Oligomerization of glycerol – a critical review

Martin, Andreas; Richter, M.

doi:10.1002/ejlt.201000386

Cited by 159 publications

(138 citation statements)

References 44 publications

(86 reference statements)

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“…Low-weight polyglycerols have wide applications in cosmetics, food, polymer and plastic industry [5,10,11]. When reactions are performed at temperatures higher than 493 K, double dehydration of glycerol can lead to acrolein, a secondary undesired and toxic product [1][2][3].…”

Section: Introductionmentioning

confidence: 99%

Influence of acid–base properties of calcined MgAl and CaAl layered double hydroxides on the catalytic glycerol etherification to short-chain polyglycerols

Pérez-Barrado

Pujol

Aguiló

et al. 2015

Chemical Engineering Journal

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h i g h l i g h t s• One-pot etherification reaction of glycerol towards short-chain polyglycerols.• Calcined MgAl-LDH and calcined CaAl-LDH were used as catalysts.• Basicity and acidity of the catalysts influenced the catalytic results.• Stronger basic sites and lower acidity favoured short-chain polyglycerols.• Higher temperature of calcination favoured a higher degree of polymerisation.g r a p h i c a l a b s t r a c t a b s t r a c t Several MgAl-LDHs (HT) and CaAl-LDHs (HC) were synthesized in different conditions and later calcined at 723 K, resulting in catalysts (cHT and cHC), with different acid-base properties. Calcined samples were tested in the etherification reaction of glycerol towards short-chain oligomers (di-to pentaglycerol). All catalysts were characterised by XRPD, ICP, N2 physisorption and TEM techniques. The basicity was evalKeywords: Glycerol etherification Short-chain polyglycerol CaAl layered double hydroxides MgAl layered double hydroxides Acid-base properties uated using the CO2-TPD technique and the acidity by cyclohexylamine adsorption. Catalytic results were correlated with catalysts properties. Catalysts with higher acidity showed higher conversion (96% for a cHT and 75% for a cHC) but also higher selectivity to other products, with main contribution of acrolein (88% for a cHT and 58% for a cHC). In contrast, catalysts with lower acidity resulted in lower conversion (24% for a cHT and 40% for a cHC) but higher selectivity towards di-and triglycerol (100% and 64%, respectively). The formation of triglycerol and other low-weight polyglycerols (tetra-and pentaglycerol) was favoured in catalysts with low acidity and strong basic sites. When the temperature of calcination was raised to 1073 K for one cHC, the acidity decreased and the number of strong basic sites increased, resulting in higher selectivity to triglycerol (20%), the formation of tetra-and pentaglycerol (15% and 6%, respectively) and the decrease of the acrolein amount.

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Section: Introductionmentioning

confidence: 99%

Influence of acid–base properties of calcined MgAl and CaAl layered double hydroxides on the catalytic glycerol etherification to short-chain polyglycerols

Pérez-Barrado

Pujol

Aguiló

et al. 2015

Chemical Engineering Journal

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“…Oligoglycerols (di-and/or triglycerol, n =2 or 3) ar e more hydrophilic than higher ones (n≥4) therefore have higher solubility in polar solvents. With the increase in n, the viscosity of polyglycerol increases with its color changing from white to deep yellow (Martin and Richter, 2011). Oligoglycerols are considered to have more promising applications than high polyglycerol (n≥4).…”

Section: Introductionmentioning

confidence: 99%

Optimization of oligoglycerol fatty acid esters preparation catalyzed by Lipozyme 435

