Biomass gasification in a fluidized bed reactor: effect of temperature on properties and oxidative reactivity of chars

Introduction: Biomass gasification is a promising alternative to fossil fuels for the synthesis of highly energetic products via Fischer-Tropsch or methanation processes. It is a thermochemical conversion occurring at high temperatures with many simultaneous reactions. For temperatures above 350°C, biomass undergoes a thermal decomposition called pyrolysis which leads to the formation of volatile products either condensable (steam and tars) or incondensable (H2, CO, CO2, CH4 and C2Hx) and a solid residue called char [1]. Then, the char reacts with steam and carbon dioxide at temperatures greater than 700°C to produce syngas. These transformations are endothermic. Therefore, a contribution of energy is required to maintain the temperature and the different reactions. One of the most encouraging and advanced technology is dual fluidized beds [2]. Its principle relies on the circulation of a media (sand, olivine or catalyst particles) which acts as a heat carrier between an endothermic reactor, where biomass gasification produces syngas, and an exothermic reactor where combustion of a part of the char from the gasification of biomass produces heat. Therefore, it is of importance to carefully understand the effect of operating conditions on char structure and composition which are directly related to its reactivity in combustion and steam gasification. During pyrolysis of biomass, many changes occur in the solid structure including (1) the loss of functional groups on the carbon surface, (2) ordering of the carbon microstructure to tend to a graphitic crystalline form, (3) the formation of pores which directly influence the surface area, (4) the modification in ash content and its distribution that affect the catalytic activity of chars. Together, these changes are responsible for the steam gasification and combustion reactivity of the chars. Please click Additional Files below to see the full abstract

Adsorption of nucleotides on biomimetic apatite: The case ofadenosine 5' triphosphate (ATP)

ATP is a well-known energy supplier in cells. The idea to associate ATP to pharmaceutical formulations/biotechnological devices to promote cells activity by potentially modulating their microenvironment thus appears as an appealing novel approach. Since biomimetic nanocrystalline apatites have shown great promise for biomedical applications (bone regeneration, cells diagnostics/therapeutics,...), thanks to a high surface reactivity and an intrinsically high biocompatibility, the present contribution was aimed at exploring ATP/apatite interactions. ATP adsorption on a synthetic carbonated nanocrystalline apatite preliminarily characterized (by XRD, FTIR, Raman, TG-DTA and SEM-EDX) was investigated in detail, pointing out a good agreement with Sips isothermal features. Adsorption characteristics were compared to those previously obtained on monophosphate nucleotides (AMP, CMP), unveiling some specificities. ATP was found to adsorb effectively onto biomimetic apatite: despite smaller values of the affinity constant KS and the exponential factor m, larger adsorbed amounts were reached for ATP as compared to AMP for any given concentration in solution. m<1 suggests that the ATP/apatite adsorption process is mostly guided by direct surface bonding rather than through stabilizing intermolecular interactions. Although standard ∆Gads° was estimated to only -4kJ/mol, the large value of Nmax led to significantly negative effective ∆Gads values down to -33kJ/mol, reflecting the spontaneous character of adsorption process. Vibrational spectroscopy data (FTIR and Raman) pointed out spectral modifications upon adsorption, confirming chemical-like interactions where both the triphosphate group of ATP and its nucleic base were involved. The present study is intended to serve as a basis for future research works involving ATP and apatite nanocrystals/nanoparticles in view of biomedical applications (e.g. bone tissue engineering, intracellular drug delivery,...)

