Adsorption du Cr (VI) sur la lignine activée

La présente étude porte sur les potentialités de la lignine issue de la cuisson sulfate de l’alfa grass à éliminer le Cr (VI) des solutions aqueuses. Les variations du pH, de la concentration initiale du Cr (VI), de la température, du temps de contact, de la dose de l’adsorbant et leurs effets sur la capacité d’adsorption sont vérifiés expérimentalement. L’adsorption du Cr (VI) sur la lignine est maximale en milieu acide de pH = 2. Elle est optimale à une concentration initiale Cr (VI) de 180 mg•L-1, une dose de lignine de 4 g•L-1 et à un temps de contact maximal de 80 min. Les résultats de l’étude sont exploités à l’aide des équations de Langmuir, de Lagergren et d’Arrhenius afin de déterminer les divers paramètres d’équilibre tels que la capacité maximale d’adsorption, l’énergie d’adsorption, d’interaction et d’activation et les constantes d’équilibre adsorbat-adsorbant. L’application du modèle de Langmuir pour les données expérimentales d’isotherme d’adsorption a permis d’obtenir une capacité maximale d’adsorption de 75,8 mg•g-1 à 40 °C. Le paramètre sans dimension (RL) dont les valeurs sont situées entre 0,060 et 0,818 (0<RL<1) indique une adsorption du Cr (VI) par la lignine effective. Les paramètres thermodynamiques obtenus révèlent que l’adsorption est spontanée et endothermique. L’interaction de la lignine avec les ions chromate est rapide et sa cinétique suit l’équation de vitesse de sorption réversible de deuxième ordre de Lagergren dont les constantes de vitesse d’adsorption à l’équilibre augmentent en même temps que la température.Cette étude confirme que la lignine possède un potentiel d’adsorption important faisant d’elle un moyen efficace pour l’élimination du Cr (VI) des solutions aqueuses.Activated lignin with a surface area of 1023 m2•g-1 was prepared from sulfate lignin that was treated by 30% H2O2 and carbonized at 300°C, in order to test the adsorption of chromium (VI) from aqueous solution. The influence of contact time, pH, initial concentration of adsorbent and adsorbate, and temperature on the adsorption capacity were investigated. The maximum removal of Cr (VI) was found to be 92% at pH = 2 and with a contact time of 80 min. Optimal concentrations of lignin and Cr (VI) were found to be 4 g•L-1 and 180 mg•L-1, respectively. The adsorption kinetics were tested according to pseudo-first-order and pseudo-second-order equations. The analytical data fitted a pseudo-second-order equation well, and the rate of removal of chromium was found to increase with increasing temperature. The activation energy for the adsorption process was found to be 18.19 kJ•mol-1. The Langmuir and Freundlich adsorption isotherm models were applied to describe the isotherm and to obtain the isotherm constants for the adsorption of Cr (VI) on lignin. These constants and correlation coefficients of the isotherm models were calculated and compared. Results indicated that Cr (VI) uptake could be described by the Langmuir adsorption model. The maximum adsorption capacity (qm) of Cr (VI) on lignin was 75.8 mg•g-1 at a temperature of 40°C. The dimensionless equilibrium parameter (RL) signified a favorable adsorption of Cr (VI) on lignin and was found to lie between 0,060 and 0,818 (0< RL<1). The thermodynamic parameters ΔG°, ΔS° and ΔH° were calculated and it was shown that the reaction was spontaneous and endothermic in nature. This study indicates that lignin has the potential to become an effective adsorbent for removal of Cr (VI) from waste water

CHROMIUM (VI) ADSORPTION ONTO ACTIVATED KRAFT LIGNIN PRODUCED FROM ALFA GRASS (STIPA TENACISSIMA)

Activated lignin having a surface area of 1023 m2 g-1 has been prepared from sulfate lignin that was treated by 30% H2O2 and carbonized at 300 °C in order to test the chromium (VI) adsorption from aqueous solution. The influence of contact time, pH, initial concentrations of adsorbent and adsorbate, and temperature on the adsorption capacity were investi-gated. The maximum removal of Cr(VI) was found to be 92.36 % at pH=2 and a contact time of 80 min. Optimal concentration of lignin and Cr(VI) were found to be 3.8 g L-1 and 180 mg L-1, respectively. The adsorption kinetics data fitted well with a pseudo-second-order equation, and the rate of removal of chromium was found to speed up with increasing temperature. Activation energy for the adsorption process was found to be 18.19 kJ mol-1. The Langmuir and Freundlich adsorption isotherm models were applied to describe the isotherm and isotherm constants for the adsorption of Cr (VI) on lignin. These constants and correlation coefficients of the isotherm models were calculated and compared. Results indicated that Cr (VI) uptake could be described by the Langmuir adsorption model. The maximum adsorption capacity (qm) of Cr (VI) on lignin was 75.75 mg g-1 at 40°C. The dimensionless equilibrium parameter (RL) signified a favorable adsorption of Cr (VI) on lignin and was found to be between 0.0601 and 0.818 (0<RL<1). The thermodynamic parameters such as ΔG°, ΔS°, and ΔH° were calculated, and it was found that the reaction was spontaneous and endothermic in nature. This study indicates that lignin has the potential to become an effective and economical adsorbent for removal Cr (VI) from waste water

