Zirconia and alumina based catalysts for steam reforming of naphthalene

The present paper deals with experimentation of ZrO2 and Al2O3-supported catalysts for conversion of naphthalene, chosen as tar model compound of pyrolysis or gasification syngas. In particular, the reforming capacity of active metals and promoters such as Co, Ni, Fe, Cr, Ce and Pt was tested in a fixed bed reactor at temperature from 400 to 900 °C. As regards ZrO2-supported catalysts, the best results were achieved by the Ni/Fe/Pt catalyst with 96% naphthalene conversion, 78% and 280% as CO and H2 production yield at 800 °C. Regarding Al2O3-supported catalysts, they were more active on average than the zirconia ones, achieving a very good performance even at 500 °C (90–100% naphthalene conversion, 30–40% CO yield and 300–350% H2 yield at 550 °C). Influence of different amounts of alumina, montmorillonite and carbon on carrier composition as well as pellets’ size were also studied. Both zirconia and alumina catalysts showed deactivation at higher temperatures due to coke deposition, resulting in a strong H2 production drop. Regeneration of catalysts by O2 and steam as well as activation by H2 were also studied. The activated catalyst was able to convert more than 99% naphthalene at 450 °C with a CO and H2 production yield of 26% and 420%, respectively.

The role of organoclay in promoting co-continuous morphology in high-density poly(ethylene)/poly(amide) 6 blends

The effect of organically modified clay on the morphology, rheology and mechanical properties of high-density polyethylene (HDPE) and polyamide 6 (PA6) blends (HDPE/PA6 = 75/25 parts) is studied. Virgin and filled blends were prepared by melt compounding the constituents using a twin-screw extruder. The influence of the organoclay on the morphology of the hybrid was deeply investigated by means of wide-angle X-ray diffractometry, transmission and scanning electron microscopies and quantitative extraction experiments. It has been found that the organoclay exclusively places inside the more hydrophilic polyamide phase during the melt compounding. The extrusion process promotes the formation of highly elongated and separated organoclay-rich PA6 domains. Despite its low volume fraction, the filled minor phase eventually merges once the extruded pellets are melted again, giving rise to a co-continuous microstructure. Remarkably, such a morphology persists for long time in the melt state. A possible compatibilizing action related to the organoclay has been investigated by comparing the morphology of the hybrid blend with that of a blend compatibilized using an ethylene–acrylic acid (EAA) copolymer as a compatibilizer precursor. The former remains phase separated, indicating that the filler does not promote the enhancement of the interfacial adhesion. The macroscopic properties of the hybrid blend were interpreted in the light of its morphology. The melt state dynamics of the materials were probed by means of linear viscoelastic measurements. Many peculiar rheological features of polymer-layered silicate nanocomposites based on single polymer matrix were detected for the hybrid blend. The results have been interpreted proposing the existence of two distinct populations of dynamical species: HDPE not interacting with the filler, and a slower species, constituted by the organoclay-rich polyamide phase, which slackened dynamics stabilize the morphology in the melt state. In the solid state, both the reinforcement effect of the filler and the co-continuous microstructure promote the enhancement of the tensile modulus. Our results demonstrate that adding nanoparticles to polymer blends allows tailoring the final properties of the hybrid, potentially leading to high-performance materials which combine the advantages of polymer blends and the merits of polymer nanocomposites.

