A comparative study of straw, perennial grasses and hardwoods in terms of fast pyrolysis products

The aim of this study is to characterise and compare fast pyrolysis product yields from straw, high yielding perennial grasses and hardwoods. Feedstocks selected for this study include: wheat straw (Triticum aestivum), switch grass (Panicum virgatum), miscanthus (Miscanthus x giganteus), willow short rotation coppice (Salix viminalis) and beech wood (Fagus sylvatica). The experimental work is divided into two sections: analytical (TGA and Py-GC-MS) and laboratory scale processing using a continuously fed bubbling fluidized bed reactor with a capacity of up to 1 kg/h. Pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) has been used to quantify pyrolysis products and simulate fast pyrolysis heating rates, in order to study potential key light and medium volatile decomposition products found in these feedstocks. Py-GC-MS quantification results show that the highest yields of furfural (0.57 wt.%), 2-furanmethanol (0.18 wt.%), levoglucosan (0.73 wt.%), 1,2-benzenediol (0.27 wt.%) and 2-methoxy-4-vinylphenol (0.38 wt.%) were found in switch grass, and that willow SRC produced the highest yield of phenol (0.33 wt.%). The bio-oil higher heating value was highest for switch grass (22.3 MJ/kg). Water content within the bio-oil is highest in the straw and perennial grasses and lowest in the hardwood willow SRC. The high bio-oil and char heating value and low water content found in willow SRC, makes this crop an attractive energy feedstock for fast pyrolysis processing, if the associated production costs and harvest yields can be maintained at current reported values. The bio-oil from switch grass has the highest potential for the production of high value chemicals. © 2013 Elsevier Ltd. All rights reserved.

Thermochemical characterisation of agricultural wastes from West Africa

Thermochemical characterisation of agricultural biomass wastes from West African region has been carried out and their potential use as feedstock in thermochemical conversion processes determined. Proximate, ultimate, structural compositions, calorific values, thermogravimetry (TGA) and derivative thermogravimetry (DTG) analyses were carried out on corn straw and cobs, rice straw and husks, cocoa pod, jatropha curcas and moringa olifiera seed cakes, parinari polyandra fruit shell and sugarcane bagasse. Moringa olifiera seed cakes and cocoa pods were found to contain the highest moisture contents. Rice straw was found to contain a high ash content of 45.76. wt.%. The level of nitrogen and sulphur in all the samples were very low. Rice husk was found to have the highest lignin contents while corn cob low lignin contents indicate a potential feedstock source for quality bio-oil production using thermochemical process. © 2013.

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.

Characterization of engineered biochar for soil management

Pyrolysis is an energy conversion technology which by heating organic materials in the absence of oxygen, produces liquid, gaseous, and solid fuel products. Biochar, the solid product, can also be used as a soil amendment and, simultaneously, enables us to sequester carbon in the soil. By controlling the pyrolysis process, it is possible to engineer biochar suitable for the remediation of specific soil management problems. This research uses a characterization method more suited to producing biochar for soil amendment purposes than the existing biochar fuel characterization standards. This is the first research to use wastewater irrigated willow as a pyrolysis feedstock. The extensive characterization of biochar produced over a range of temperatures (410-810°C) yielded data on key properties relevant to soil under management: low surface area (1.4 to 5.4 m2/g), low bulk density (0.15-0.18 g/cm3), high pH values (7.8-9.4) and high water-holding capacity (1.8 to 4.3 cm3/g). Extraction experiments demonstrated low bioavailability of char nutrients (N, P, K, Ca, and Mg). This research also studied this artificial nitrogen cycle of pyrolysis: nitrogen accumulated in the wood from the wastewater and high levels of nitrogen remained in the biochar in a stable form not directly available to plants. Copyright © 2013 American Institute of Chemical Engineers Environ Prog.

