A kinetic reaction model for biomass pyrolysis processes in Aspen Plus

This paper presents a novel kinetic reaction model for biomass pyrolysis processes. The model is based on the three main building blocks of lignocellulosic biomass, cellulose, hemicellulose and lignin and can be readily implemented in Aspen Plus and easily adapted to other process simulation software packages. It uses a set of 149 individual reactions that represent the volatilization, decomposition and recomposition processes of biomass pyrolysis. A linear regression algorithm accounts for the secondary pyrolysis reactions, thus allowing the calculation of slow and intermediate pyrolysis reactions. The bio-oil is modelled with a high level of detail, using up to 33 model compounds, which allows for a comprehensive estimation of the properties of the bio-oil and the prediction of further upgrading reactions. After showing good agreement with existing literature data, our own pyrolysis experiments are reported for validating the reaction model. A beech wood feedstock is subjected to pyrolysis under well-defined conditions at different temperatures and the product yields and compositions are determined. Reproducing the experimental pyrolysis runs with the simulation model, a high coincidence is found for the obtained fraction yields (bio-oil, char and gas), for the water content and for the elemental composition of the pyrolysis products. The kinetic reaction model is found to be suited for predicting pyrolysis yields and product composition for any lignocellulosic biomass feedstock under typical pyrolysis conditions without the need for experimental data

Impact of potassium and phosphorus in biomass on the properties of fast Pyrolysis bio-oil

This study investigates fast pyrolysis bio-oils produced from alkali-metal-impregnated biomass (beech wood). The impregnation aim is to study the catalytic cracking of the pyrolysis vapors as a result of potassium or phosphorus. It is recognized that potassium and phosphorus in biomass can have a major impact on the thermal conversion processes. When biomass is pyrolyzed in the presence of alkali metal cations, catalytic cracking of the pyrolysis liquids occurs in the vapor phase, reducing the organic liquids produced and increasing yields of water, char, and gas, resulting in a bio-oil that has a lower calorific value and an increased chance of phase separation. Beech wood was impregnated with potassium or phosphorus (K impregnation and P impregnation, respectively) in the range of 0.10-2.00 wt %. Analytical pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) was used to examine the pyrolysis products during thermal degradation, and thermogravimetric analysis (TGA) was used to examine the distribution of char and volatiles. Both potassium and phosphorus are seen to catalyze the pyrolytic decomposition of biomass and modify the yields of products. 3-Furaldehyde and levoglucosenone become more dominant products upon P impregnation, pointing to rearrangement and dehydration routes during the pyrolysis process. Potassium has a significant influence on cellulose and hemicellulose decomposition, not just on the formation of levoglucosan but also other species, such as 2(5H)-furanone or hydroxymethyl-cyclopentene derivatives. Fast pyrolysis processing has also been undertaken using a laboratory-scale continuously fed bubbling fluidized-bed reactor with a nominal capacity of 1 kg h-1 at the reaction temperature of 525 °C. An increase in the viscosity of the bio-oil during the stability assessment tests was observed with an increasing percentage of impregnation for both additives. This is because bio-oil undergoes polymerization while placed in storage as a result of the inorganic content. The majority of inorganics are concentrated in the char, but small amounts are entrained in the pyrolysis vapors and, therefore, end up in the bio-oil

Review of physicochemical properties and analytical characterization of lignocellulosic biomass

Lignocellulosic biomass is the most abundant and renewable material in the world for the production of biofuels. Using lignocellulosic biomass derived biofuels could reduce reliance on fossil fuels and contribute to climate change mitigation. A profound understanding of the physicochemical properties of lignocellulosic biomass and the analytical characterization methods for those properties is essential for the design and operation of associated biomass conversion processing facilities. The present article aims to present a comprehensive review of physicochemical properties of lignocellulosic biomass, including particle size, grindability, density, flowability, moisture sorption, thermal properties, proximate analysis properties, elemental composition, energy content and chemical composition. The corresponding characterization techniques for these properties and their recent development are also presented. This review is intended to provide the readers systematic knowledge in the physicochemical properties of lignocellulosic biomass and characterization techniques for the conversion of biomass and the application of biofuels