Fixed bed downdraft gasification of paper industry wastes

The two main wastes generated from secondary fibre paper mills are rejects (composed mainly of plastics and fibres) and de-inking sludge, both of which are evolved from the pulping process during paper manufacture. The current practice for the disposal of these wastes is either by land-spreading or land-filling. This work explores the gasification of blends of pre-conditioned rejects and de-inking sludge pellets with mixed wood chips in an Imbert type fixed bed downdraft gasifier with a maximum feeding capacity of 10kg/h. The producer gases evolved would generate combined heat and power (CHP) in an internal combustion engine. The results show that as much as 80wt.% of a brown paper mill's rejects (consisting of 20wt.% mixed plastics and 80wt.% paper fibres) could be successfully gasified in a blend with 20wt.% mixed wood chips. The producer gas composition was 16.24% H, 23.34% CO, 12.71% CO 5.21% CH and 42.49% N (v/v%) with a higher heating value of 7.3MJ/Nm. After the removal of tar and water condensate the producer gas was of sufficient calorific value and flow rate to power a 10kWe gas engine. Some blends using rejects from other mill types were not successful, and the limiting factor was usually the agglomeration of plastics present within the fuel.

In situ catalytic upgrading of bio-oil using supported molybdenum carbide

The aim of this work is to improve some of the less desirable properties of bio-oil via the catalytic fast pyrolysis of sugarcane bagasse using a novel supported molybdenum carbide (20 wt.% MoC/AlO ) catalyst. Proximate and elemental analysis of the bagasse were carried out to determine the moisture, ash, carbon, hydrogen, nitrogen and oxygen content. The ground pellets were classified in sieves to a size range of 0.25-1 mm and were pyrolysed in a 300 g h fluidised bed reactor at 500 C. MoC/AlO replaced the sand in the fluidised bed reactor in different proportions (0 wt.%, 12 wt.%, 25 wt.% and 50 wt.%) to investigate the effect of this catalyst on the pyrolysis products. Bio-oil yield results showed that ground sugarcane bagasse pellets gave high organic yields in the bio-oil of 60.5 wt.% on dry feed with a total liquid yield of 73.1 wt.% on dry feed without catalyst. Increasing the catalyst proportions in the fluidised bed reduced bio-oil yields, significantly reduced sugars (as a-levoglucosan) concentration and increased furanics and phenolics concentration in the bio-oil. It was observed that the higher the concentration of the 20 wt.% MoC/AlO catalyst in the fluidised bed the lower the viscosity of the bio-oil. © 2013 Elsevier B.V. All rights reserved.

Bone marrow-derived mesenchymal stem cells become anti-angiogenic when chondrogenically or osteogenically differentiated:implications for bone and cartilage tissue engineering

Osteochondral tissue repair requires formation of vascularized bone and avascular cartilage. Mesenchymal stem cells stimulate angiogenesis both in vitro and in vivo but it is not known if these proangiogenic properties change as a result of chondrogenic or osteogenic differentiation. We investigated the angiogenic/antiangiogenic properties of equine bone marrow-derived mesenchymal stem cells (eBMSCs) before and after differentiation in vitro. Conditioned media from chondrogenic and osteogenic cell pellets and undifferentiated cells was applied to endothelial tube formation assays using Matrigel™. Additionally, the cell secretome was analysed using LC-MS/MS mass spectrometry and screened for angiogenesis and neurogenesis-related factors using protein arrays. Endothelial tube-like formation was supported by conditioned media from undifferentiated eBMSCs. Conversely, chondrogenic and osteogenic conditioned media was antiangiogenic as shown by significantly decreased length of endothelial tube-like structures and degree of branching compared to controls. Undifferentiated cells produced higher levels of angiogenesis-related proteins compared to chondrogenic and osteogenic pellets. In summary, eBMSCs produce an array of angiogenesis-related proteins and support angiogenesis in vitro via a paracrine mechanism. However, when these cells are differentiated chondrogenically or osteogenically, they produce a soluble factor(s) that inhibits angiogenesis. With respect to osteochondral tissue engineering, this may be beneficial for avascular articular cartilage formation but unfavourable for bone formation where a vascularized tissue is desired. © Copyright 2014, Mary Ann Liebert, Inc.