Assessing economically viable carbon reductions for the production of ammonia from biomass gasification

Greenhouse gas emissions from fertiliser production are set to increase before stabilising due to the increasing demand to secure sustainable food supplies for a growing global population. However, avoiding the impacts of climate change requires all sectors to decarbonise by a very high level within several decades. Economically viable carbon reductions of substituting natural gas reforming with biomass gasification for ammonia production are assessed using techno-economic and life cycle assessment. Greenhouse gas savings of 65% are achieved for the biomass gasification system and the internal rate of return is 9.8% at base-line biomass feedstock and ammonia prices. Uncertainties in the assumptions have been tested by performing sensitivity analysis, which show, for example with a ±50% change in feedstock price, the rate of return ranges between -0.1% and 18%. It would achieve its target rate of return of 20% at a carbon price of £32/t CO, making it cost competitive compared to using biomass for heat or electricity. However, the ability to remain competitive to investors will depend on the volatility of ammonia prices, whereby a significant decrease would require high carbon prices to compensate. Moreover, since no such project has been constructed previously, there is high technology risk associated with capital investment. With limited incentives for industrial intensive energy users to reduce their greenhouse gas emissions, a sensible policy mechanism could target the support of commercial demonstration plants to help ensure this risk barrier is resolved. © 2013 The Authors.

Decision support for lifecycle planning and risk management of small-scale biomass combined heat and power (bCHP) projects in the UK

Biomass is projected to account for approximately half of the new energy production required to achieve the 2020 primary energy target in the UK. Combined heat and power (CHP) bioenergy systems are not only a highly efficient method of energy conversion, at smaller-scales 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 incumbent; a high carbon centralised energy system. Unidentified or unmitigated barriers occurring during the project lifecycle may not only negatively impact on the project but could ultimately lead to project failure. The research develops a decision support system (DSS) for small-scale (500 kWe to 10 MWe) biomass combustion CHP project development and risk management in the early stages of a potential project’s lifecycle. By supporting developers in the early stages of project development with financial, scheduling and risk management analysis, the research aims to reduce the barriers identified and streamline decision-making. A fuzzy methodology is also applied throughout the developed DSS to support developers in handling the uncertain or approximate information often held at the early stages of the project lifecycle. The DSS is applied to a case study of a recently failed (2011) small-scale biomass CHP project to demonstrate its applicability and benefits. The application highlights that the proposed development within the case study was not viable. Moreover, further analysis of the possible barriers with the DSS confirmed that some possible modifications to be project could have improved this, such as a possible change of feedstock to a waste or residue, addressing the unnecessary land lease cost or by increasing heat utilisation onsite. This analysis is further supported by a practitioner evaluation survey that confirms the research contribution and objectives are achieved.

The influence of harvest and storage on the properties of and fast pyrolysis products from Miscanthus x giganteus

The research investigates the fuel property variations associated with the time of harvest and the duration of storage of Miscanthus x giganteus over a one year period. The crop has been harvested at three different times: early (September 2009), conventional (April 2010) and late (June 2010). Once harvested the crop was baled and stored. Biomass properties of samples taken from different storage zones were compared. The thermochemical properties have been investigated using a range of analytical equipment including thermogravimetric analysis (TGA) and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS). In addition, bio-oil has been produced from the early, conventional and late harvest using a laboratory scale (300gh) fast pyrolysis unit. The potential organic liquid yield (ondry basis, also excluding the reaction water generated) based on the laboratory fast pyrolysis processing undertaken in this study, was found to vary between 2.82 and 3.18 dry tha for the early and the late harvest respectively. The bio-oil organic yield was reduced by approximately 11% (0.36tha) between the early and the late harvest. Char yield was also reduced by approximately 18% (0.61tha). The highest gas yield (18.03%-1.60tha) was observed for the conventional harvest. Gas chromatography-mass spectrometry (GC-MS) analysis of the bio-oil shows that levoglucosan, methylbenzaldehyde and 1,2-benzenediol all increase as a consequence of delayed harvest. It was also observed that by delaying the harvest time the O:C atomic ratio is reduced and a more carbonaceous feedstock is produced. © 2013 Elsevier Ltd.

