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Upstream product

• 56-81-5 glycerol 
• 57-13-6 urea 
• 931-40-8 4-hydroxymethyl-1,3-dioxolan-2-one 

Relevant academic research and scientific papers

Solvent-Free Production of Glycerol Carbonate from Bioglycerol with Urea Over Nanostructured Promoted SnO2 Catalysts

Abstract: In this study nanostructured MoO3 and WO3 promoted SnO2 solid acid catalysts were explored for the production of glycerol carbonate via carbonylation of bioglycerol with urea. The investigated reference SnO2 and promoted catalysts were synthesized by fusion and wet-impregnation methods, respectively. The physicochemical properties of the prepared catalysts were thoroughly analyzed by XRD, Raman, BET surface area, TEM, FTIR, pyridine adsorbed FTIR, NH3-TPD, and XPS techniques. It was found from the characterization studies that integration of SnO2 with MoO3 and WO3 promoters leads to remarkable structural, textural, and acidic properties. Especially, a high quantity of acidic sites were observed over the MoO3/SnO2 catalyst (~ 81.45?μmol?g?1) followed by WO3/SnO2 (61.81?μmol?g?1) and pure SnO2 (46.47?μmol?g?1), which played a key role in the carbonylation of bioglycerol with urea. The BET specific surface area and oxygen vacancies of SnO2 were significantly enhanced after the addition of MoO3 and WO3 promoters. TEM images revealed the formation of nanosized particles with a diameter of around 5–25?nm for the synthesized catalysts. The MoO3/SnO2 catalyst exhibited a high conversion and selectivity towards glycerol carbonate in comparison to other catalysts. The observed better performance is attributed to unique properties of MoO3/SnO2 catalyst including smaller crystallite size, high specific surface area, abundant oxygen vacancies, and more number of acidic sites. This catalyst also exhibited remarkable stability with no significant loss of activity in the recycling experiments. Graphic Abstract: Nanostructured MoO3/SnO2 solid acid catalyst exhibited an excellent catalytic activity and a high selectivity to glycerol carbonate in the carbonylation of bioglycerol with urea under solvent-free and mild conditions.[Figure not available: see fulltext.]

Heterometallic metal-organic framework-templated synthesis of porous Co3O4/ZnO nanocage catalysts for the carbonylation of glycerol

The efficient synthesis of glycerol carbonate (GLC) has recently received great attention due to its significance in reducing excess glycerol in biodiesel production as well as its promising applications in several industrial fields. However, the achievement of high conversion and high selectivity of GLC from glycerol in heterogeneous catalytic processes remains a challenge due to the absence of high-performance solid catalysts. Herein, highly porous nanocage catalysts composed of well-mixed Co3O4 and ZnO nanocrystals were successfully fabricated via a facile heterometallic metal-organic framework (MOF)-templated synthetic route. Benefiting from a high porosity and the synergistic effect between Co3O4 and ZnO, the as-prepared composite catalysts exhibited a significantly enhanced production efficiency of GLC in the carbonylation reaction of glycerol with urea compared to the single-component counterparts. The yield of GLC over the Co50Zn50-350 catalyst reached 85.2%, with 93.3% conversion and near 91% GLC selectivity, and this catalytic performance was superior to that over most heterogeneous catalysts. More importantly, the proposed templated synthetic strategy of heterometallic MOFs facilitates the regulation of catalyst composition and surface structure and can therefore be potentially extended in the tailoring of other metal oxide composite catalysts.

Facile synthesis of glycerol carbonate via glycerolysis of urea catalysed by silicotungstates impregnated into MCM-41

The present contribution includes the solvent free environmentally benign route towards synthesis of glycerol carbonate via glycerolysis of urea. The parent as well as mono lacunary silicotungstates impregnated into MCM-41 were used as efficient catalysts

Investigation of glycerolysis of urea over various ZnMeO (Me = Co, Cr, and Fe) mixed oxide catalysts

In this study, we investigated the glycerolysis of urea over various ZnMeO (Me = Co, Cr, and Fe) mixed oxide catalysts. ZnMeO mixed oxide catalysts were prepared by a co-precipitation method for two Zn/Me ratios, resulting in Zn-rich mixed oxide (Zn2MeO) and Zn-poor mixed oxide (ZnMe2O). In the glycerolysis of urea, the Zn2MeO catalysts exhibited higher glycerol conversion and glycerol carbonate yields than the ZnMe2O catalysts due to the predominance of homogeneous catalysis through Zn isocyanate (NCO) complexes from the Zn2MeO catalysts. Specifically, Zn2CrO was the best catalyst, with the highest yield of glycerol carbonate. Fourier transform infrared (FT-IR) and thermogravimetric analysis (TGA) results of the spent catalysts clearly demonstrated the dominant formation of a solid Zn NCO complex over the spent Zn2CrO catalyst, a unique feature indicating that the better catalytic performance of Zn2CrO was due to the additional heterogeneous reaction route through the solid Zn NCO complex.

Method for preparing high-added-value chemical product through catalysis of glycerin

The invention discloses a method for preparing a high-added-value chemical product through catalysis of glycerin. According to the synthesis method, the fact that activated glycerin is converted into a high-added-value glycerin derivative is taken as a target, activating reaction is carried out in a hydroxyl functionalized ionic liquid system, and glycerin conversion rate data is obtained through a nuclear magnetic characterization means, so that the activation degree of glycerin is evaluated. The preparation method provided by the invention is simple and mild in reaction conditions and replaces a conventional method taking metal as a catalyst; since an ionic liquid catalytic reaction system is used, so that good environment friendliness and repeatability are realized, an ionic liquid preparation process is environment-friendly and good atom economy is realized.