Experiments on the generation of activated carbon from biomass

Activated carbon is generated from various waste biomass sources like rice straw, wheat straw, wheat straw pellets, olive stones, pistachios shells, walnut shells, beech wood and hardcoal. After drying the biomass is pyrolysed in the temperature range of 500-600 °C at low heating rates of 10 K/min. The activation of the chars is performed as steam activation at temperatures between 800 °C and 900 °C. Both the pyrolysis and activation experiments were run in lab-scale facilities. It is shown that nut shells provide high active surfaces of 1000-1300 m/g whereas the active surface of straw matters does hardly exceed 800 m/g which might be a result of the high ash content of the straws and the slightly higher carbon content of the nut shells. The active surface is detected by BET method. Besides the testing of a many types of biomass for the suitability as base material in the activated carbon production process, the experiments allow for the determination of production parameters like heating rate and pyrolysis temperature, activation time and temperature as well as steam flux which are necessary for the scale up of the process chain. © 2006 Elsevier B.V. All rights reserved.

Thermo-chemical conversion of straw:Haloclean : a performance enhanced low temperature pyrolysis

Haloclean a performance enhanced low temperature pyrolysis for biomass developed by Forschungszentrum Karlsruhe and Sea Marconi Is closing the gap between classical and fast pyrolysis approaches. For pyrolysis of straw (chaffed-, finely ground and pellets) temperature ranges between 320 to 420°C and residence times of only 1 to 5 minutes can be realized. Liquid yields of up to 45 wt-% and 35 wt-% of solids are possible. Solid yields can be increased up to 73 wt-% while loosing 4.5 % of the feed energy by pyrolysis gases only. Toxicity tests of the fractions do not show relevant numbers.

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.

Energy production from biomass and waste derived intermediate pyrolysis oils

This study investigates the use of Pyroformer intermediate pyrolysis system to produce alternative diesel engines fuels (pyrolysis oil) from various biomass and waste feedstocks and the application of these pyrolysis oils in a diesel engine generating system for Combined Heat and Power (CHP) production. The pyrolysis oils were produced in a pilot-scale (20 kg/h) intermediate pyrolysis system. Comprehensive characterisations, with a view to use as engine fuels, were carried out on the sewage sludge and de-inking sludge derived pyrolysis oils. They were both found to be able to provide sufficient heat for fuelling a diesel engine. The pyrolysis oils also presented poor combustibility and high carbon deposition, but these problems could be mitigated by means of blending the pyrolysis oils with biodiesel (derived from waste cooking oil). The blends of SSPO (sewage sludge pyrolysis oil) and biodiesel (30/70 and 50/50 in volumetric ratios) were tested in a 15 kWe Lister type stationary generating system for up to 10 hours. There was no apparent deterioration observed in engine operation. With 30% SSPO blended into biodiesel, the engine presents better overall performance (electric efficiency), fuel consumption, and overall exhaust emissions than with 50% SSPO blend. An overall system analysis was carried out on a proposed integrated Pyroformer-CHP system. Combined with real experimental results, this was used for evaluating the costs for producing heat and power and char from wood pellets and sewage sludge. It is concluded that the overall system efficiencies for both types of plant can be over 40%; however the integrated CHP system is not economically viable. This is due to extraordinary project capital investment required.

