Modelling the kinetics of transesterification reaction of sunflower oil with ethanol in microreactors

Transesterification reaction of vegetable oil with ethanol leads to ethyl esters, used to date for applications principally in food and cosmetic industry. To open the application field to biofuels (to substitute current fuels resulting from fossil resources), the process efficiency has to be developed to be economically profitable. In this work, the sunflower oil ethanolysis was performed in a micro-scaled continuous device, inducing better control for heat and mass transfer in comparison with batch processes. Moreover, this device ensures kinetic data acquisition at the first seconds of the reaction, which was not feasible in a conventional batch process. These data were used to model occurring phenomena and to determine kinetic constants and mass transfer coefficients. A single set of these parameters is able to represent the evolution of the reaction media composition function of time for five ethanol to oil molar ratios (6.0, 9.0, 16.2, 22.7 and 45.4). The model was validated in reaction and diffusion mode. Finally, it was subsequently used to simulate reactions with other operational conditions and to propose other process implementation

On-line monitoring of the transesterification reaction carried out in microreactors using near infrared spectroscopy

Biodiesel can be produced from vegetable oils, animal fats, and waste cooking oils by transesterification with ethanol (also called ethanolysis) in order to substitute fossil fuels. In this work, the batch ethanolysis of high oleic sunflower oil was transferred into a continuous microstructured device, which induces a better control of heat and mass transfers. Various parameters were studied, notably the initial ethanol to oil molar ratio. An innovative method using NIR spectroscopy was also developed to on-line monitor the transesterification reaction of high oleic sunflower oil with ethanol in microreactors (circular PFA tube 1/1600 OD, 0.0200 ID). The reactions were monitored directly in the microreactors through sequential scans of the reaction medium by the means of an adequate probe. The asset of the method is that no sample collection or preparation is necessary. Partial Least Squares regression was used to develop calibration and prediction models between NIR spectral data and analytical data obtained by a reference method (gas chromatography with flame ionization detection, GC–FID). This method is fast, safe, reliable, nondestructive and inexpensive contrary to conventional procedures, such as gas chromatography and high performance liquid chromatography generally used to determine the composition of crude transesterification medium

On-line monitoring of the transesterification reaction between triglycerides and ethanol using near infrared spectroscopy combined with gas chromatography

Many analytical procedures have been developed to determine the composition of reaction mixtures during transesterification of vegetable oils with alcohols. However, despite their accuracy, these methods are time consuming and cannot be easily used for on-line monitoring. In this work, a fast analytical method was developed to on-line monitor the transesterification reaction of high oleic sunflower oil with ethanol using Near InfraRed spectroscopy and a multivariate approach. The reactions were monitored through sequential scans of the reaction medium with a probe in a one-liter batch reactor without collecting and preparing samples. To calibrate the NIR analytical method, gas chromatography-flame ionization detection was used as a reference method. The method was validated by studying the kinetics of the EtONa-catalyzed transesterification reaction. Activation energy (51.0 kJ/mol) was also determined by considering a pseudo second order kinetics model

Production of artificial fingermarks. Part II – The use of a modified inkjet printer for the deposition of synthetic secretions

This study is the second part of a larger body of research dedicated to the production of synthetic secretions and the use of an inkjet printer to deposit realistic artificial fingermarks. An artificial emulsion combining eccrine and sebaceous compounds, which was described and tested in the first part of this research, was used as it showed a promising compatibility with common detection techniques. An inkjet printer was modified to print the emulsion on two different substrates: paper (porous) and acetate (non-porous). After optimisation of the printing parameters, multiple fingermarks were printed and processed with a range of standalone detection techniques: 1,2-indanedione-zinc, ninhydrin, Oil Red O, and physical developer on paper, and cyanoacrylate fuming, rhodamine 6G, gold/zinc vacuum metal deposition, and silver black powder on acetate. The detection techniques were also applied in sequence, which is considered one of the biggest advantages of the emulsion over simpler amino acid mixtures that are usable with amino acid reagents only. Natural fingermarks deposited by a single donor were processed with the same techniques for comparison. The effect of water immersion was also investigated, where fingermarks printed on paper were immersed in water for 15 min, before being processed with 1,2-indanedione-zinc and Oil Red O. The results showed that realistic-looking fingermarks could be printed on paper and that printing on acetate was also possible albeit of lower quality due to the nature of the substrate. The artificial fingermarks were successfully enhanced by all the detection techniques tested, at the notable exception of physical developer. The results obtained were very similar to what is generally observed with real fingermarks, and it was observed that the impact of water immersion on the artificial fingermarks was comparable as well. These findings open new perspectives for the development of multi-target quality control test strips or for the standardisation of proficiency testing and interlaboratory collaborative exercises where ground truth is crucial to guarantee comparable results and objective assessment

Développement de nouveaux procédés de transestérification de triglycérides en microréacteurs - Applications : biocarburants, biodétergents, biosolvants

