Towards triglycerides-based biorefineries: Hydrolysis-reforming-hydrogenation in one-pot over Ni/γ-Al2O3 based catalysts

Crisóstomo, Camilo A.B; Almeida, T. S. S.; Soares, Ricardo R.

doi:10.1016/j.cattod.2020.07.020

Cited by 10 publications

(7 citation statements)

References 46 publications

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“…Intersecting reports concern nickel phosphides, carbides, and nitrides. Since then and during the last years, the investigation has continued intensively on the aforementioned issues [ 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 ]. These studies have shown that the selective deoxygenation (SDO) of triglycerides (very small extent fragmentation of the side chains of triglycerides) results in n-alkanes in the diesel range (n-C 15 –n-C 18 ) which can be achieved at 240–360 °C and a hydrogen pressure of 10–80 bar [ 7 ].…”

Section: Introductionmentioning

confidence: 99%

Nickel—Alumina Catalysts for the Transformation of Vegetable Oils into Green Diesel: The Role of Preparation Method, Activation Temperature, and Reaction Conditions

et al. 2023

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Two nickel alumina catalysts containing 60 wt. % Ni were synthesized by wet impregnation and co-precipitation in order to study the effect of preparation methods on the catalytic efficiency concerning the transformation of sunflower oil into green diesel. The effect of activation temperature on the catalytic efficiency of the most active catalyst was also studied. The catalysts were characterized using various techniques and which were evaluated in the aforementioned reaction using a semi-batch reactor. The catalyst prepared by co-precipitation exhibited a higher specific surface area and smaller mean crystal size of the nickel nanoparticle (higher nickel metallic surface). These justify its higher efficiency with respect to the corresponding catalyst synthesized by wet impregnation. The increase in the activation temperature from 400 to 600 °C increased the size of the nickel nanoparticles through sintering, thus destroying the small pores. These led to a decrease in the nickel surface and specific surface area and, thus, to a decrease in the catalytic efficiency. The optimization of the reaction conditions over the most active catalyst (prepared by co-precipitation and activated at 400 °C) leads to the complete transformation not only of the sunflower oil (edible oil) but also of waste cooking oil (non-edible oil) into green diesel. The liquid produced after the hydrotreatment for these two feedstocks for 7 h, at H2 pressure 40 bar and temperature 350 °C using 100 mL of oil and 1 g of catalyst was composed of 97 and 96 wt. % of green diesel, respectively.

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Section: Introductionmentioning

confidence: 99%

Nickel—Alumina Catalysts for the Transformation of Vegetable Oils into Green Diesel: The Role of Preparation Method, Activation Temperature, and Reaction Conditions

et al. 2023

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“…The increase in W content in the Ni/ATW5 B nanomaterial caused an increase in the intensity of the peak at 120 • C with respect to the Ni/ATW1 A nanomaterial, this result suggesting that it has more available metal sites [92]. Crisóstomos et al [94] attributed the peaks in a range of temperatures (<400 • C) to the desorption of nickel particles dispersed on the support that come from the reduction of non-stoichiometric NiAl 2 O 4 that corresponds to a stronger metal-support interaction having resistance to sintering [42].…”

Section: Tpr-hmentioning

confidence: 97%

γ-Valerolactone Production from Levulinic Acid Hydrogenation Using Ni Supported Nanoparticles: Influence of Tungsten Loading and pH of Synthesis

et al. 2022

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γ-Valerolactone (GVL) has been considered an alternative as biofuel in the production of carbon-based chemicals; however, the use of noble metals and corrosive solvents has been a problem. In this work, Ni supported nanocatalysts were prepared to produce γ-Valerolactone from levulinic acid using methanol as solvent at a temperature of 170 °C utilizing 4 MPa of H2. Supports were modified at pH 3 using acetic acid (CH3COOH) and pH 9 using ammonium hydroxide (NH4OH) with different tungsten (W) loadings (1%, 3%, and 5%) by the Sol-gel method. Ni was deposited by the suspension impregnation method. The catalysts were characterized by various techniques including XRD, N2 physisorption, UV-Vis, SEM, TEM, XPS, H2-TPR, and Pyridine FTIR. Based on the study of acidity and activity relation, Ni dispersion due to the Lewis acid sites contributed by W at pH 9, producing nanoparticles smaller than 10 nm of Ni, and could be responsible for the high esterification activity of levulinic acid (LA) to Methyl levulinate being more selective to catalytic hydrogenation. Products and by-products were analyzed by 1H NMR. Optimum catalytic activity was obtained with 5% W at pH 9, with 80% yield after 24 h of reaction. The higher catalytic activity was attributed to the particle size and the amount of Lewis acid sites generated by modifying the pH of synthesis and the amount of W in the support due to the spillover effect.