Low temperature sintering semiconducting barium strontium titanate

Low temperature sintering has become a very important research area in ceramics processing and sintering as a promising process to obtain grain size below 100nm. For electronic ceramics, low temperature sintering is particularly difficult, because not only the required microstructure but also the desired electronic properties should be obtained. In this dissertation, the effect of liquid sintering aids and particle size (micrometer and nanometer) on sintering temperature and Positive Temperature Coefficient Resistivity (PTCR) property are investigated for Ba1-xSrxTiO3 (BST) doped with 0.2-0.3mol% Sb3+ (x = 0.1, 0.2, 0.3, 0.4 and 0.5). Different sintering aids with low melting point are used as sintering aids to decrease the sintering temperature for micrometer size BST particles. Micrometer size and nanometer size Ba1-xSrxTiO 3 (BST) particles are used to demonstrate the particle size effect on the sintering temperature for semiconducting BST. To reduce the sintering temperature, three processes are developed, i.e. 1 using sol-gel nanometer size Sb3+ doped powders with a sintering aid; 2 using micrometer size powders plus a sintering aid; and 3 using nanometer size Sb3+ doped powders with sintering aids. Grain size effect on PTCR characteristics is investigated through comparison between micrometer size powder sintered pellets and nanometer size powder sintered pellets. The former has lower resistivity at temperatures below the Curie temperature (Tc) and high resistivity at temperatures above the Curie temperature (Tc) along with higher ρ max/ρmin ratio (ρmax is the highest resistivity at temperatures above Tc, ρmin is the lowest resistivity at temperatures below Tc), whereas the latter has both higher ρ max and ρmin. Also, ρmax/ρmin is smaller than that of pellets with larger grain size. The reason is that the solid with small grain size has more grain boundaries than the solid with large grain size. The contribution z at room temperature and high temperature and a lower ρmax/ρmin ratio value.

Elemental analysis and forensic comparison of soils by laser-induced breakdown spectroscopy (LIBS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS)

The elemental analysis of soil is useful in forensic and environmental sciences. Methods were developed and optimized for two laser-based multi-element analysis techniques: laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and laser-induced breakdown spectroscopy (LIBS). This work represents the first use of a 266 nm laser for forensic soil analysis by LIBS. Sample preparation methods were developed and optimized for a variety of sample types, including pellets for large bulk soil specimens (470 mg) and sediment-laden filters (47 mg), and tape-mounting for small transfer evidence specimens (10 mg). Analytical performance for sediment filter pellets and tape-mounted soils was similar to that achieved with bulk pellets. An inter-laboratory comparison exercise was designed to evaluate the performance of the LA-ICP-MS and LIBS methods, as well as for micro X-ray fluorescence (μXRF), across multiple laboratories. Limits of detection (LODs) were 0.01-23 ppm for LA-ICP-MS, 0.25-574 ppm for LIBS, 16-4400 ppm for μXRF, and well below the levels normally seen in soils. Good intra-laboratory precision (≤ 6 % relative standard deviation (RSD) for LA-ICP-MS; ≤ 8 % for μXRF; ≤ 17 % for LIBS) and inter-laboratory precision (≤ 19 % for LA-ICP-MS; ≤ 25 % for μXRF) were achieved for most elements, which is encouraging for a first inter-laboratory exercise. While LIBS generally has higher LODs and RSDs than LA-ICP-MS, both were capable of generating good quality multi-element data sufficient for discrimination purposes. Multivariate methods using principal components analysis (PCA) and linear discriminant analysis (LDA) were developed for discriminations of soils from different sources. Specimens from different sites that were indistinguishable by color alone were discriminated by elemental analysis. Correct classification rates of 94.5 % or better were achieved in a simulated forensic discrimination of three similar sites for both LIBS and LA-ICP-MS. Results for tape-mounted specimens were nearly identical to those achieved with pellets. Methods were tested on soils from USA, Canada and Tanzania. Within-site heterogeneity was site-specific. Elemental differences were greatest for specimens separated by large distances, even within the same lithology. Elemental profiles can be used to discriminate soils from different locations and narrow down locations even when mineralogy is similar.

