Jean-Stéphane Condoret

From an industrial point of view, the continuous process for biodiesel production with supercritical methanol (SCM) is more appropriate than the batch process. However, lab-scale studies on the continuous process have shown that the maximum conversion always remains slightly lower than that obtained in the batch process. This work proposes a simple compressible flow model to predict the conversion of methanol and oils into methyl esters (ME) along the length of a tubular reactor and further demonstrates the effect of the development of the compressibility factor of the reaction mixture upon the conversion efficiency to ME. The governing equation was derived from a general molar balance in the tubular reactor using transesterification kinetics of refined-bleached-deodorized (RBD) palm oil in SCM coupled with a suitable thermodynamic model with adjusted binary interaction parameters. Vapor-liquid equilibrium data for triolein + methanol, methyl oleate + methanol and glycerol + methanol mixtures were obtained from the literature and then refitted with the thermodynamic model consisting of the Peng-Robinson equation of state and MHV2 mixing rules to find the set of adequate interaction parameters. In order to check the validity of the proposed model, the predicted ME contents were compared with observed values in a lab-scale continuous reactor at various operating temperatures, pressures and methanol to oil molar ratios. The proposed model proved to be adequate for predicting the final conversion to ME for operating temperatures below 320°C, when the thermal degradation reactions of unsaturated fatty acids did not interfere. Our results also illustrate the importance of taking into account the development of the compressibility factor with time and reactor length, since this was shown to be the cause of the lower transesterification reaction rate in the tubular SCM process. The findings in this work could be employed as a knowledgebase to further develop a better model for continuous production of biodiesel with SCM in a tubular reactor.

In this work, 2 Eucalyptus species extracts ( Eucalyptus cinerea and Eucalyptus camaldulensis) were prepared by hydrodistillation (HD) and supercritical carbon dioxide extraction (SCE) techniques. The best yields of E. cinerea and E. camaldulensis (27.5 and 8.8 g/kg, respectively) were obtained using SCE at 90 bar, 40 °C compared to HD (23 and 6.2 g/kg, respectively). Extracts were quantified by gas chromatography‐flame ionization detection and identified by gas chromatography‐mass spectrometry. 1,8‐cineole and p‐menth‐1‐en‐8‐ol were the major compounds of E. cinerea essential oil obtained by HD (64.89% and 8.15%, respectively) or by SCE (16.1% and 31.87%, respectively). Whereas, in case of E. camaldulensis , 1,8‐cineole (45.71%) and p‐cymene (17.14%) were the major compounds obtained by HD, and 8,14‐cedranoxide (43.79%) and elemol (6.3%) by SCE. Their antioxidant activity was assessed using 2 methods: 2,2‐azino‐di‐3‐ethylbenzothialozine‐sulphonic acid radical cation (ABTS ^•+ ) and 2,2‐diphenyl‐1‐picrylhydrazyl radical (DPPH ^• ). In the SCE extracts from both E. cinerea and E. camaldulensis , a promising radical scavenging activity was observed with ABTS ^•+ , (65 and 128 mg/L, respectively). The total phenolics composition of the extracts was measured and the range was 2 to 60 mg of gallic acid equivalent/g dry plant material. The SCE method was superior to HD, regarding shorter extraction times (30 min for SCE compared with 4 h for HD), a low environmental impact, allows production of nondegraded compounds and being part of green chemistry.

BACKGROUND: Microorganisms have often been considered for the production of oils and fats as an alternative to agricultural and animal resources. Extraction experiments were performed using a strain of the yeast Yarrowia lipolytica (Y. lipolytica), a high‐lipid‐content yeast. Three different methods were tested: Soxhlet extraction, accelerated solvent extraction (ASE) and supercritical carbon dioxide (SCCO₂) extraction using ethanol as a co‐solvent. Also, high pressure solubility measurements in the systems ‘CO₂ + yeast oil’ and ‘CO₂ + ethanol + yeast oil’ were carried out.RESULTS: The solubility experiments determined that, at the conditions of the supercritical extractor (40 °C and 20 MPa), a maximum concentration of 10 mg of yeast oil per g of solvent can be expected in pure CO₂. 10% w/w of ethanol in the solvent mixture increased this value to almost 15 mg of yeast oil per g of solvent. Different pretreatments were necessary to obtain satisfactory yields in the extraction experiments. The Soxhlet and the ASE method were not able to complete the lipid extraction. The ‘SCCO₂ + ethanol’ extraction curves revealed the influence of the different pretreatments on the extraction mechanism.CONCLUSION: Evaluating the effectiveness of a given pretreatment, ASE reduced the amount of material and solvent used compared with Soxhlet. In all three cases, the best total extraction performance was obtained for the ethanol‐macerated yeast (EtM). Addition of ethanol to the solvent mixture enhanced the oil solubility. Oil can be extracted from Y. lipolytica in two different steps: a non‐selective ethanol extraction followed by TAG‐selective SCCO₂ purification. © 2012 Society of Chemical Industry

