design and energy management. © Emerald Group Publishing Limited.

Cost and performance analysis of new wood-fuelled power plant concepts

The objective of the thesis was to analyse several process configurations for the production of electricity from biomass. Process simulation models using AspenPlus aimed at calculating the industrial performance of power plant concepts were built, tested, and used for analysis. The criteria used in analysis were performance and cost. All of the advanced systems appear to have higher efficiencies than the commercial reference, the Rankine cycle. However, advanced systems typically have a higher cost of electricity (COE) than the Rankine power plant. High efficiencies do not reduce fuel costs enough to compensate for the high capital costs of advanced concepts. The successful reduction of capital costs would appear to be the key to the introduction of the new systems. Capital costs account for a considerable, often dominant, part of the cost of electricity in these concepts. All of the systems have higher specific investment costs than the conventional industrial alternative, i.e. the Rankine power plant; Combined beat and power production (CUP) is currently the only industrial area of application in which bio-power costs can be considerably reduced to make them competitive. Based on the results of this work, AsperiPlus is an appropriate simulation platform. How-ever, the usefulness of the models could be improved if a number of unit operations were modelled in greater detail. The dryer, gasifier, fast pyrolysis, gas engine and gas turbine models could be improved.

The design and engineering of a reactor test facility for thermal processing of biomass

This thesis describes the design and engineering of a pressurised biomass gasification test facility. A detailed examination of the major elements within the plant has been undertaken in relation to specification of equipment, evaluation of options and final construction. The retrospective project assessment was developed from consideration of relevant literature and theoretical principles. The literature review includes a discussion on legislation and applicable design codes. From this analysis, each of the necessary equipment units was reviewed and important design decisions and procedures highlighted and explored. Particular emphasis was placed on examination of the stringent demands of the ASME VIII design codes. The inter-relationship of functional units was investigated and areas of deficiency, such as biomass feeders and gas cleaning, have been commented upon. Finally, plant costing was summarized in relation to the plant design and proposed experimental programme. The main conclusion drawn from the study is that pressurised gasification of biomass is far more difficult and expensive to support than atmospheric gasification. A number of recommendations have been made regarding future work in this area.

Fluidized bed gasification of biomass

A fluidized bed process development unit of 0.8 m internal diameter was designed on basis of results obtained from a bench scale laboratory unit. For the scaling up empirical models from the literature were used. The process development unit and peripheral equipment were constructed, assembled and commissioned, and instruments were provided for data acquisition. The fluidization characteristics of the reactor were determined and were compared to the design data. An experimental programme was then carried out and mass and energy balances were made for all the runs. The results showed that the most important independent experimental parameter was the air factor, with an optimum at 0.3. The optimum higher heating value of the gas produced was 6.5 MJ/Nm3, while the thermal efficiency was 70%. Reasonably good agreement was found between the experimental results, theoretical results from a thermodynamic model and data from the literature. It was found that the attainment of steady state was very sensitive to a continuous and constant feedstock flowrate, since the slightest variation in feed flow resulted in fluctuations of the gas quality. On the basis of the results a set of empirical relationships was developed, which constitutes an empirical model for the prediction of the performance of fluidized bed gasifiers. This empirical model was supplemented by a design procedure by which fluidized bed gasifiers can be designed and constructed. The design procedure was then extended to cover feedstock feeding and gas cleaning in a conceptual design of a fluidized bed gasification facility. The conceptual design was finally used to perform an economic evaluation of a proposed gasification facility. The economics of this plant (retrofit application) were favourable.

Genotypic and environmentally derived variation in the cell wall composition of Miscanthus in relation to its use as a biomass feedstock