Low Temperature Sintering Semiconductive Barium Strontium Titanate

Low temperature sintering has become a very important research area in ceramics processing and sintering as a promising process to obtain grain size below 100nm. For electronic ceramics, low temperature sintering is particularly difficult, because not only the required microstructure but also the desired electronic properties should be obtained. In this dissertation, the effect of liquid sintering aids and particle size (micrometer and nanometer) on sintering temperature and Positive Temperature Coefficient Resistivity (PTCR) property are investigated for Ba1-xSrxTiO3 (BST) doped with 0.2-0.3mol% Sb3+ (x = 0.1,0.2,0.3,0.4 and 0.5). Different sintering aids with low melting point are used as sintering aids to decrease the sintering temperature for micrometer size BST particles. Micrometer size and nanometer size Ba1-xSrxTiO3 (BST) particles are used to demonstrate the particle size effect on the sintering temperature for semiconducting BST. To reduce the sintering temperature, three processes are developed, i.e. 1 using sol-gel nanometer size Sb3+ doped powders with a sintering aid; 2 using micrometer size powders plus a sintering aid; and 3 using nanometer size Sb3+ doped powders with sintering aids. Grain size effect on PTCR characteristics is investigated through comparison between micrometer size powder sintered pellets and nanometer size powder sintered pellets. The former has lower resistivity at temperatures below the Curie temperature (Tc) and high resistivity at temperatures above the Curie temperature (Tc) along with higher ñmax/ñmin ratio (ñmax is the highest resistivity at temperatures above Tc, ñmin is the lowest resistivity at temperatures below Tc), whereas the latter has both higher ñmax and ñmin. Also, ñmax/ñmin is smaller than that of pellets with larger grain size. The reason is that the solid with small grain size has more grain boundaries than the solid with large grain size. The contribution z at room temperature and high temperature and a lower ñmax/ñmin ratio value.

Observations and rare earth element composition of manganese nodules during Atlantis cruise AT266, Blake Plateau

An area of about 22,000 km² on the northern Blake Plateau, off the coast of South Carolina, contains an estimated 2 billion metric tons of phosphorite concretions, and about 1.2 billion metric tons of mixed ferromanganese-phosphorite pavement. Other offshore phosphorites occur between the Blake Plateau and known continental deposits, buried under variable thicknesses of sediments. The phosphorite resembles other marine phosphorites in composition, consisting primarily of carbonate-fluorapatite, some calcite, minor quartz and other minerals. The apatite is optically pseudo-isotropic and contains about 6% [CO3]**2- replacing [PO4]**3- in its structure. JOIDES drillings and other evidence show that the phosphorite is a lag deposit derived from Miocene strata correlatable with phosphatic Middle Tertiary sediments on the continent. It has undergone variable cycles of erosion, reworking, partial dissolution and reprecipitation. Its present form varies from phosphatized carbonate debris, loose pellets, and pebbles, to continuous pavements, plates, and conglomeratic boulders weighing hundreds of kilograms. No primary phosphatization is currently taking place on the Blake Plateau. The primary phosphate-depositing environment involved reducing conditions and required at least temporary absence of the powerful Gulf Stream current that now sweeps the bottom of the Blake Plateau and has eroded away the bulk of the Hawthorne-equivalent sediments with which the phosphorites were once associated.

Antarctic sympagic meiofauna in winter

This study of Antarctic sympagic meiofauna in pack ice during late winter compares communities between the perennially ice-covered western Weddell Sea and the seasonally ice-covered southern Indian Ocean. Sympagic meiofauna (proto- and metazoans > 20 µm) and eggs > 20 µm were studied in terms of diversity, abundance and carbon biomass, and with respect to vertical distribution. Metazoan meiofauna had significantly higher abundance and biomass in the western Weddell Sea (medians: 31.1 * 10**3/m**2 and 6.53 mg/m**2, respectively) than in the southern Indian Ocean (medians: 1.0 * 10**3 /m**2 and 0.06 mg/m**2, respectively). Metazoan diversity was also significantly higher in the western Weddell Sea. Furthermore, the two regions differed significantly in terms of meiofauna community composition, as revealed through multivariate analyses. The overall diversity of sympagic meiofauna was high, and integrated abundance and biomass of total meiofauna were also high in both regions (0.6 - 178.6 * 10**3/m**2 and 0.02 - 89.70 mg/m**2, respectively), mostly exceeding values reported earlier from the western Weddell Sea in winter. We attribute the differences in meiofauna communities between the two regions to the older first-year ice and multi-year ice that is present in the western Weddell Sea, but not in the southern Indian Ocean. Our study indicates the significance of perennially ice-covered regions for the establishment of diverse and abundant meiofauna communities. Furthermore, it highlights the potential importance of sympagic meiofauna for the organic matter pool and trophic interactions in sea ice.

