The aim of this work was to develop bioprocesses to produce a high-value microbial product, bacterial cellulose (BC), utilizing the industrial side-stream of Corinthian currants finishing (CFS), with/without the addition of N-sources and cheese whey, and at various process conditions (temperature, pH level, and sugar concentration). For the optimization of BC production, the response surface methodology based on the central composite design was applied. Among the possible retrieved combinations, the most ideal conditions for BC in CFS extracts supplemented with N-source were 28 °C, pH 6.42, and 46.24 g/L concentration of sugars. In a similar manner, the best conditions for BC production in CFS/whey mixtures were pH 6.36, 50.4% whey percentage in the mixture, and 1.7% yeast extract. The textural characteristics of the produced BC, at different times of production and using different drying methods, were studied by scanning electron microscopy, X-ray diffractometry, porosimetry, Fourier-transform infrared spectroscopy, and thermogravimetric/differential thermal analysis, revealing increased porosity of BC compared with delignified cellulosic materials of plant origin, and a level of crystallinity that depended on the BC production time. The proposed methodology can be used to produce foods with potential prebiotic properties, using the highly nutritious CFS and the abundant cheese whey effluent as raw materials.
The transformation of sunflower oil (SO) and waste cooking oil (WCO) into green diesel over co-precipitated nickel–zirconia catalysts was studied. Two series of catalysts were prepared. The first series included catalysts with various Ni loadings prepared using zirconium oxy-chloride, whereas the second series included catalysts with 60–80 wt % Ni loading prepared using zirconium oxy-nitrate as zirconium source. The catalysts were characterized and evaluated in the transformation of SO into green diesel. The best catalysts were also evaluated for green diesel production using waste cooking oil. The catalysts performance for green diesel production is mainly governed by the Ni surface exposed, their acidity, and the reducibility of the ZrO2. These characteristics depend on the preparation method and the Zr salt used. The presence of chlorine in the catalysts drawn from the zirconium oxy-chloride results to catalysts with relatively low Ni surface, high acidity and hardly reduced ZrO2 phase. These characteristics lead to relatively low activity for green diesel production, whereas they favor high yields of wax esters. Ni-ZrO2 catalysts with Ni loading in the range 60–80 wt %, prepared by urea hydrothermal co-precipitation method using zirconium oxy-nitrate as ZrO2 precursor salt exhibited higher Ni surface, moderate acidity, and higher reducibility of ZrO2 phase. The latter catalysts were proved to be very promising for green diesel production.
A series of nickel–alumina catalysts promoted by copper containing 1, 2, and 5 wt. % Cu and 59, 58, and 55 wt. % Ni, respectively, (symbols: 59Ni1CuAl, 58Ni2CuAl, 55Ni5CuAl) and a non-promoted catalyst containing 60 wt. % Ni (symbol: 60NiAl) were prepared following a one-step co-precipitation method. They were characterized using various techniques (N2 sorption isotherms, XRD, SEM-EDX, XPS, H2-TPR, NH3-TPD) and evaluated in the selective deoxygenation of sunflower oil using a semi-batch reactor (310 °C, 40 bar of hydrogen, 96 mL/min hydrogen flow rate, and 100 mL/1 g reactant to catalyst ratio). The severe control of the co-precipitation procedure and the direct reduction (without previous calcination) of precursor samples resulted in mesoporous nano-structured catalysts (most of the pores in the range 3–5 nm) exhibiting a high surface area (192–285 m2 g−1). The promoting action of copper is demonstrated for the first time for catalysts with a very small Cu/Ni weight ratio (0.02–0.09). The effect is more pronounced in the catalyst with the medium copper content (58Ni2CuAl) where a 17.2% increase of green diesel content in the liquid products has been achieved with respect to the non-promoted catalyst. The copper promoting action was attributed to the increase in the nickel dispersion as well as to the formation of a Ni-Cu alloy being very rich in nickel. A portion of the Ni-Cu alloy nanoparticles is covered by Ni0 and Cu0 nanoparticles in the 59Ni1CuAl and 55Ni5CuAl catalysts, respectively. The maximum promoting action observed in the 58Ni2CuAl catalyst was attributed to the finding that, in this catalyst, there is no considerable masking of the Ni-Cu alloy by Ni0 or Cu0. The relatively low performance of the 55Ni5CuAl catalyst with respect to the other promoted catalysts was attributed, in addition to the partial coverage of Ni-Cu alloy by Cu0, to the remarkably low weak/moderate acidity and relatively high strong acidity exhibited by this catalyst. The former favors selective deoxygenation whereas the latter favors coke formation. Copper addition does not affect the selective-deoxygenation reactions network, which proceeds predominantly via the dehydration-decarbonylation route over all the catalysts studied.
7 September 2021 in Industrial & Engineering Chemistry Research
Four Ni catalysts and one Mo–Ni catalyst supported on montmorillonite were synthesized, characterized by various techniques and evaluated, under solvent-free conditions, for the production of green diesel from waste cooking oil. The optimum Ni content was found to be 20 wt.%. The addition of 2 wt.% Mo to the catalyst resulted in a considerable increase in the amount of green diesel hydrocarbons. The Mo species, moreover, led to a decrease in the (C15 + C17)/(C16 + C18) ratio, which is beneficial from the viewpoint of carbon atom economy. The promoting action of Mo was mainly attributed to the synergy between the oxygen vacancies on the surface of the well-dispersed Mo(V) and Mo(VI) oxides and the neighboring Ni0 sites. The optimum reaction conditions, for achieving a proportion of liquid product in the green diesel hydrocarbons (C15–18) equal to 96 wt.%, were found to be 350 °C, 3 g of catalyst per 100 mL of waste cooking oil and 13 h reaction time. These conditions correspond to an LHSV of 2.5 h−1, a value that is considered quite reliable from the viewpoint of industrial applications. Thus, the cheap and abundant mineral montmorillonite is proved a promising support for developing efficient Ni–Mo catalysts for green diesel production.