Fifteen Miscanthus genotypes grown in five locations across Europe were analysed to investigate the influence of genetic and environmental factors on cell wall composition. Chemometric techniques combining near infrared reflectance spectroscopy (NIRS) and conventional chemical analyses were used to construct calibration models for determination of acid detergent lignin (ADL), acid detergent fibre (ADF), and neutral detergent fibre (NDF) from sample spectra. Results generated were subsequently converted to lignin, cellulose and hemicellulose content and used to assess the genetic and environmental variation in cell wall composition of Miscanthus and to identify genotypes which display quality traits suitable for exploitation in a range of energy conversion systems. The NIRS calibration models developed were found to predict concentrations with a good degree of accuracy based on the coefficient of determination (R2), standard error of calibration (SEC), and standard error of cross-validation (SECV) values. Across all sites mean lignin, cellulose and hemicellulose values in the winter harvest ranged from 76–115 g kg-1, 412–529 g kg-1, and 235–338 g kg-1 respectively. Overall, of the 15 genotypes Miscanthus x giganteus and Miscanthus sacchariflorus contained higher lignin and cellulose concentrations in the winter harvest. The degree of observed genotypic variation in cell wall composition indicates good potential for plant breeding and matching feedstocks to be optimised to different energy conversion processes.

Drying of biomass for second generation synfuel production

Drying is a major and challenging step in the pre-treatment of biomass for production of second generation synfuels for transport. The biomass feedstocks are mostly wet and need to be dried from 30 to 60 wt% moisture content to about 10-15 wt%. The present survey aims to define and evaluate a few of the most promising optimised concepts for biomass pre-treatment scheme in the production of second generation synfuels for transport. The most promising commercially available drying processes were reviewed, focusing on the applications, operational factors and emissions of dryers. The most common dryers applied now for biomass in bio-energy plants are direct rotary dryers, but the use of steam drying techniques is increasing. Steam drying systems enable the integration of the dryer to existing energy sources. In addition to integration, emissions and fire or explosion risks have to be considered when selecting a dryer for the plant. In steam drying there will be no gaseous emissions, but the aqueous effluents need often treatment. Concepts for biomass pre-treatment were defined for two different cases including a large-scale wood-based gasification synfuel production and a small-scale pyrolysis process based on wood chips and miscanthus bundles. For the first case a pneumatic conveying steam dryer was suggested. In the second case the flue gas will be used as drying medium in a direct or indirect rotary dryer.

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.

Biomass production in short rotation effluent-irrigated plantations in North-West India

This study estimates above-ground biomass in high density plantations of six important semi-arid tree species at Palwal (70 km from Delhi) irrigated with secondary treated sewage water at the rate of 0, 25, 50 and 100% of daily net evaporation potential (EP). In 2.5 y old plantations (plant spacing, 2 m x 2 m for single stem species and 2 m x 1 m for multi-stem species), Melia azedarach showed fairly high biomass production (38.4 t/ha) followed by Ailanthus excelsa (27.2 t/ha). Order of biomass production (kg / tree) was: Eucalyptus tereticornis (24.1) > A. excelsa (21.8) > M. azedarach (12.6) > Populus deltoides clone G 48 (8.3) > Alstonia scholaris (6.6)> Pongamia pinnata (3.7). Survival of plants after 2.5 y ranged from 25.2% in P. deltoides to 71.7% in P. pinnata, and had a significant effect on biomass production per unit area. ANOVA shows that levels of irrigation (0 - 100%) did not have statistically significant effect on plant growth. Correlation between diameter and biomass was found highly significant (p< 0.01) with R2 nearing to 1.