Supersymmetry Breaking in the Early Universe

Supersymmetry breaking in the early universe induces scalar soft potentials with curvature of order the Hubble constant. This has a dramatic effect on the coherent production of scalar fields along flat directions. For the moduli problem it generically gives a concrete realization of the problem by determining the field value subsequent to inflation. However it might suggest a solution if the minimum of the induced potential coincides with the true minimum. The induced Hubble scale mass also has important implications for the Affleck-Dine mechanism of baryogenesis. This mechanism requires large squark or slepton expectation values to develop along flat directions in the early universe. This is generally not the case if the induced mass squared is positive, but does occur if it is negative. The resulting baryon to entropy ratio depends mainly on the dimension of the nonrenormalizable operator in the superpotential which stabilizes the flat direction, and the reheat temperature after inflation. Unlike the original scenario, it is possible to obtain an acceptable baryon asymmetry without subsequent entropy releases.Comment: 11 pages, requires phyzz

Theoretical Analysis of Double Logistic Distributed Activation Energy Model for Thermal Decomposition Kinetics of Solid Fuels

The distributed activation energy model (DAEM) has been widely used to analyze the thermal decomposition of solid fuels such as lignocellulosic biomass and its components, coal, microalgae, oil shale, waste plastics, and polymer etc. The DAEM with a single distribution of activation energies cannot describe those reactions well since the thermal decomposition normally involves multiple sub-processes of various components. The double DAEM employs a double distribution to represent the activation energies. The Gaussian distribution is usually used to represent the activation energies. However, it is not sufficiently accurate for addressing the activation energies in the initial and final stages of the thermal decomposition reactions of solid fuels. Compared to the Gaussian distribution, the logistic distribution is slightly thicker at the curve tail and suits better to describe the activation energy distribution. In this work, a theoretical analysis of the double logistic DAEM for the thermal decomposition kinetics of solid fuels has been systematically investigated. After the derivation of the double logistic DAEM, its numerical calculation method and the physical meanings of the model parameters have been presented. Three typical types of simulated double logistic DAEM processes have been obtained according to the overlapped situation of two derivative conversion peaks, namely separated, overlapped and partially overlapped processes. It is found that, for the partially overlapped process, the form of the minor peak (overlapped peak or peak shoulder) depends on the values of the frequency factor and heating rate. Considering the simulated processes and related examples from literature, the double logistic DAEM has been remarked as a more reliable tool with abundant flexibility to explain the thermal decomposition of various solid fuels. More accurate results are expected if the double logistic DAEM is coupled with the computational fluid dynamics (CFD) simulation for those reactions mentioned above

Now the wars are over: The past, present and future of Scottish battlefields

Battlefield archaeology has provided a new way of appreciating historic battlefields. This paper provides a summary of the long history of warfare and conflict in Scotland which has given rise to a large number of battlefield sites. Recent moves to highlight the archaeological importance of these sites, in the form of Historic Scotland’s Battlefields Inventory are discussed, along with some of the problems associated with the preservation and management of these important cultural sites

Comparative study on catalytic and non-catalytic pyrolysis of olive mill solid wastes

In this study, catalytic and non-catalytic fast pyrolysis of dried olive husk and olive kernels was carried out. A bubbling fluidised bed reactor was used for the non-catalytic processing of the solid olive wastes. In-situ catalytic upgrading of biomass fast pyrolysis vapours was performed in a fixed bed bench-scale reactor at 500 °C, for catalyst screening purposes. A maximum bio-oil yield of 47.35 wt.% (on dry biomass) was obtained from non-catalytic fast pyrolysis at a reaction temperature of 450 °C, while the bio-oil yield was decreased at 37.14 wt.% when the temperature was increased to 500 °C. In the case of the fixed bed unit tests, the highest liquid (52.66 wt.%) and organics (30.99 wt.%) yield was achieved with the use of the non-catalytic silica sand. Depending on the catalytic material, the liquid yield ranged from 47.03 to 43.96 wt.% the organic yield from 21.15 to 16.34 wt.% on dry biomass. Solid products were increased from 28.23 wt.% for the non-catalytic run to 32.81 wt.% on dry biomass, when MgO (5% Co) was used