In this review, we describe the use of supercritical CO₂ (scCO₂) in several cellulose applications. The focus is on different technologies that either exist or are expected to emerge in the near future. The applications are wide from the extraction of hazardous wastes to the cleaning and reuse of paper or production of glucose. To put this topic in context, cellulose chemistry and its interactions with scCO₂ are described. The aim of this study was to discuss the new emerging technologies and trends concerning cellulosic materials processed in scCO₂ such as cellulose drying to obtain aerogels, foams and other microporous materials, impregnation of cellulose, extraction of highly valuable compounds from plants and metallic residues from treated wood. Especially, in the bio-fuel production field, we address the pre-treatment of cellulose in scCO₂ to improve fermentation to ethanol by cellulase enzymes. Other reactions of cellulosic materials such as organic inorganic composites fabrication and de-polymerisation have been considered. Cellulose treatment by scCO₂ has been discussed as well. Finally, other applications like deacidification of paper and cellulosic membranes fabrication in scCO₂ have been reviewed. Examples of the discussed technologies are included as well.

Friedel-Crafts acylation is among the most fundamental and useful reactions to yield aromatic ketones but it is one of the less acceptable in terms of unwanted polluting by-products or atom economy because of the overconsumption of catalyst which is used in stoichiometric quantities in the conventional process. This route is nevertheless widely used in the fine chemical industry.In recent years, awareness of the impact of industrial activities on the environment has led chemists to work on new chemical routes, less dangerous and more environmentally friendly.We considered here the acylation of a benzofurane derivative by an acyl chloride, as an intermediary step for a pharmaceutical product. In this study, one of the first alternatives was to replace conventional catalysts (FeCl3 or AlCl3), by reusable solid catalysts. Indeed, a wide variety of new solid catalysts, more efficient and less polluting, has now emerged (zeolites, ion-exchange resins…). In this work, these catalysts were first tested in “conventional” conditions, i.e., using an organic solvent (1,2-dichlorobenzene in our case), to determine the best one, in terms of reactivity, lifetime and reusability. The zeolite Y was found the most appropriate.However, the use of an organic solvent still remains questionable and the use of supercritical carbon dioxide as the solvent was also considered. Its inherent properties include non-flammability, mild critical conditions, tuneable solubility near to the critical point and very low environmental impact. The reaction was operated using a continuous high pressure fixed bed. Results concerning yield and selectivity are presented.

Natural cellulose fibres have been employed for packaging applications for a long time. Their use, however, has been hampered by their high hydrophilicity and their moisture sensitivity. It has, thus, been proposed to circumvent this problem through the hydrophobic modification of their surface thanks to the use of molecular grafting approaches.In this work, we describe the use of a novel solvent-free chemical pathway for molecular grafting that we have coined chromatogenic chemistry. It involves a reaction between a solid substrate and a reagent which is in a vapour-liquid equilibrium and diffuses within the solid substrate through a mechanism of adsorption/desorption akin to gas chromatography.Chromatogenic chemistry phenomenon has been studied and modelled through the extensive use of a new specific test, the Droplet Surface Migration Test. It involves the deposition upon a porous substrate of a small amount of reagent and in studying its subsequent migration and grafting. Whatman paper and various long chain acid chlorides were used for this modelling. The acid chloride carboxylic ends react with the external hydroxyl groups of cellulose fibres to give rise to the formation of long chain hydrophobic ester bonds. Upon immersion of the paper sheet in distilled water, a hydrophobic spot, extending well over the initial depot zone, could then be clearly visualized, allowing to follow conveniently the reagent migration and reaction. Grafting densities were performed by using the HPLC technique.The results obtained through the use of this test allowed a better understanding of chromatogenic chemistry phenomenon and an identification of the main parameters which affect the process: the nature of the reagent, the temperature, the reaction time, the nature of the substrate, etc. We have more particularly shown that the diffusion and grafting yields were maximal for a specific temperature which increases with the boiling point and therefore with the chain length of the reagents. We have proposed that this temperature should correspond to a compromise between the diffusion and reactivity properties of the reagent, its evaporation and its degradation by hydrolysis.