Planar solid oxide fuel cell modeling and optimization targeting the stack's temperature gradient minimization

Minimization of undesirable temperature gradients in all dimensions of a planar solid oxide fuel cell (SOFC) is central to the thermal management and commercialization of this electrochemical reactor. This article explores the effective operating variables on the temperature gradient in a multilayer SOFC stack and presents a trade-off optimization. Three promising approaches are numerically tested via a model-based sensitivity analysis. The numerically efficient thermo-chemical model that had already been developed by the authors for the cell scale investigations (Tang et al. Chem. Eng. J. 2016, 290, 252-262) is integrated and extended in this work to allow further thermal studies at commercial scales. Initially, the most common approach for the minimization of stack's thermal inhomogeneity, i.e., usage of the excess air, is critically assessed. Subsequently, the adjustment of inlet gas temperatures is introduced as a complementary methodology to reduce the efficiency loss due to application of excess air. As another practical approach, regulation of the oxygen fraction in the cathode coolant stream is examined from both technical and economic viewpoints. Finally, a multiobjective optimization calculation is conducted to find an operating condition in which stack's efficiency and temperature gradient are maximum and minimum, respectively.

Outlook and application status of the Rolls-Royce Fuel Cell Systems SOFC

Rolls-Royce fuel cell systems is developing megawatt scale power systems based on solid oxide fuel cell technology. The hybrid design promises to meet challenging energy efficiency, cost and performance targets in a grid friendly fashion. Analysis and testing to date indicate that those targets can be met and enable a wealth of fuel cell applications to meet customer and existing grid and modern grid requirements. Working with a global development team, a series of laboratory tests and evaluations are completed and future field test and evaluation and demonstration planned.

Development and validation of a computationally efficient pseudo 3D model for planar SOFC integrated with a heating furnace

Efficient numerical models facilitate the study and design of solid oxide fuel cells (SOFCs), stacks, and systems. Whilst the accuracy and reliability of the computed results are usually sought by researchers, the corresponding modelling complexities could result in practical difficulties regarding the implementation flexibility and computational costs. The main objective of this article is to adapt a simple but viable numerical tool for evaluation of our experimental rig. Accordingly, a model for a multi-layer SOFC surrounded by a constant temperature furnace is presented, trained and validated against experimental data. The model consists of a four-layer structure including stand, two interconnects, and PEN (Positive electrode-Electrolyte-Negative electrode); each being approximated by a lumped parameter model. The heating process through the surrounding chamber is also considered. We used a set of V-I characteristics data for parameter adjustment followed by model verification against two independent sets of data. The model results show a good agreement with practical data, offering a significant improvement compared to reduced models in which the impact of external heat loss is neglected. Furthermore, thermal analysis for adiabatic and non-adiabatic process is carried out to capture the thermal behaviour of a single cell followed by a polarisation loss assessment. Finally, model-based design of experiment is demonstrated for a case study.

Alkaline nitro-benzene oxidation of model compounds and solid fuel derivatives

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A legal perspective of integrated surface mining, solid waste landfill reclamation and land conservation

In the area of international environmental law this thesis proposes the formulation of one-step planning and permitting regulation for the integrated utilisation of new surface mines as depositories for municipal solid waste. Additionally, the utilisation of abandoned and currently operated surface mines is proposed as solid waste landfills as an integral step in their reclamation. Existing laws, litigation and issues in the United Kingdom, the U.S. and Canada are discussed because of their common legal system, language and heritage. The critical shortage of approved space for disposal of solid waste has caused an urgent and growing problem for both the waste disposal industry and society. Surface mining can serve three important environmental and societal functions inuring to the health and welfare of the public: (1) providing basic minerals for goods and construction; (20 sequentially, to provide critically needed, safe burial sites for society's wastes, and (3) to conserve land by dual purpose use and to restore derelict land to beneficial surface use. Currently, the first two functions are treated environmentally, and in regulation, as two different siting problems, yet they both are earth-disturbing and excavating industries requiring surface restoration. The processes are largely duplicative and should be combined for better efficiency, less earth disturbance, conservation of land, and for fuller and better reclamation of completed surface mines returning the surfaces to greater utility than present mined land reclamation procedures. While both industries are viewed by a developed society and its communities as "bad neighbours", they remain essential and critical for mankind's existence and welfare. The study offers successful examples of the integrated process in each country. The study argues that most non-fuel surface mine openings, if not already safe, can economically, through present containment technology, be made environmentally safe for use as solid waste landfills. Simultaneously, the procedure safeguards and monitors protection of ground and surface waters from landfill contamination.