Novel biomass conversion routes:ammonia from biomass, and marine macroalgae for energy

This thesis presents a techno-economic investigation of the generation of electricity from marine macroalgae (seaweed) in the UK (Part 1), and the production of anhydrous ammonia from synthesis gas (syngas) generated from biomass gasification (Part 2). In Part 1, the study covers the costs from macroalgae production to the generation of electricity via a CHP system. Seven scenarios, which varied the scale and production technique, were investigated to determine the most suitable scale of operation for the UK. Anaerobic digestion was established as the most suitable technology for macroalgae conversion to CHP, based on a number of criteria. All performance and cost data have been taken from published literature. None of the scenarios assessed would be economically viable under present conditions, although the use of large-scale electricity generation has more potential than small-scale localised production. Part 2 covers the costs from the delivery of the wood chip feedstock to the production of ammonia. Four cases, which varied the gasification process used and the scale of production, were investigated to determine the most suitable scale of operation for the UK. Two gasification processes were considered, these were O2-enriched air entrained flow gasification and Fast Internal Circulating Fluidised Bed. All performance and cost data have been taken from published literature, unless otherwise stated. Large-scale (1,200 tpd) ammonia production using O2-enriched air entrained flow gasification was determined as the most suitable system, producing the lowest ammonia-selling price, which was competitive to fossil fuels. Large-scale (1,200 tpd) combined natural gas/biomass syngas ammonia production also generated ammonia at a price competitive to fossil fuels.

Catalytic intermediate pyrolysis of Brunei rice husk for bio-oil production

Rice husks from Brunei were subjected via intermediate pyrolysis for bio-oil production. Two main objectives were set out for this study. The application of intermediate pyrolysis on Brunei rice husk for the production of bio-oil is the main objective of this experiment. Characterisation of the rice husks was inclusive as a pre-requisite step to assess the suitability as feedstock for production of liquid fuels. Following on from the characterisation results, a temperature of 450°C was established as the optimum temperature for the production of bio-oil. A homogenous bio-oil was obtained from the pyrolysis of dry rice husk, and the physicochemical properties and chemical compositions were analysed. The second objective is the introduction of catalysts into the pyrolysis process which aims to improve the bio-oil quality, and maximise the desired liquid bio-oil properties. The incorporation of the catalysts was done via a fixed tube reactor into the pyrolysis system. Ceramic monoliths were used as the catalyst support, with montmorillonite clay as a binder to attach the catalysts onto the catalyst support. ZSM-5, Al-MCM-41, Al-MSU-F and Brunei rice husk ash (BRHA) together with its combination were adopted as catalysts. Proposed criterions dictated the selection of the best catalysts, subsequently leading to the optimisation process for bio-oil production. ZSM-5/Al-MCM-41 proved the most desirable catalyst, which increases the production of aromatics and phenols, decreased the organic acids and improved the physicochemical properties such as the pH, viscosity, density and H:C molar ratios. Variation in the ratio and positioning of both catalysts were the significant key factor for the catalyst optimisation study.

European biorefineries:implications for land, trade and employment

Biorefineries are expected to play a major role in a future low carbon economy and substantial investments are being made to support this vision. However, it is important to consider the wider socio-economic impacts of such a transition. This paper quantifies the potential trade, employment and land impacts of economically viable European biorefinery options based on indigenous straw and wood feedstocks. It illustrates how there could be potential for 70-80 European biorefineries, but not hundreds. A single facility could generate tens of thousands of man-years of employment and employment creation per unit of feedstock is higher than for biomass power plants. However, contribution to national GDP is unlikely to exceed 1% in European member states, although contributions to national agricultural productivity may be more significant, particularly with straw feedstocks. There is also a risk that biorefinery development could result in reduced rates of straw incorporation into soil, raising concerns that economically rational decisions to sell rather than reincorporate straw could result in increased agricultural land-use or greenhouse gas emissions. © 2013.