Strontium-loaded mineral bone cements as sustained release systems : Compositions, release properties, and effects on human osteoprogenitor cells

This study aims to evaluate in vitro the release properties and biological behavior of original compositions of strontium (Sr)-loaded bone mineral cements. Strontium was introduced into vaterite CaCO3-dicalcium phosphate dihydrate cement via two routes: as SrCO3 in the solid phase (SrS cements), and as SrCl2 dissolved in the liquid phase (SrL cements), leading to different cement compositions after setting. Complementary analytical techniques implemented to thoroughly investigate the release/dissolution mechanism of Sr-loaded cements at pH 7.4 and 37°C during 3 weeks revealed a sustained release of Sr and a centripetal dissolution of the more soluble phase (vaterite) limited by a diffusion process. In all cases, the initial burst of the Ca and Sr release (highest for the SrL cements) that occurred over 48 h did not have a significant effect on the expression of bone markers (alkaline phosphatase, osteocalcin), the levels of which remained overexpressed after 15 days of culture with human osteoprogenitor (HOP) cells. At the same time, proliferation of HOP cells was significantly higher on SrS cements. Interestingly, this study shows that we can optimize the sustained release of Sr2þ, the cement biodegradation and biological activity by controlling the route of introduction of strontium in the cement paste

Evidences for liquid encapsulation in PMMA ultra-thin film grown by liquid injection Photo-CVD

This paper deals with the characterization of ultra-thin films of PMMA grown by an original photoassisted Chemical Vapor Deposition process equipped with a pulsed liquid injection system to deliver the monomer. The nanometric thick films showed a good ability to encapsulate a liquid phase as microdroplets protected by a thin polymeric tight membrane in the form of blisters. Techniques that are capable to analyze these heterogeneous structures at micro- and nanoscopic scale such as Raman Confocal Spectroscopy and Atomic Force Microscopy were used to characterize these polymer films. The liquid droplets were found to be monomer encapsulated by a PMMA film. The specific properties of these ultra-thin films exhibit self-healing capabilities at microscopic scale making them attractive for functionalization of surfaces and interfaces

Development of a new family of monolithic calcium (pyro)phosphate glasses by soft chemistry

The development of bioactive phosphate-based glasses is essential in biomaterials science, and especially for bone substitution applications. In this context, the preparation of amorphous calcium-phosphorus hydroxide/oxide monoliths at low temperature is a key challenge for being able to develop novel hybrid materials for these applications. We herein report for the first time the synthesis and physical chemical characterisation of a novel family of pyrophosphate-based glasses (with the formula: {[(Ca2+)1−x(H+/K+)2x]2[(P2O74−)1−y(PO43−)4y/3]} n(H2O)), which were prepared by soft chemistry using low temperatures (T<70°C) and water as a solvent. The effect of the initial Ca/Pyrophosphate ratio on the structure and morphology of these pyrophosphate glasses was investigated in detail. Depending on this ratio, a glass (mixed calcium pyro- and orthophosphate) or a glass-ceramic (Ca10K4(P2O7)6•9H2O crystals embedded in the amorphous phase) was obtained. The proportion of the crystalline phase increased with an increase in the Ca/Pyrophosphate ratio in the batch solution. As expected for a glass, the formation of the glassy material was demonstrated not to be thermodynamically but rather kinetically driven, and the washing step was found to be crucial to prevent crystallisation. The stability of the amorphous phase was discussed considering the structural degrees of freedom of pyrophosphate entities, ionic strength of the initial solution and the inhibitory effect of orthophosphate ions. Overall, this new strategy of preparation of monolithic calcium-(pyro)phosphate based glasses using soft chemistry in water is highly promising in view of preparing new functional organic-inorganic hybrids for bone substitution applications

Cyclic oxidation of high-silicon spheroidal graphite iron

In service, automotive exhaust manifolds are submitted to rapid thermal cycling up to 700–750 °C. To simulate an increase in exhaust gas temperature, a high-silicon cast iron was tested for rapid thermal cycling up to 800 °C. In addition to the well-known duplex oxide scale, rapid cyclic oxidation promotes the formation of a columnar zone at the substrate/oxide interface that has never been reported. It is evidenced that this columnar zone proceeds from a repetitive process. Based on detailed metallographic analysis using optical observations, in-situ XRD, micro-analyses and Raman spectroscopy, a mechanism explaining the formation of this columnar zone is proposed

Effect of the deposition route on the microstructure of plasma-sprayed hydroxyapatite coatings