The intermediate pyrolysis of de-inking sludge to produce a sustainable liquid fuel

De-inking sludge is a waste product generated from secondary fibre paper mills who manufacture recycled paper into new paper sheets; it refers directly to the solid residues which evolve during the de-inking stage of the paper pulping process. The current practice for the disposal of this waste is either by land-spreading, land-filling or incineration which are unsustainable. This work has explored the intermediate pyrolysis of pre-conditioned de-inking sludge pellets in a recently patented 20 kg/h intermediate pyrolysis reactor (The Pyroformer). The reactor is essentially two co-axial screws which are configured in such a way as to circulate solids within the reactor and thus facilitate in the cracking of tars. The potential application of using the volatile organic vapours and permanent gases evolved would be to generate both combined heat and power (CHP) located at paper making sites. The results show that de-inking sludge could be successfully pyrolysed and the organic vapours produced were composed of a mixture of aromatic hydrocarbons, phenolic compounds and some fatty acid methyl esters as detected by liquid GC-MS. The calorific value of the oil after condensing was between 36 and 37 MJ/kg and the liquid fuel properties were also determined, permanent gases were detected by a GC-TCD and were composed of approximately 24% CO, 6% CH and 70% CO (v/v%). The solid residue from pyrolysis also contained a small residual calorific value, and was largely composed of mainly calcium based inert metal oxides. The application of applying intermediate pyrolysis to de-inking sludge for both CHP production and waste reduction is in principle a feasible technology which could be applied at secondary fibre paper mills. © 2013 Elsevier B.V. All rights reserved.

New solid bases for biodiesel synthesis

Biodiesel is a promising non-toxic and biodegradable renewable fuel, synthesized by the homogeneous base-catalyzed transesterification of vegetable oils or animal fats with methanol or ethanol. Removal of the base, typically Na or K alkoxide, after reaction is a major problem since aqueous quenching results in stable emulsions and saponification. The use of a solid base catalyst offers several process advantages including the elimination of a quenching step (and associated basic water waste) to isolate the products, and the opportunity to operate in a continuous process. The synthesis and characterization of a series of Li-doped CaO and Mg-Al hydrotalcite solid base catalysts were presented and their physicochemical properties were correlated with their activity in biodiesel synthesis. Both catalysts were effective solid bases for the transesterification of triglycerides to the methyl ester, with catalyst activity related to the electronic properties of Li and Mg dopants. This is an abstract of a paper presented at the 230th ACS National Meeting (Washington, DC 8/28/2005-9/1/2005).

A CFD study of biomass pyrolysis in a downer reactor equipped with a novel gas-solid separator - I:hydrodynamic performance

This study presents the first part of a CFD study on the performance of a downer reactor for biomass pyrolysis. The reactor was equipped with a novel gas-solid separation method, developed by the co-authors from the ICFAR (Canada). The separator, which was designed to allow for fast separation of clean pyrolysis gas, consisted of a cone deflector and a gas exit pipe installed inside the downer reactor. A multi-fluid model (Eulerian-Eulerian) with constitutive relations adopted from the kinetic theory of granular flow was used to simulate the multiphase flow. The effects of the various parameters including operation conditions, separator geometry and particle properties on the overall hydrodynamics and separation efficiency were investigated. The model prediction of the separator efficiency was compared with experimental measurements. The results revealed distinct hydrodynamic features around the cone separator, allowing for up to 100% separation efficiency. The developed model provided a platform for the second part of the study, where the biomass pyrolysis is simulated and the product quality as a function of operating conditions is analyzed. Crown Copyright © 2014 Published by Elsevier B.V. All rights reserved.

