931-40-8Relevant academic research and scientific papers
Catalytic performance of functionalized IRMOF-3 for the synthesis of glycerol carbonate from glycerol and urea
Lee, Sun-Do,Park, Gyung-Ah,Kim, Dong-Woo,Park, Dae-Won
, p. 4551 - 4556 (2014)
A functionalized isoreticular metal organic framework material, F-IRMOF-3, having a quaternary ammonium group was prepared by fast precipitation and solvothermal method. The synthesized MOFs exhibited good catalytic performance in the synthesis of glycerol carbonate (GC) from glycerol and urea. F-IRMOF-3 having a larger alkyl chain structure and a more nucleophilic counter anion than the synthesized congeners, exhibited better reactivity in the synthesis of GC. The introduction of a ZnO defect into the F-IRMOF-3 structure by fast precipitation was more advantageous for the glycerolysis of urea than the conventional solvothermal method because of the incorporation of acid-base bifunctional active sites by the former method. The effects of reaction parameters such as temperature, reaction time, catalyst loading, and degree of vacuum on the reactivity were also investigated. The F-IRMOF-3 catalyst can be easily recovered and reused without considerable loss of its initial activity. Copyright
Monitoring the catalytic synthesis of glycerol carbonate by real-time attenuated total reflection FTIR spectroscopy
Calvino-Casilda,Mul,Fernández,Rubio-Marcos,Ba?ares
, p. 106 - 112 (2011)
In situ Attenuated Total Reflectance FTIR spectroscopy was used to study the carbonylation of glycerol with urea. Cobalt oxide nanoparticles, Co 3O4, hierarchically dispersed on zinc oxide microparticles, ZnO, were used as catalysts. The present work demonstrates that in situ real-time attenuated total reflection ATR-FTIR spectroscopy is a valuable tool for monitoring reaction progress and analyzing the reaction mechanism of the synthesis of glycerol carbonate. ATR-FTIR spectroscopy during the carbonylation reaction of glycerol with urea reveals differences in reactivity of various Co3O4/ZnO catalysts, and in particular demonstrates that the first (fast) step in the conversion of glycerol with urea is the formation of glycerol urethane, whereas the consecutive conversion to glycerol carbonate is relatively slow. In addition, possible interactions of the catalytically active sites with in particular the product glycerol carbonate were also evaluated. Interactions of the 2-hydroxyethyl chain of the product with the surface of the catalysts were identified, suggesting product inhibition might be of relevance to the reaction kinetics.
Enzymatic processing of renewable glycerol into value-added glycerol carbonate
Cushing, Kerri A.,Peretti, Steven W.
, p. 18596 - 18604 (2013)
Increased production of biodiesel has led to excess glycerol production worldwide, which has resulted in a significant drop in glycerol prices. Glycerol carbonate is a multifunctional compound used as chemical intermediates, solvents, additives and monomers. In this study, the enzymatic synthesis of glycerol carbonate from glycerol and a dialkyl carbonate was investigated. Glycerol carbonate was formed when reacting glycerol with dimethyl carbonate, diethyl carbonate or dibutyl carbonate in the presence of Candida antarctica lipase B (Novozym 435), using tert-butanol as a solvent. Nearly 100% glycerol conversion was reached after 12 h, with glycerol carbonate being the primary product. The effects of reaction parameters including solvent choice and biocatalyst loading were also examined. The highest activity was found at restricted water conditions and when using tert-butanol as a solvent.
Efficient synthesis of glycerol carbonate from glycerol and urea with lanthanum oxide as a solid base catalyst
Wang, Liguo,Ma, Yubo,Wang, Ying,Liu, Shimin,Deng, Youquan
, p. 1459 - 1462 (2011)
Lanthanum oxide catalyst prepared by precipitation method and calcined at 600 °C exhibited better catalytic activity in the catalytic synthesis of glycerol carbonate from glycerol and urea with TOF up to 1506 mmol/g?h. It was proposed that the lanthanum oxide catalyst with more strong basic sites (Td > 400 °C) exhibited higher catalytic activity. Accordingly, the catalyst containing appropriate amount of La2O 2CO3 phase exhibited higher catalytic activity. Moreover, the recycling experiments demonstrated that the catalytic activity can be essentially preserved during the recycling tests investigated.