Risk and uncertainty in supply markets and sustainability-related innovation

tentially valuable innovations. In energy policy, much attention is given to analysing and incentivising customer demand, but new technologies also need new supply markets, to provide products and services to build, operate and maintain the innovative technology. This paper addresses the impact of supply constraints on the long-term viability of sustainability related innovations, using the case of energy from waste (EfW). Uncertainties in the pricing and availability of feedstock (i.e. waste) deter potential investors in EfW projects. We draw on prior supply management research to conceptualise the problem, and identify what steps might be taken to address it. Based on this analysis, we propose a research agenda aimed at purchasing and supply scholars and centred on the need to understand better how markets evolve and how stakeholders can (legitimately) influence the evolution of supply markets to support the adoption of sustainability related innovation. Within this broad case, specific themes are recommended for further investigation.

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.

Waste 4:electronic-scrap recycling

The Haloclean process, a rotary kiln process for pyrolysis, developed by researchers at the Forschungszentrum Karlsruhe, Germany makes it possible to recover copper and precious metals from the scrap, ready for recycling. Pyrolysis neatly turns brominated electronic scrap plastics into recyclable copper and methanol feedstock while removing the halogens. The process has demonstrated its ability to recycle brominated electronic scrap in extensive parametric studies. A method suitable for the selective production of HBr in the presence of chlorine is the treatment of the pyrolysis oils with molten polypropylene. This treatment is offers the possibility to use the gas and liquid fraction from pyrolysis of electronic scrap as fossil fuel substitute in copper smelter processes or as feedstock for methanol production via gasification.

Recent developments in heterogeneous catalysis for the sustainable production of biodiesel

The quest for energy security and widespread acceptance of the anthropogenic origin of rising CO2 emissions and associated climate change from combusting fossil derived carbon sources, is driving academic and commercial research into new routes to sustainable fuels to meet the demands of a rapidly rising global population. Biodiesel is one of the most readily implemented and low cost, alternative source of transportation fuels to meet future societal demands. However, current practises to produce biodiesel via transesterification employing homogeneous acids and bases result in costly fuel purification processes and undesired pollution. Life-cycle calculations on biodiesel synthesis from soybean feedstock show that the single most energy intensive step is the catalytic conversion of TAGs into biodiesel, accounting for 87% of the total primary energy input, which largely arises from the quench and separation steps. The development of solid acid and base catalysts that respectively remove undesired free fatty acid (FFA) impurities, and transform naturally occurring triglycerides found within plant oils into clean biodiesel would be desirable to improve process efficiency. However, the microporous nature of many conventional catalysts limits their ability to convert bulky and viscous feeds typical of plant or algal oils. Here we describe how improved catalyst performance, and overall process efficiency can result from a combination of new synthetic materials based upon templated solid acids and bases with hierarchical structures, tailored surface properties and use of intensified process allowing continuous operation.

Bifunctional SO4/ZrO2 catalysts for 5-hydroxymethylfufural (5-HMF) production from glucose

The telescopic conversion of glucose to fructose and then 5-hydroxymethylfurfural (5-HMF), the latter a potential, bio-derived platform chemical feedstock, has been explored over a family of bifunctional sulfated zirconia catalysts possessing tuneable acid-base properties. Characterisation by acid-base titration, XPS, XRD and Raman reveal that submonolayer SO4 coverages offer the ideal balance of basic and Lewis-Brønsted acid sites required to respectively isomerise glucose to fructose, and subsequently dehydrate fructose to 5-HMF. A constant acid site normalised turnover frequency is observed for fructose dehydration to 5-HMF, confirming a common Brønsted acid site is responsible for this transformation. This journal is © The Royal Society of Chemistry.