Nanoporous solid acid and base catalysts for sustainable biofuels production

Dwindling fossil fuel reserves, and growing concerns over CO2 emissions and associated climate change, are driving the quest for renewable feedstocks to provide alternative, sustainable fuel sources. Catalysis has a rich history of facilitating energy efficient, selective molecular transformations, and in a post-petroleum era will play a pivotal role in overcoming the scientific and engineering barriers to economically viable, and sustainable, biofuels derived from renewable resources. The production of second generation biofuels, derived from biomass sourced from inedible crop components, e.g. agricultural or forestry waste, or alternative non-food crops such as Switchgrass or Jatropha Curcas that require minimal cultivation, necessitate new heterogeneous catalysts and processes to transform these polar and viscous feedstocks [1]. Here we show how advances in the rational design of nanoporous solid acids and bases, and their utilisation in novel continuous reactors, can deliver superior performance in the energy-efficient esterification and transesterification of bio-oil components into biodiesel [2-4]. Notes: [1] K. Wilson, A.F. Lee, Cat. Sci. Tech. 2012 ,2, 884. [2] J. Dhainaut, J.-P. Dacquin, A. F. Lee, K. Wilson, Green Chem. 2010 , 12, 296. [3] C. Pirez, J.-M. Caderon, J.-P. Dacquin, A.F. Lee, K. Wilson, ACS Catal. 2012 , 2, 1607. [4] J.J. Woodford, J.-P. Dacquin, K. Wilson, A.F. Lee, Energy Environ. Sci. 2012 , 5, 6145.

Optimising the nanoporous architecture of solid acid and base catalysts for biodiesel synthesis

Dwindling oil reserves and growing concerns over CO2 emissions and associated climate change are driving the utilisation of renewable feedstocks as alternative, sustainable fuel sources. While rising oil prices are improving the commercial feasibility of biodiesel production, many current processes still employ homogeneous acid and/or base catalysts to transform plant or algae oil into the fatty acid methyl ester (FAME) components of biodiesel. Fuel purification requires energy intensive aqueous quench and neutralization steps, thus the rational design of new high activity catalysts is required to deliver biodiesel as a major player in the 21st century sustainable energy portfolio. Advances in the development of heterogeneous catalysts for biodiesel synthesis require catalysts with pore architectures designed to improve the accessibility of bulky viscous reactants typical of plant oils. Here we discuss how improvements to active site accessibility and catalyst activity in transesterification or esterification reactions can be achieved either by designing hierarchical pore networks or by pore expansion and use of interconnected pore architectures.

The intermediate pyrolysis of de-inking sludge to produce a sustainable liquid fuel

De-inking sludge is a waste product generated from secondary fibre paper mills who manufacture recycled paper into new paper sheets; it refers directly to the solid residues which evolve during the de-inking stage of the paper pulping process. The current practice for the disposal of this waste is either by land-spreading, land-filling or incineration which are unsustainable. This work has explored the intermediate pyrolysis of pre-conditioned de-inking sludge pellets in a recently patented 20 kg/h intermediate pyrolysis reactor (The Pyroformer). The reactor is essentially two co-axial screws which are configured in such a way as to circulate solids within the reactor and thus facilitate in the cracking of tars. The potential application of using the volatile organic vapours and permanent gases evolved would be to generate both combined heat and power (CHP) located at paper making sites. The results show that de-inking sludge could be successfully pyrolysed and the organic vapours produced were composed of a mixture of aromatic hydrocarbons, phenolic compounds and some fatty acid methyl esters as detected by liquid GC-MS. The calorific value of the oil after condensing was between 36 and 37 MJ/kg and the liquid fuel properties were also determined, permanent gases were detected by a GC-TCD and were composed of approximately 24% CO, 6% CH and 70% CO (v/v%). The solid residue from pyrolysis also contained a small residual calorific value, and was largely composed of mainly calcium based inert metal oxides. The application of applying intermediate pyrolysis to de-inking sludge for both CHP production and waste reduction is in principle a feasible technology which could be applied at secondary fibre paper mills. © 2013 Elsevier B.V. All rights reserved.