Transesterification of Glycerol to Glycerol Carbonate Using KF/Al 2O3 Catalyst: The Role of Support and Basicity
Sandesh, Swetha,Shanbhag, Ganapati V.,Halgeri
, p. 1226 - 1234 (2013)
Glycerol carbonate was synthesized by transesterification of glycerol with dimethyl carbonate using KF supported catalyst. KF was impregnated on various oxides and non-oxide supports like Al2O3, SiO2, ZnO, ZrO2,
Zinc hydroxystannate: A promising solid acid-base bifunctional catalyst
Sandesh, Swetha,Shanbhag, Ganapati V.,Halgeri
, p. 974 - 977 (2014)
Zinc hydroxystannate is shown to be a highly active and selective solid bifunctional catalyst for carbonylation of glycerol with urea. It has strong basicity with Lewis acidic Zn, low hygroscopicity and good thermal stability which makes it a potential catalyst for heterogeneous acid-base catalysed reactions. The Royal Society of Chemistry 2014.
Design of a technical Mg-Al mixed oxide catalyst for the continuous manufacture of glycerol carbonate
Lari,De Moura,Weimann,Mitchell,Mondelli,Pérez-Ramírez
, p. 16200 - 16211 (2017)
The availability of a heterogeneous catalyst, which contains cheap and abundant elements, has a scalable synthesis, is highly active and stable, retains its performance upon shaping into a technical form and can be operated in continuous mode, would pave the way for a more ecological and economical production of glycerol carbonate from glycerol and urea. Here, we show that a mixed oxide of Mg and Al is a promising active phase for this reaction. The solid comprises widely available and non-toxic metals, is easily obtained through the thermal decomposition of a hydrotalcite-like material and can almost match the product yield of state-of-the-art Zn-based catalysts, while displaying an outstanding resistance against leaching, which causes the rapid dissolution of the latter. In-depth characterisation uncovered that Lewis-basic centres are crucial to activate glycerol through dehydrogenation. Their concentration was maximised by optimising the composition and calcination temperature of the precursor, thus reaching up to 60% glycerol carbonate yield. Millimeter-sized extrudates featuring comparable basic properties to the powder sample, a well-developed meso- and macroporosity and high mechanical stability are obtained using a natural clay, bentonite, as a binder and thermally activating the hydrotalcite only after shaping. Upon testing in a continuous reactor under tuned conditions of temperature and pressure and in the presence of an aprotic solvent, the system attains the same glycerol yield as in the batch tests. During 100 h on stream, its activity decreases by 20% due to fouling, but can be fully restored upon burning-off of the carbonaceous deposits. This work discloses the development of a green material that exhibits high efficacy in a sustainable transformation, highlighting key parameters that should be generally taken into account in the design of an industrially relevant chemocatalytic technology.
Ultrasound assisted enzyme catalyzed synthesis of glycerol carbonate from glycerol and dimethyl carbonate
Waghmare, Govind V.,Vetal, Mangesh D.,Rathod, Virendra K.
, p. 311 - 316 (2015)
The present work illustrates the transesterification of glycerol to glycerol carbonate (GlyC) from dimethyl carbonate (DMC) using commercial immobilized lipase (Novozym 435) under ultrasonic irradiation. The experiments were performed in a batch reactor placed in an ultrasonic water bath using a sequence of experimental protocol to evaluate the effects of temperature, molar ratios of substrates, enzyme loading, duty cycle and ultrasound power on the conversion of glycerol to GlyC. It has been found that ultrasound-assisted lipase-catalyzed transesterification of glycerol would be a potential alternative to conventional alkali-catalyzed method, as high conversion (99.75%) was obtained at mild operating conditions: molar ratio of DMC to glycerol 3:1, catalyst amount of 13% (w/w), lower power input (100 W), duty cycle 50% and temperature (60 °C) in a relatively short reaction time (4 h) using Novozym 435 as catalyst. Ultrasound reduces the reaction time up to 4 h as compared to conventional stirring method (14 h) catalyzed by Novozym 435. The repeated use of the catalyst under the optimum experimental condition resulted in decay in both enzyme activity and product conversion.
Valorization of bio-glycerol: New catalytic materials for the synthesis of glycerol carbonate via glycerolysis of urea
Aresta, Michele,Dibenedetto, Angela,Nocito, Francesco,Ferragina, Carla
, p. 106 - 114 (2009)
The glycerolysis of urea plays an important role in the conversion of glycerol into glycerol carbonate because it is a phosgene-free process that uses easily available and low-cost raw materials that have a low toxicity. γ-Zirconium phosphate shows a good
Catalytic performance of ion-exchanged montmorillonite with quaternary ammonium salts for the glycerolysis of urea
Lee, Sun-Do,Park, Moon-Seok,Kim, Dong-Woo,Kim, Il,Park, Dae-Won
, p. 127 - 133 (2014)
Various quaternary ammonium salt (QX) ionic liquids immobilized onto montmorillonite clay (Q-MMT) were prepared by ion-exchange reaction between the tetra-alkyl ammonium salts and ions in the clay interlayer. The Q-MMTs were characterized by elemental ana