Dynamic Life Cycle Assessment Modeling Approaches for Transboundary Energy Feedstocks

The rise of the twenty-first century has seen the further increase in the industrialization of Earth’s resources, as society aims to meet the needs of a growing population while still protecting our environmental and natural resources. The advent of the industrial bioeconomy – which encompasses the production of renewable biological resources and their conversion into food, feed, and bio-based products – is seen as an important step in transition towards sustainable development and away from fossil fuels. One sector of the industrial bioeconomy which is rapidly being expanded is the use of biobased feedstocks in electricity production as an alternative to coal, especially in the European Union.

As bioeconomy policies and objectives increasingly appear on political agendas, there is a growing need to quantify the impacts of transitioning from fossil fuel-based feedstocks to renewable biological feedstocks. Specifically, there is a growing need to conduct a systems analysis and potential risks of increasing the industrial bioeconomy, given that the flows within it are inextricably linked. Furthermore, greater analysis is needed into the consequences of shifting from fossil fuels to renewable feedstocks, in part through the use of life cycle assessment modeling to analyze impacts along the entire value chain.

To assess the emerging nature of the industrial bioeconomy, three objectives are addressed: (1) quantify the global industrial bioeconomy, linking the use of primary resources with the ultimate end product; (2) quantify the impacts of the expaning wood pellet energy export market of the Southeastern United States; (3) conduct a comparative life cycle assessment, incorporating the use of dynamic life cycle assessment, of replacing coal-fired electricity generation in the United Kingdom with wood pellets that are produced in the Southeastern United States.

To quantify the emergent industrial bioeconomy, an empirical analysis was undertaken. Existing databases from multiple domestic and international agencies was aggregated and analyzed in Microsoft Excel to produce a harmonized dataset of the bioeconomy. First-person interviews, existing academic literature, and industry reports were then utilized to delineate the various intermediate and end use flows within the bioeconomy. The results indicate that within a decade, the industrial use of agriculture has risen ten percent, given increases in the production of bioenergy and bioproducts. The underlying resources supporting the emergent bioeconomy (i.e., land, water, and fertilizer use) were also quantified and included in the database.

Following the quantification of the existing bioeconomy, an in-depth analysis of the bioenergy sector was conducted. Specifically, the focus was on quantifying the impacts of the emergent wood pellet export sector that has rapidly developed in recent years in the Southeastern United States. A cradle-to-gate life cycle assessment was conducted in order to quantify supply chain impacts from two wood pellet production scenarios: roundwood and sawmill residues. For reach of the nine impact categories assessed, wood pellet production from sawmill residues resulted in higher values, ranging from 10-31% higher.

The analysis of the wood pellet sector was then expanded to include the full life cycle (i.e., cradle-to-grave). In doing to, the combustion of biogenic carbon and the subsequent timing of emissions were assessed by incorporating dynamic life cycle assessment modeling. Assuming immediate carbon neutrality of the biomass, the results indicated an 86% reduction in global warming potential when utilizing wood pellets as compared to coal for electricity production in the United Kingdom. When incorporating the timing of emissions, wood pellets equated to a 75% or 96% reduction in carbon dioxide emissions, depending upon whether the forestry feedstock was considered to be harvested or planted in year one, respectively.

Finally, a policy analysis of renewable energy in the United States was conducted. Existing coal-fired power plants in the Southeastern United States were assessed in terms of incorporating the co-firing of wood pellets. Co-firing wood pellets with coal in existing Southeastern United States power stations would result in a nine percent reduction in global warming potential.