L’objectif de la thèse est d’étudier de nouveaux types de réacteurs permettant de dépasser les limites des technologies actuelles pour la transestérification de triglycérides avec de l’éthanol (ou bioéthanol). La réaction de transestérification est équilibrée et peut s’écrire globalement de la manière suivante : Triglycéride + 3EtOH ---> 3 RCO2Et + Glycérol. Cette réaction se décompose en trois réactions successives. La première étape est la conversion des triglycérides en diglycérides ; elle est suivie de la conversion des diglycérides en monoglycérides, qui sont finalement transformés en glycérol, en formant une molécule d’ester éthylique à chaque étape

Development of continuous processes for vegetable oil alcoholysis in microfluidic devices

Biodiesel can be produced from vegetable oils, animal fats, and waste cooking oils by transesterification with ethanol (also called ethanolysis) in order to substitute fossil fuels. In this work, we were interested in the transesterification reaction of sunflower oil with ethanol, which leads to ethyl esters, used to date for applications principally in food and cosmetic industry. To open the application field to biofuels (to substitute current fuels resulting from fossil resources), the process efficiency has to be developed to be economically profitable. The batch reaction of vegetable oil ethanolysis was transposed to a micro-scaled continuous device (PFA tube of 508 mm internal diameter), inducing better heat and mass transfer. Study of the influence of the operational conditions (reactants flow, initial ethanol to oil molar ratio, temperature. . .) revealed the favourable reaction parameters necessary to reach high conversions and yields. In these conditions, it is possible to acquire kinetics data at the first seconds of the reaction, which was not feasible in a conventional batch process. These data were used to model occurring phenomena and to determine kinetic constants and transfer coefficients. The model was subsequently used to simulate reactions with other operational conditions. To acquire these data in microreactors, an on-line analysis method by Near InfraRed (NIR) spectroscopy was developed by using gas chromatography as a reference method. PLS models were then set up to quantify on-line the major compounds contents during the reaction

Mesure d'angles par double formation de voies appliquée à la tomographie acoustique sous-marine

National audienceCet article traite de la tomographie acoustique océanique utilisant les angles de départ et les angles d'arrivée des ondes sonores. Dans ce but, deux antennes (en émission et en réception) sont utilisées pour séparer les arrivées acoustiques et mesurer leur temps de trajet, direction de réception et direction d'émission. Ces mesures sont ensuite utilisées dans un processus d'inversion visant à retrouver la carte des variations de vitesse du son au sein du milieu de propagation (guide d'onde océanique peu profond). L'apport de ces travaux est double : (1) ils montrent qu'il est possible de faire de la tomographie acoustique océanique en utilisant les angles d'émission et de réception, ce qui n'avait jamais été fait à ce jour ; (2) ils permettent de se passer de synchronisation émetteur-récepteur haute précision, qui est un problème technique délicat à régler en pratique. Cet article présente des résultats de tomographie acoustique océanique sur des données simulées. Les résultats obtenus à partir des seuls angles d'émission et de réception sont équivalents à ceux obtenus à partir des temps de trajet des ondes acoustiques, nécessitant la synchronisation émetteur-récepteur

Time-angle ocean acoustic tomography using sensitivity kernels: Numerical and experimental inversion results

International audienceIn shallow water acoustic tomography, broadband mid-frequency acoustic waves (1 to 5 kHz) follow multiple ray-like paths to travel through the ocean. Travel-time (TT) variations associated to these raypaths are classically used to estimate sound speed perturbations of the water column using the ray theory. In this shallow water environment, source and receiver arrays, combined with adapted array processing, provide the measurement of directions-of-arrival (DOA) and directions-of-departure (DOD) of each acoustic path as new additional observables to perform ocean acoustic tomography. To this aim, the double-beamforming technique is used to extract the TT, DOA and DOD variations from the array-to-array acoustic records. Besides, based on the first order Born approximation, we introduce the time-angle sensitivity kernels to link sound speed perturbations to the three observable variations. This forward problem is then inverted with the maximum a posteriori method using both the extracted-observable variations and the proposed sensitivity kernels. Inversion results obtained on numerical data, simulated with a parabolic equation code, are presented. The inversion algorithm is performed with the three observables separately, namely TT, DOA and DOD. The three observables are then used jointly in the inversion process. The results are discussed in the context on ocean acoustic tomography

Profilométrie par déphasage en mouvement pour applications industrielles

National audienceLa profilométrie par déphasage est une méthode éprouvée pour reconstruire des surfaces de manière dense et précise. Par contre la scène doit rester immobile pendant l'acquisition d'une séquence de plusieurs images. De plus, il existe des méthodes de stéréo active qui s'affranchissent de la contrainte d'immobilité de la scène mais qui imposent d'autres limitations comme par exemple la continuité de la surface et de la texture ou une résolution de reconstruction considérablement réduite. Nous présentons une nouvelle technique de reconstruction aussi dense et précise que la profilométrie par déphasage et qui permet une translation de la scène pendant l'acquisition de la séquence d'images. Cela la rend intéressante pour des applications industrielles. Nous étudions sa performance à l'aide de simulations et donnons une démonstration sur un exemple réel