Plasma-spray (PS) is the most common technique used to cover orthopaedic titanium-based implant surfaces with hydroxyapatite (HA - Ca10(PO4)6OH2). The objective of the current work was to explore the influence of the precursor nature and characteristics (mainly powder size, Ca/P ratio, and density) on the morphology and the microstructure of HA coatings, deposited either by conventional atmospheric plasma spray (APS) or by rf-suspension plasma spray (rf-SPS). Two powders with different size distribution, density and shape were sprayed with same operating APS conditions. In parallel two water-based suspensions with distinct particle size and chemistry (Ca/P ratio) were implemented in rf-SPS. The morphology of both APS and rf-SPS coatings observed by SEM exhibits micro and sub-micro sized structures respectively, with similar porosity and thickness. The difference in precursor particle size does not affect the coating structure in rf-SPS, unlike in APS conditions. Superimposition of topography and phases maps performed from profilometry and Raman cartographies showed no direct correlation between the surface profile and composition. But such analysis highlighted the heterogeneity of the phases composing the coating surface, opening the possibility of a better understanding of biological behaviour

Automatization of membrane contactors and applications for the management of dissolved gases in wines

Over the last decade, several distinct research groups tested possible uses of membrane contactors for the wine industry, notably for the management of dissolved gases in wines, adjustment of the O2 concentration while reducing the O2 concentration at the same time. Other experiments were done with partial alcohol reduction and addition of N2 to wines. The contactor’s heart is its Liqui-Cel™ membrane where the two separate circuits meet. The membrane’s hydrophobic characteristics allows a liquid to get in contact with a gas, without dispersing into it. The directions that these gases take through the membrane depend on their partial pressure differences within the two circuits. However, other factors need to be considered to determine exact exchange rates for each target gas. The present article describes the new membrane contactor prototype that was co-developed by the University of applied Sciences and Arts, Viticulture and Enology at Changins, Switzerland, and the School of Engineering and Architecture at Fribourg, Switzerland. The prototype was designed for small scale operations. Flow rates, temperatures and internal pressures can be instantly measured and graphically visualized. Also, O2 concentrations are measured inside the liquid. CO2 concentrations in the liquid can be measured with a device that is connected to the liquid circuit through a bypass after the membranes.Während mehr als zehn Jahren testeten verschiedene Forschungsgruppen Einsatzmöglichkeiten von Membran-Kontaktoren für die Weinindustrie. Im Besonderen wurde die genaue Einstellung von gelösten Gasen im Wein untersucht, z. B. die Anpassung der CO2-Konzentration und gleichzeitige Reduzierung der O2-Konzentration. Teilweise Alkoholreduktion und Zugabe von N2 zum Wein sind weitere Möglichkeiten. Das Herzstück des Kontaktors ist seine Liqui-Cel™-Membran, wo sich zwei getrennte Kreisläufe treffen. Die wasserabstossenden Eigenschaften der Membran ermöglichen es einer Flüssigkeit, mit einem Gas in Kontakt zu treten, ohne sich darin zu verteilen. Die Richtung, die diese Gase durch die Membran nehmen, hängt von ihren unterschiedlichen Partialdrücken innerhalb der beiden Kreisläufe ab. Es müssen jedoch noch andere Faktoren berücksichtigt werden, um den genauen Austausch für jedes Gas zu ermitteln. Dieser Artikel beschreibt den neuen Prototyp eines Membran-Kontaktors, der von den Fachhochschulen für Weinbau und Önologie in Changins, Schweiz, und für Technik und Architektur in Freiburg, Schweiz, entwickelt wurde. Der Prototyp ist für die Anwendung mit kleinen Mengen vorgesehen. Fliessgeschwindigkeiten, Temperaturen und interner Druck können inline gemessen und grafisch dargestellt werden. Auch die O2-Konzentration kann im Flüssigkeitskreislauf gemessen werden. Die Konzentration von CO2 in der Flüssigkeit kann mit einem Gerät, welches nach den Membranen über einen Bypass an den Flüssigkeitskreislauf angeschlossen ist gemessen werden