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“…11,12 For the hydrogenation reactions, high hydrogen (H 2 ) pressures (∼15 bar) and temperatures close to 200 °C are required. 3 Based on the above, it is evident that two major issues must be addressed: (i) the integration of the hydrolysis and hydrogenation reactions in a one-pot process and (ii) the replacement of high-pressure H 2 , which requires substantial infrastructure expenses at an industrial scale, acting as an economic obstacle to the development of a sustainable hydrogenation industry. The first challenge is rather complex, as both reactions need to occur in the same reactor using a suitable catalyst; this is probably why there is a lack of literature dealing with such a process in the oleochemistry field.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, there has been growing industrial interest in developing technologies to transform vegetable oils and animal fats into valuable products. Modifying the chemical structure of oils and fats is possible and profitable through hydrolysis, − hydrogenation, − and transesterification, − to name just a few processes. Hydrogenated fatty acids represent a crucial commodity within the oleochemistry industry, finding applications in the pharmaceutical, food, cosmetic, and lubricant industries .…”

Section: Introductionmentioning

confidence: 99%

“…The usual way of obtaining saturated fatty acids is through the hydrolysis of the oil, followed by hydrogenation in separate processes under different conditions. Hydrolysis reactions can be successfully carried out by the Twitchell, Eisenlohr, and Colgate-Emery processes. , For the hydrogenation reactions, high hydrogen (H 2 ) pressures (∼15 bar) and temperatures close to 200 °C are required …”

Section: Introductionmentioning

confidence: 99%

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Cooperative Catalytic Transfer for One-Pot Hydrolysis/Hydrogenation of Refined Palm Oil Using Formic Acid as a Hydrogen Source

Pinzon,

Romano,

Garcia

et al. 2024

Ind. Eng. Chem. Res.

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Significant biorefinery operations demand hydrolysis and hydrogenation reactions that require high hydrogen pressures. However, the necessity of reducing our reliance on fossil fuels for hydrogen generation drives the development of alternative hydrogen source technologies. Thus, employing hydrogen donor molecules under milder conditions is a promising approach. Herein, we present an industrially viable approach to producing saturated free fatty acids through a one-pot hydrolysis and hydrogenation reaction. In this process, formic acid (FA) acts as the hydrogen donor, while a commercial Ni/SiO 2 catalyst facilitates the hydrogenation of the fatty acid using the hydrogen generated during the decomposition of the FA. The reaction conditions were 190 °C, 20 bar of initial pressure, 750 rpm, 5:1 molar water/oil ratio, and 3 wt % Ni/SiO 2 catalyst (as a function of oil mass) using two different levels of FA. It was found that FA is a suitable catalyst for the hydrolysis reaction of palm oil, achieving a high conversion of free fatty acids. Also, an average iodine value of 19 gI 2 /100 g was obtained, and an extent of hydrogenation of 64% was achieved, indicating partial hydrogenation. The GC-FID results showed a selectivity toward hydrogenation of polyunsaturated fatty acid chains and low conversion of oleic acid. Also, we showed that qualitative and semiquantitative analyses validate the results, elucidating the conversion of triglycerides into fatty acids and providing insights into compound compositions. Infrared spectroscopy and thin-layer chromatography support these findings. Thus, such results are a promising route for saturated fatty acid production in a one-pot reaction.

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Towards triglycerides-based biorefineries: Hydrolysis-reforming-hydrogenation in one-pot over Ni/γ-Al2O3 based catalysts

Cited by 10 publications

References 46 publications

Nickel—Alumina Catalysts for the Transformation of Vegetable Oils into Green Diesel: The Role of Preparation Method, Activation Temperature, and Reaction Conditions

Nickel—Alumina Catalysts for the Transformation of Vegetable Oils into Green Diesel: The Role of Preparation Method, Activation Temperature, and Reaction Conditions

γ-Valerolactone Production from Levulinic Acid Hydrogenation Using Ni Supported Nanoparticles: Influence of Tungsten Loading and pH of Synthesis

Cooperative Catalytic Transfer for One-Pot Hydrolysis/Hydrogenation of Refined Palm Oil Using Formic Acid as a Hydrogen Source

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