Viscosity of aged bio-oils from fast pyrolysis of beech wood and miscanthus:shear rate and temperature dependence

The viscosity of four aged bio-oil samples was measured experimentally at various shear rates and temperatures using a rotational viscometer. The experimental bio-oils were derived from fast pyrolysis of beech wood at 450, 500, and 550 °C and Miscanthus at 500 °C (in this work, they were named as BW1, BW2, BW3, and MXG) in a bubbling fluidized bed reactor. The viscosity of all bio-oils was kept constant at various shear rates at the same temperature, which indicated that they were Newtonian fluids. The viscosity of bio-oils was strongly dependent upon the temperature, and with the increase of the temperature from 30 to 80 °C, the viscosity of BW1, BW2, BW3, and MXG decreased by 90.7, 93.3, 92.6, and 90.2%, respectively. The Arrhenius viscosity model, which has been commonly used to represent the temperature dependence of the viscosity of many fluids, did not fit the viscosity-temperature experimental data of all bio-oils very well, especially in the low- and high-temperature regions. For comparison, the Williams-Landel-Ferry (WLF) model was also used. The results showed that the WLF model gave a very good description of the viscosity-temperature relationship of each bio-oil with very small residuals and the BW3 bio-oil had the strongest viscosity-temperature dependence

Adult Social Work and High Risk Domestic Violence Cases

Summary This article focuses on adult social work’s response in England to high-risk domestic violence cases and the role of adult social workers in Multi-Agency Risk and Assessment Conferences. (MARACs). The research was undertaken between 2013-2014 and focused on one city in England and involved the research team attending MARACs, Interviews with 20 adult social workers, 24 MARAC attendees, 14 adult service users at time T1 (including follow up interviews after six months, T2), focus groups with IDVAs and Women’s Aid and an interview with a Women’s Aid service user. Findings The findings suggest that although adult social workers accept the need to be involved in domestic violence cases they are uncertain of what their role is and are confused with the need to operate a parallel domestic violence and adult safeguarding approach, which is further, complicated by issues of mental capacity. MARACS are identified as overburdened, under-represented meetings staffed by committed managers. However, they are in danger of becoming managerial processes neglecting the service users they are meant to protect. Applications The article argues for a re-engagement of adult social workers with domestic violence that has increasingly become over identified with child protection. It also raises the issue whether MARACS remain fit for purpose and whether they still represent the best possible response to multi-agency coordination and practice in domestic violence

Hobson’s choice? Constraints on accessing spaces of creative production

Successful creative production is often documented to occur in urban areas that are more likely to be diverse, a source of human capital and the site of dense interactions. These accounts chart how, historically, creative industries have clustered in areas where space was once cheap in the city centre fringe and inner city areas, often leading to the development of a creative milieu, and thereby stimulating further creative production. Historical accounts of the development of creative areas demonstrate the crucial role of accessible low-cost business premises. This article reports on the findings of a case study that investigated the location decisions of firms in selected creative industry sectors in Greater Manchester. The study found that, while creative activity remains highly concentrated in the city centre, creative space there is being squeezed and some creative production is decentralizing in order to access cheaper premises. The article argues that the location choices of creative industry firms are being constrained by the extensive city centre regeneration, with the most vulnerable firms, notably the smallest and youngest, facing a Hobson’s choice of being able to access low-cost premises only in the periphery. This disrupts the delicate balance needed to sustain production and begs the broader question as to how the creative economy fits into the existing urban fabric, alongside the competing demands placed on space within a transforming industrial conurbation