The Influence of Active Phase Loading on the Hydrodeoxygenation (HDO) of Ethylene Glycol over Promoted MoS2_{2}/MgAl2_{2}O4_{4} Catalysts

The hydrodeoxygenation (HDO) of ethylene glycol over MgAl$_{2}$O$_{4}$ supported NiMo and CoMo catalysts with around 0.8 and 3 wt% Mo loading was studied in a continuous flow reactor setup operated at 27 bar H$_{2}$ and 400 °C. A co-feed of H2S of typically 550 ppm was beneficial for both deoxygenation and hydrogenation and for enhancing catalyst stability. With 2.8-3.3 wt% Mo, a total carbon based gas yield of 80-100 % was obtained with an ethane yield of 36-50 % at up to 118 h on stream. No ethylene was detected. A moderate selectivity towards HDO was obtained, but cracking and HDO were generally catalyzed to the same extent by the active phase. Thus, the C2/C1 ratio of gaseous products was 1.1-1.5 for all prepared catalysts independent on Mo loading (0.8-3.3 wt%), but higher yields of C1-C3 gas products were obtained with higher loading catalysts. Similar activities were obtained from Ni and Co promoted catalysts. For the low loading catalysts (0.83-0.88 wt% Mo), a slightly higher hydrogenation activity was observed over NiMo compared to CoMo, giving a relatively higher yield of ethane compared to ethylene. Addition of 30 wt% water to the ethylene glycol feed did not result in significant deactivation. Instead, the main source of deactivation was carbon deposition, which was favored at limited hydrogenation activity and thus, was more severe for the low loading catalysts

Hydrodeoxygenation (HDO) of aliphatic oxygenates and phenol over NiMo/MgAl2_{2}O4_{4}: Reactivity, inhibition, and catalyst reactivation

This study provides new insights into sustainable fuel production by upgrading bio-derived oxygenates by catalytic hydrodeoxygenation (HDO). HDO of ethylene glycol (EG), cyclohexanol (Cyc), acetic acid (AcOH), and phenol (Phe) was investigated using a Ni-MoS$_{2}$/MgAl$_{2}$O$_{4}$ catalyst. In addition, HDO of a mixture of Phe/EG and Cyc/EG was studied as a first step towards the complex mixture in biomass pyrolysis vapor and bio-oil. Activity tests were performed in a fixed bed reactor at 380–450 °C, 27 bar H2, 550 vol ppm H2S, and up to 220 h on stream. Acetic acid plugged the reactor inlet by carbon deposition within 2 h on stream, underlining the challenges of upgrading highly reactive oxygenates. For ethylene glycol and cyclohexanol, steady state conversion was obtained in the temperature range of 380–415 °C. The HDO macro-kinetics were assessed in terms of consecutive dehydration and hydrogenation reactions. The results indicate that HDO of ethylene glycol and cyclohexanol involve different active sites. There was no significant influence from phenol or cyclohexanol on the rate of ethylene glycol HDO. However, a pronounced inhibiting effect from ethylene glycol on the HDO of cyclohexanol was observed. Catalyst deactivation by carbon deposition could be mitigated by oxidation and re-sulfidation. The results presented here demonstrate the need to address differences in oxygenate reactivity when upgrading vapors or oils derived from pyrolysis of biomass

Reaction rate reconstruction from biomass concentration measurement in bioreactors using modified second-order sliding mode algorithms

This paper deals with the estimation of unknown signals in bioreactors using sliding observers. Particular attention is drawn to estimate the specific growth rate of microorganisms from measurement of biomass concentration. In a recent article, notions of high-order sliding modes have been used to derive a growth rate observer for batch processes. In this paper we generalize and refine these preliminary results. We develop a new observer with a different error structure to cope with other types of processes. Furthermore, we show that these observers are equivalent, under coordinate transformations and time scaling, to the classical super-twisting differentiator algorithm, thus inheriting all its distinctive features. The new observers’ family achieves convergence to timevarying unknown signals in finite time, and presents the best attainable estimation error order in the presence of noise. In addition, the observers are robust to modeling and parameter uncertainties since they are based on minimal assumptions on bioprocess dynamics. In addition, they have interesting applications in fault detection and monitoring. The observers performance in batch, fed-batch and continuous bioreactors is assessed by experimental data obtained from the fermentation of Saccharomyces Cerevisiae on glucose.This work was supported by the National University of La Plata (Project 2012-2015), the Agency for the Promotion of Science and Technology ANPCyT (PICT2007-00535) and the National Research Council CONICET (PIP112-200801-01052) of Argentina; the Technical University of Valencia (PAID-02-09), the CICYT (DPI2005-01180) and AECID (A/024186/09) of Spain; and by the project FEDER of the European Union.De Battista, H.; Picó Marco, JA.; Garelli, F.; Navarro Herrero, JL. (2012). Reaction rate reconstruction from biomass concentration measurement in bioreactors using modified second-order sliding mode algorithms. Bioprocess and Biosystems Engineering. 35(9):1-11. https://doi.org/10.1007/s00449-012-0752-yS111359Aborhey S, Williamson D (1978) State amd parameter estimation of microbial growth process. Automatica 14:493–498Bastin G, Dochain D (1986) On-line estimation of microbial specific growth rates. Automatica 22:705–709Bastin G, Dochain D (1990) On-line estimation and adaptive control of bioreactors. Elsevier, AmsterdamBejarano F, Fridman L (2009) Unbounded unknown inputs estimation based on high-order sliding mode differentiator. In: Proceedings of the 48th IEEE conference on decision and control, pp 8393–8398Corless M, Tu J (1998) State and input estimation for a class of uncertain systems. 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Data for: Edge effects of low-impact seismic lines for oil exploration on upland forest vegetation in northern Alberta (Canada)

Data on edge influence of low impact seismic lines on vegetation and environmental variables in sub-boreal upland forest of north-west Alberta, Canada

Viscosities of heavy oils-in-toluene and partially deasphalted heavyoils-in-heptol in the study of asphaltenes self-interactions

Interparticle interactions of the soluble asphaltenes in partially deasphalted heavy oils in toluene-heptane (heptol) mixtures are compared to those of several heavy oils diluted in toluene only. Viscosity-volume fraction (eta-Phi) relationships for the heavy oils and bitumen in toluene were almost identical. However, the asphaltenes in toluene associated and scaled differently from its source oil. Four classical viscosity models were used to describe the data, and scaling was interpreted on the basis of asphaltenes association, as in macromolecular interactions, The Pal-Rhodes model showed deviation from sphericity with solvation constants for heavy oils in toluene and C-5 asphaltenes in toluene, at 1.4-1.6 and 3.7, respectively. The Krieger-Dougherty (KH) model indicated high interparticle interaction factors, and maximum packing factors of similar to 1 suggested polydispersity. Neither models fit the data for deasphalted oils. The Leighton-Acrivos model showed that W the maximum packing fraction (Phi(max)) for all oils was similar, (ii) the asphaltenes alone in toluene had the highest self-associations, and (iii) the deasphalted oils showed Phi(max) values close to the theoretical values (0.58). From the Einstein equations, intrinsic viscosities [eta] of deasphalted oils in heptol gave aspect ratios (length to radius, L/R) of the asphaltenes at 10 (i.e., rodlike molecules). The K-H model gave [eta] of similar to 4 and L/R approximate to 3.5 for heavy oils in toluene; however, for asphaltenes in toluene, the model gave [eta] approximate to 10.6 and L/R approximate to 5.8 (i.e., less-rodlike molecules)