PRODUCTION OF DISSOLVING GRADE PULP FROM ALFA

Alfa, also known as Stipa tenacissimaI or “halfa”, is grown in North Africa and south Spain. Due to its short fiber length, paper made from alfa pulp retains bulk and takes block letters well. In this study alfa was evaluated for bleached pulp production. Two cellulose pulps with different chemical compositions were pulped by a conventional kraft process. One sample was taken from the original alfa material and another from alfa that had been pretreated by diluted acid. The pulp produced from the pretreated alfa was bleached by the elemental-chlorine-free sequences DEPD and DEDP. The yield, Kappa number, brightness, and α- cellulose content of bleached and unbleached pulps were evaluated. The results showed that during the chemical pulping process, treated alfa cooked more easily than the original alfa. The treated alfa pulp also showed very good bleaching, reaching a brightness level of 94.8% ISO with a yield of 93.6% at an α-cellulose content 96.8(%) with a DEDP bleaching sequence, compared to 83.2% ISO brightness level, 92.8% yield, and 95.1% α-cellulose content for bleached pulp with a DEPD bleaching sequence. Therefore, this alfa material could be considered as a worthwhile choice for cellulosic fiber supply

Towards the Formal Verification of Model Transformations: An Application to Kermeta

Model-Driven Engineering (MDE) is becoming a popular engineering methodology for developing large-scale software applications, using models and transformations as primary principles. MDE is now being successfully applied to domain-specific languages (DSLs), which target a narrow subject domain like process management, telecommunication, product lines, smartphone applications among others, providing experts high-level and intuitive notations very close to their problem domain. More recently, MDE has been applied to safety-critical applications, where failure may have dramatic consequences, either in terms of economic, ecologic or human losses. These recent application domains call for more robust and more practical approaches for ensuring the correctness of models and model transformations. Testing is the most common technique used in MDE for ensuring the correctness of model transformations, a recurrent, yet unsolved problem in MDE. But testing suffers from the so-called coverage problem, which is unacceptable when safety is at stake. Rather, exhaustive coverage is required in this application domain, which means that transformation designers need to use formal analysis methods and tools to meet this requirement. Unfortunately, two factors seem to limit the use of such methods in an engineer’s daily life. First, a methodological factor, because MDE engineers rarely possess the effective knowledge for deploying formal analysis techniques in their daily life developments. Second, a practical factor, because DSLs do not necessarily have a formal explicit semantics, which is a necessary enabler for exhaustive analysis. In this thesis, we contribute to the problem of formal analysis of model transformations regarding each perspective. On the conceptual side, we propose a methodological framework for engineering verified model transformations based on current best practices. For that purpose, we identify three important dimensions: (i) the transformation being built; (ii) the properties of interest ensuring the transformation’s correctness; and finally, (iii) the verification technique that allows proving these properties with minimal effort. Finding which techniques are better suited for which kind of properties is the concern of the Computer-Aided Verification community. Consequently in this thesis, we focus on studying the relationship between transformations and properties. Our methodological framework introduces two novel notions. A transformation intent gathers all transformations sharing the same purpose, abstracting from the way the transformation is expressed. A property class captures under the same denomination all properties sharing the same form, abstracting away from their underlying property languages. The framework consists of mapping each intent with its characteristic set of property classes, meaning that for proving the correctness of a particular transformation obeying this intent, one has to prove properties of these specific classes. We illustrate the use and utility of our framework through the detailed description of five common intents in MDE, and their application to a case study drawn from the automative software domain, consisting of a chain of more than thirty transformations. On a more practical side, we study the problem of verifying DSLs whose behaviour is expressed with Kermeta. Kermeta is an object-oriented transformation framework aligned with Object Management Group standard specification MOF (Meta-Object Facility). It can be used for defining metamodels and models, as well as their behaviour. Kermeta lacks a formal semantics: we first specify such a semantics, and then choose an appropriate verification domain for handling the analysis one is interested in. Since the semantics is defined at the level of Kermeta’s transformation language itself, our work presents two interesting features: first, any DSL whose behaviour is defined using Kermeta (more precisely, any transformation defined with Kermeta) enjoys a de facto formal underground for free; second, it is easier to define appropriate abstractions for targeting specific analysis for this full-fledged semantics than defining specific semantics for each possible kind of analysis. To illustrate this point, we have selected Maude, a powerful rewriting system based on algebraic specifications equipped with model-checking and theorem-proving capabilities. Maude was chosen because its underlying formalism is close to the mathematical tools we use for specifying the formal semantics, reducing the implementation gap and consequently limiting the possible implementation mistakes. We validate our approach by illustrating behavioural properties of small, yet representative DSLs from the literature