Solar thermal collectors for use in hybrid solar-biomass power plants in India

This thesis examined solar thermal collectors for use in alternative hybrid solar-biomass power plant applications in Gujarat, India. Following a preliminary review, the cost-effective selection and design of the solar thermal field were identified as critical factors underlying the success of hybrid plants. Consequently, the existing solar thermal technologies were reviewed and ranked for use in India by means of a multi-criteria decision-making method, the Analytical Hierarchy Process (AHP). Informed by the outcome of the AHP, the thesis went on to pursue the Linear Fresnel Reflector (LFR), the design of which was optimised with the help of ray-tracing. To further enhance collector performance, LFR concepts incorporating novel mirror spacing and drive mechanisms were evaluated. Subsequently, a new variant, termed the Elevation Linear Fresnel Reflector (ELFR) was designed, constructed and tested at Aston University, UK, therefore allowing theoretical models for the performance of a solar thermal field to be verified. Based on the resulting characteristics of the LFR, and data gathered for the other hybrid system components, models of hybrid LFR- and ELFR-biomass power plants were developed and analysed in TRNSYS®. The techno-economic and environmental consequences of varying the size of the solar field in relation to the total plant capacity were modelled for a series of case studies to evaluate different applications: tri-generation (electricity, ice and heat), electricity-only generation, and process heat. The case studies also encompassed varying site locations, capacities, operational conditions and financial situations. In the case of a hybrid tri-generation plant in Gujarat, it was recommended to use an LFR solar thermal field of 14,000 m2 aperture with a 3 tonne biomass boiler, generating 815 MWh per annum of electricity for nearby villages and 12,450 tonnes of ice per annum for local fisheries and food industries. However, at the expense of a 0.3 ¢/kWh increase in levelised energy costs, the ELFR increased saving of biomass (100 t/a) and land (9 ha/a). For solar thermal applications in areas with high land cost, the ELFR reduced levelised energy costs. It was determined that off-grid hybrid plants for tri-generation were the most feasible application in India. Whereas biomass-only plants were found to be more economically viable, it was concluded that hybrid systems will soon become cost competitive and can considerably improve current energy security and biomass supply chain issues in India.

Phosphorus catalysis in the pyrolysis behaviour of biomass

Phosphorus is a key plant nutrient and as such, is incorporated into growing biomass in small amounts. This paper examines the influence of phosphorus, present in either acid (HPO) or salt ((NH)PO) form, on the pyrolysis behaviour of both Miscanthus × giganteus, and its cell wall components, cellulose, hemicellulose (xylan) and lignin (Organosolv). Pyrolysis-gas chromatography-mass spectrometry (PY-GC-MS) is used to examine the pyrolysis products during thermal degradation, and thermogravimetric analysis (TGA) is used to examine the distribution of char and volatiles. Phosphorus salts are seen to catalyse the pyrolysis and modify the yields of products, resulting in a large increase in char yield for all samples, but particularly for cellulose and Miscanthus. The thermal degradation processes of cellulose, xylan and Miscanthus samples occur in one step and the main pyrolysis step is shifted to lower temperature in the presence of phosphorus. A small impact of phosphorus was observed in the case of lignin char yields and the types of pyrolysis decomposition products produced. Levoglucosan is a major component produced in fast pyrolysis of cellulose. Furfural and levoglucosenone become more dominant products upon P-impregnation pointing to new rearrangement and dehydration routes. The P-catalysed xylan decomposition route leads to a much simpler mixture of products, which are dominated by furfural, 3-methyl-2-cyclopenten-1-one and one other unconfirmed product, possibly 3,4-dihydro-2-methoxy-2H-pyran or 4-hydroxy-5,6-dihydro-(2H)-pyran-2-one. Phosphorus-catalysed lignin decomposition also leads to a modified mixture of tar components and desaspidinol as well as other higher molecular weight component become more dominant relative to the methoxyphenyl phenols, dimethoxy phenols and triethoxy benzene. Comparison of the results for Miscanthus lead to the conclusion that the understanding of the fast pyrolysis of biomass can, for the most part, be gained through the study of the individual cell wall components, provided consideration is given to the presence of catalytic components such as phosphorus.

A barrier and techno-economic analysis of small-scale bCHP (biomass combined heat and power) schemes in the UK

bCHP (Biomass combined heat and power) systems are highly efficient at smaller-scales when a significant proportion of the heat produced can be effectively utilised for hot water, space heating or industrial heating purposes. However, there are many barriers to project development and this has greatly inhibited deployment in the UK. Project viability is highly subjective to changes in policy, regulation, the finance market and the low cost fossil fuel incumbent. The paper reviews the barriers to small-scale bCHP project development in the UK along with a case study of a failed 1.5MWel bCHP scheme. The paper offers possible explanations for the project's failure and suggests adaptations to improve the project resilience. Analysis of the project's: capital structuring contract length and bankability; feedstock type and price uncertainty, and plant oversizing highlight the negative impact of the existing project barriers on project development. The research paper concludes with a discussion on the effects of these barriers on the case study project and this industry more generally. A greater understanding of the techno-economic effects of some barriers for small-scale bCHP schemes is demonstrated within this paper, along with some methods for improving the attractiveness and resilience of projects of this kind. © 2014 Elsevier Ltd.