Sustainable valorisation of glycerol via acetalization as well as carboxylation reactions over silicotungstates anchored to zeolite Hβ

A simple, green and effective pathway towards valorisation of glycerol to value added products has been demonstrated. In this context, catalysts comprising parent as well as lacunary silicotungstates anchored to large pore zeolite Hβ have been synthesized and characterized by various physicochemical methods. Parent silicotungstic acid based catalyst proved to be better catalyst in terms of conversion of glycerol showing 73% conversion for carboxylation reaction and 97% conversion of glycerol towards acetalization reaction. The better activity of the catalyst was correlated with its strong acidic character. It was observed that by tuning the acidity of parent silicotungstate by formation of lacunary silicotungstate leads to the increase in the selectivity of 5-membered dioxolane from 68% to 78% and selectivity of glycerol carbonate from 72% to 75%. Both the catalysts were reusable up to four cycles under the investigated reaction conditions. The probable mechanisms for both the reactions are also discussed.

An accelerated route of glycerol carbonate formation from glycerol using waste boiler ash as catalyst

Waste boiler ash was successfully utilised as catalyst for the direct synthesis of glycerol carbonate from glycerol and urea. A series of catalysts were prepared using various calcination temperatures. The physico-chemical properties of the catalysts have been investigated by using XRD, BET, TGA, FESEM-EDX, ICP-MS, Hammett test and CO2-TPD. From the study it was found that boiler ash had significant catalytic activity towards conversion of glycerol into glycerol carbonate. It is believed that the potassium metal ion which detaches from potassium silicate had a major impact on the catalytic data where the potassium ion being a weak Lewis acid causes selective catalytic transformation of glycerol into glycerol carbonate. The mechanistic pathway through glycerol carbamate intermediate was confirmed through time online analysis study using 13C-NMR and ATR-FTIR, respectively. However, the selective transformation of glycerol carbamate into glycerol carbonate is reported to be different where it is formed in an accelerated manner. The highest catalytic activity resulted in an average percentage of 93.6 ± 0.4% glycerol conversion, 90.1 ± 1.0% glycerol carbonate selectivity and 84.3 ± 1.1% glycerol carbonate yield. Besides, for the first time the novel idea of using waste material, specifically boiler ash, is proposed as a catalyst for synthesis of glycerol carbonate from glycerol and urea. The current research employed suggests an alternative route for proper disposal of waste boiler ash.

Formation of glycerol carbonate from glycerol and urea catalysed by metal monoglycerolates

Polymeric monoglycerolate complexes of zinc and cobalt can act as homogeneous catalysts for the one-pot synthesis of glycerol carbonate from glycerol and urea. Effects of reaction temperature, time and glycerol to urea molar ratios on glycerol carbonate s

Aminolysis reaction of glycerol carbonate in organic and hydroorganic medium

Aminolysis reaction of glycerol carbonate with primary amine in organic and hydroorganic media leads to the formation of two hydroxyurethane isomers and a partial decomposition of glycerol carbonate into glycerol. Aminolysis with a secondary amine promotes the condensation reaction and limits the formation of glycerol. The ratio of α versus β was determined by zgig 13C NMR. This technique permits computing the yield of α and β products in the medium. The quantity of glycerol was determined by GC analysis. The ratio of the isomers and the amount of glycerol depend on the amine and the solvent. Kinetic investigations reveal that, in hydroorganic medium, the more the alkyl chain of the amine increased, the less glycerol was formed. On the contrary, in organic medium, the alkyl chain of the amine does not play a major role in the formation of glycerol.

Synthesis of glycerol carbonate from glycerol and urea with gold-based catalysts

The reaction of glycerol with urea to form glycerol carbonate is mostly reported in the patent literature and to date there have been very few fundamental studies of the reaction mechanism. Furthermore, most previous studies have involved homogeneous catalysts whereas the identification of heterogeneous catalysts for this reaction would be highly beneficial. This is a very attractive reaction that utilises two inexpensive and readily available raw materials in a chemical cycle that overall, results in the chemical fixation of CO2. This reaction also provides a route to up-grade waste glycerol produced in large quantities during the production of biodiesel. Previous reports are largely based on the utilisation of high concentrations of metal sulfates or oxides, which suffer from low intrinsic activity and selectivity. We have identified heterogeneous catalysts based on gallium, zinc, and gold supported on a range of oxides and the zeolite ZSM-5, which facilitate this reaction. The addition of each component to ZSM-5 leads to an increase in the reaction yield towards glycerol carbonate, but supported gold catalysts display the highest activity. For gold-based catalysts, MgO is the support of choice. Catalysts have been characterised by XRD, TEM, STEM and XPS, and the reaction has been studied with time-on-line analysis of products via a combination of FT-IR spectroscopy, HPLC, 13C NMR and GC-MS analysis to evaluate the reaction pathway. Our proposed mechanism suggests that glycerol carbonate forms via the cyclization of a 2,3-dihydroxypropyl carbamate and that a subsequent reaction of glycerol carbonate with urea yields the carbamate of glycerol carbonate. Stability and reactivity studies indicate that consecutive reactions of glycerol carbonate can limit the selectivity achieved and reaction conditions can be selected to avoid this. The effect of the catalyst in the proposed mechanism is discussed.