Adsorption of nucleotides on biomimetic apatite: the case of adenosine 5′ monophosphate (AMP)

This work investigates the interaction between the nucleotide adenosine 5′ monophosphate molecule (AMP) and a biomimetic nanocrystalline carbonated apatite as a model for bone mineral. The analogy of the apatite phase used in this work with biological apatite was first pointed out by complementary techniques. AMP adsorption isotherms were then investigated. Obtained data were fitted to a Sips isotherm with an exponent greater than one suggesting positive cooperativity among adsorbed molecules. The data were compared to a previous study relative to the adsorption of another nucleotide, cytidine monophosphate (CMP) onto a similar substrate, evidencing some effect of the chemical nature of the nucleic base. An enhanced adsorption was observed under acidic (pH 6) conditions as opposed to pH 7.4, which parallels the case of DNA adsorption on biomimetic apatite. An estimated standard Gibbs free energy associated to the adsorption process (DG◦ads ∼ −22 kJ/mol) intermediate between “physisorption” and “chemisorption” was found. The analysis of the solids after adsorption pointed to the preservation of the main characteristics of the apatite substrate but shifts or enhancements of Raman bands attributed to AMP showed the existence of chemical interactions involving both the phosphate and adenine parts of AMP. This contribution adds to the works conducted in view of better understanding the interaction of DNA/RNA and their constitutive nucleotides and the surface of biomimetic apatites. It could prove helpful in disciplines such as bone diagenesis (DNA/apatite interface in aged bones) or nanomedicine (setup of DNA or RNA loaded apatite systems). Also, the adsorption of nucleic acids on minerals like apatites could have played a role in the preservation of such biomolecules in the varying conditions known to exist at the origin of life on Earth, underlining the importance of dedicated adsorption studies

Synthesis and Characterisation of Hydrated Calcium Pyrophosphate Phases of Biological Interest

The details of a synthesis method for biologically relevant hydrated calcium pyrophosphates (CPPs, Ca2P2O7·nH2O) has been elucidated. Control of the pH (from 3.6 to 5.8) and the temperature (from 25 to 90 °C) during the synthesis enabled the preparation of four pure CPP phases within one hour without intermediates: monoclinic and triclinic calcium pyrophosphate dihydrate (CPPD, Ca2P2O7·2H2O), which are the two CPP phases detected in vivo in joints of arthritic patients, monoclinic tetrahydrate β (CPPT, Ca2P2O7·4H2O) and an amorphous phase (a-CPP, Ca2P2O7·nH2O). Four domains corresponding to the four different phases of hydrated calcium pyrophosphate were identified; a-CPP was synthesised over a very wide pH and temperature range (up to 90 °C) within the domain of synthesis conditions explored, including physiological conditions (pH 7.4 and 37 °C). The as-synthesised hydrated CPP phases were characterised by complementary techniques (powder X-ray diffraction, FTIR and Raman spectroscopy, scanning electron microscopy and thermogravimetry) and chemical analyses. Rietveld refinement analyses of the as-synthesised crystalline phases were performed, andthere were significant differences between the m-CPPD Xray diffraction pattern observed and previously published cell parameters. Vibrational spectroscopy allowed the crystalline and amorphous phases synthesised to be clearly distinguished and identified owing to the high flexibility of the pyrophosphate anion. Chemical analyses showed that the synthesis conditions used in this study did not allow significant hydrolysis of the pyrophosphate ions into phosphate ions, and the number of water molecules associated with each synthesised CPP phase was determined by thermogravimetric analysis. Different mechanisms of dehydration were also identified. The study of the formation of synthetic and well-characterised hydrated calcium pyrophosphate phases and their availability in large amounts in vitro could allow progress to be made on the biological role of these phases and their possible transformations. This could also aid their detection in patients suffering from disease caused by calcium salt crystals and could clarify the mechanism by which CPP crystals form and evolve in vivo