Wan¹,

Teng²,

Wang³

et al. 2015

Grasas y Aceites

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Oli goglycerol fatty acid esters (OGEs) are an important kind of polyglycerol fatty acid esters (PGEs) which have been widely used as emulsifiers in food, medicine and cosmetic industries. The aim of this study was to investigate the preparation of OGEs by the esterification of olig oglycerol with linoleic acid in a solvent-free system using Lipozyme 435 as the catalyst. The effects of substrate molar ratio, reaction time, reaction temperature, enzyme dosage, and water addition on the efficiency of esterification (EE) were studied. Single factor experiments and response surface methodology (RSM) were employed to optimize the reaction parameters. The optimum conditions were obtained as follows: reaction time 4.52 h, reaction temperature 90 °C, enzyme dosage 2 wt% (based on the total substrate mass), the molar ratio of oligoglycerol to linoleic acid 1.59:1 and no water addition. Under these conditions, the experimental EE (95.82±0.22%) fitted well with that predicted by RSM (96.15%). Similar results were obtained when the process was scaled up to a production of 500 g in a pilot bubble column reactor (BCR). The enzyme maintained 98.2% of the relative activity after 10 batches of reaction in the BCR. Electro spray ionization mass spectrum was employed to rapidly analyze the esterification products, and most species of OGEs have been identified. KEYWORDS: Biocat alysis; Bubble column reactor; Esterification; Immobilized enzyme; Lipase; Oligoglycerol fatty acid estersRESUMEN: Optimización de la preparación de ésteres grasos de oligoglicerol catalizada por Lipozyme 435. Los ésteres grasos de oligoglicerol (OGEs) son una clase importante de ésteres de ácidos grasos de poliglicerol (PGE) que han sido ampliamente utilizados como emulsionantes en alimentación, medicina y en la industria cosmé-tica. El objetivo de este estudio fue investigar la preparación de OGEs mediante la esterificación de oligoglicerol con ácido linoleico en un sistema libre de disolvente utilizando Lipozyme 435 como catalizador. Se estudiaron los efectos en la eficiencia de esterificación (EE) de la relación molar de sustratos, de los tiempos de reacción, las temperaturas de reacción, la dosis de la enzima, y de la adición de agua. Se realizaron ensayos factoriales individuales y metodología de superficie de respuesta (RSM) para optimizar los parámetros de la reacción. Las condiciones óptimas se obtuvieron como sigue: tiempo de reacción 4,52 h, temperatura de reacción 90 °C, dosis de enzima 2% en peso (basado en la masa total del sustrato), la relación molar de ácido linoleico:oligoglicerol fue de 1,59:1 sin adición de agua. Bajo estas condiciones, el EE experimental (95,82±0,22%) se corresponde bien con lo predicho mediante RSM (96,15%). Se obtiene un resultado similar cuando el proceso se escaló a una producción piloto de hasta 500 g en un reactor de columna de burbujas (BCR). La enzima mantiene el 98,2% de su actividad relativa después de 10 lotes de reacción en el BCR. Se empleó un espectrómetro de masas de ionización mediante electrosp...

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“…Also, the change of Gibbs free energy and equilibrium constants of the reaction at different temperatures are obtained considering Equations (15) and (17). Thermodynamic analysis of the glycerol dehydration was made from the standard enthalpies of formation and the Gibbs free energies of the compounds involved at different temperatures.…”

Section: The Chemical Equilibriummentioning

confidence: 99%

Catalytic Dehydration of Glycerol to Acrolein over a Catalyst of Pd/LaY Zeolite and Comparison with the Chemical Equilibrium

et al. 2017

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Glycerol dehydration to acrolein was studied with three catalysts using zeolite-Y. This zeolite in its protonic form (HY), with La (LaY) and Pd with La (Pd/LaY), was characterized by X-ray diffraction (XRD), Fourier-transform-infrared spectroscopy (FTIR) with pyridine, BET, Scanning Electron Microscope (SEM)-Energy-Dispersive Spectroscopy X-ray (EDS) and the catalytic activity tests were carried out under H 2 atmosphere. It was found that La ions exchanged in the zeolite-Y resulted in the improvement of both glycerol conversion and yield to acrolein, also a relatively constant glycerol conversion was achieved up to three hours, due to the presence of Pd on the catalyst and H 2 in the feed. The comparison of the calculated and experimental yields obtained from the catalytic tests of the Pd/LaY catalyst indicates a greater activity for the reaction to acrolein than for the reaction to acetol. The calculated equilibrium yields of the dehydration reaction from glycerol to acrolein, acetol, ethanal, methanol, and water and the experimental yields of a Pd/LaY catalyst were compared. Thermodynamically, a complete conversion of glycerol can be achieved since the general system remains exothermic and promotes the path to acetol below 480 K. Above this temperature the system consumes energy and favors the production of acrolein, reaching its maximum concentration at 600 K.

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Oligomerization of glycerol – a critical review

Cited by 159 publications

References 44 publications

Influence of acid–base properties of calcined MgAl and CaAl layered double hydroxides on the catalytic glycerol etherification to short-chain polyglycerols

Influence of acid–base properties of calcined MgAl and CaAl layered double hydroxides on the catalytic glycerol etherification to short-chain polyglycerols

Optimization of oligoglycerol fatty acid esters preparation catalyzed by Lipozyme 435

Catalytic Dehydration of Glycerol to Acrolein over a Catalyst of Pd/LaY Zeolite and Comparison with the Chemical Equilibrium

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