Tuning solid acid catalysts for glucose conversion to platform chemicals

Worldwide concern over dwindling fossil fuel reserves and impact of CO2 emissions on climate change means there is an urgent need to reduce our dependence on oil based sources of fuels and chemicals. The direct conversion of lignocellulosic derived glucose to 5-Hydroxymethylfurfural (5-HMF) is an attractive process for the production of chemicals and fuels but requires a bi-functional catalyst with acid-base or Lewis-Brönsted sites which can operate efficiently in the aqueous phase. While conventionally viewed as a superacid, the potential for tuning the acid strength in SO4/ZrO2 and potential for coupling bi-functional ZrO2-SO4/ZrO2 sites at low sulfate contents have been overlooked. Our previous work has shown effective tuning of the acid strength in SO4/ZrO2 can be used to direct selectivity in terpene isomerisation thus we rationalised control over HMF selectivity could achieved in a similar fashion. Here we report on a systematic study of the impact of acid properties of SO4/ZrO2 catalysts on the conversion of C6 sugars to 5-HMF in aqueous media and correlate the surface acid-base properties with glucose isomerisation and dehydration capabilities.

A CFD study of biomass pyrolysis in a downer reactor equipped with a novel gas-solid separator-II thermochemical performance and products

A Eulerian-Eulerian CFD model was used to investigate the fast pyrolysis of biomass in a downer reactor equipped with a novel gas-solid separation mechanism. The highly endothermic pyrolysis reaction was assumed to be entirely driven by an inert solid heat carrier (sand). A one-step global pyrolysis reaction, along with the equations describing the biomass drying and heat transfer, was implemented in the hydrodynamic model presented in part I of this study (Fuel Processing Technology, V126, 366-382). The predictions of the gas-solid separation efficiency, temperature distribution, residence time and the pyrolysis product yield are presented and discussed. For the operating conditions considered, the devolatilisation efficiency was found to be above 60% and the yield composition in mass fraction was 56.85% bio-oil, 37.87% bio-char and 5.28% non-condensable gas (NCG). This has been found to agree reasonably well with recent relevant published experimental data. The novel gas-solid separation mechanism allowed achieving greater than 99.9% separation efficiency and < 2 s pyrolysis gas residence time. The model has been found to be robust and fast in terms of computational time, thus has the great potential to aid in future design and optimisation of the biomass fast pyrolysis process.

Solid biofuel production by mechanical pre-treatment of brewers' spent grain

The brewing industry produces large amounts of by-products and wastes like brewers' spent grain (BSG). In Germany, each year approximately 2.1 million tonnes of BSG are generated. During the last years conventional routes of BSG utilization face a remarkable change, such as the decline in the demand as animal feed. Due to its high content of organic matter energetic utilization may create an additional economic value for breweries. Furthermore, in the recent past breweries tend to shift their energy supply towards more sustainable concepts. Although, a decent number of research projects were carried out already, still no mature strategy is available. However, one possible solution can be the mechanical pretreatment of BSG. This step allows optimized energy utilization by the fractionation of BSG. Due to the transfer of digestible components, such as protein, to the liquid phase, the solid phase will largely consist of combustible components. That represents an opportunity to produce a solid biofuel with lower fuelnitrogen content compared to only thermal dried BSG. Therefore, two main purposes for the mechanical pre-treatment were determined, (1) to reduce the moisture content to at least 60 % (w/w) and (2) to diminish the protein content of the solid phase by 30 %. Moreover, the combustion trials should demonstrate whether stable processes and flue gas emissions within the legal limits in Germany are feasible. The results of the mechanical pre-treatment trials showed that a decrease of the moisture and protein content has been achieved. With regard to the combustion trials inconsistent outcomes were found. On the one hand a stable combustion was realized. On the other hand the legal emission levels of NOx (500 mgm -3) and dust (50 mgm-3) could not be kept during all trials. The further research steps will focus on the optimization of the air/fuel ratio by reducing the primary and secondary air conditions. Copyright © 2014,AIDIC Servizi S.r.l.