3391-30-8

Usage

Physical state

Colorless liquid

Odor

Faint, sweet

Function

Oxidizing agent

Reactivity

High

Applications

Organic synthesis, pharmaceuticals, and fine chemicals preparation

Safety

Handle with caution, potentially hazardous if not handled properly

Upstream product

• 77-76-9 2,2-dimethoxy-propane 
• 56-81-5 glycerol 
• 67-64-1 acetone 
• 116-11-0 2-Methoxypropene 

Downstream Products

• 847682-00-2 1,3-bis(2,2-dimethyl-1,3-dioxan-5-yloxy)propan-2-yl 2-(4-(4-chlorobenzoyl)phenoxy)-2-methylpropanoate 

Relevant academic research and scientific papers

Solketal synthesis from ketalization of glycerol with acetone: A kinetic study over a sulfated zirconia catalyst

In this work, a series of acid catalysts were synthetized from a commercial zirconium oxide sulfated with a 0.5 M H2SO4 solution by wet impregnation. The characterization results show a correlation between the calcination temperature and the acid sites generated on the materials. Among the catalysts prepared, the sulfated zirconia calcined in air at 400 °C (Zr-S-400), with a molar ratio S/Zr = 0.23 was the most active one due to its larger acid density and greater acid strength caused by the generation of new Br?nsted sites. The Zr-S-400 catalyst exhibited an initial reaction rate of 0.0497 mol.min?1. g?1, and achieved a glycerol conversion of 80 % in 1 h of reaction at 40 °C (glycerol:acetone molar ratio = 1:6). The Zr-S-400 material remained stable after four catalytic cycles, demonstrating the stability of the superficial sulfate species (S/Zr ～ 0.2). In addition, the thermodynamics and kinetics of the reaction were evaluated, as well as the influence of some operating conditions such as the molar ratio of reactants and the water content in the reaction mixture. The following standard molar reaction properties were obtained: ΔHo = -11.6 ± 1.1 kJ.mol?1 and ΔGo = 4.0 ± 0.1 kJ.mol?1. Taking into account that the adsorption of water on this catalyst did not affect the number of acid sites available, a simple pseudo-homogeneous kinetic expression was developed and successfully adjusted to the experimental data in the range under study. Based on this model, the estimated activation energy of the reaction was 88.1 ± 8.9 kJ.mol?1.

Surface-functionalized mesoporous gallosilicate catalysts for the efficient and sustainable upgrading of glycerol to solketal

Two series of functionalized mesoporous Ga silicates were prepared in a straightforward and sustainable one-pot procedure using different alkyl silanes. The efficacy of the adopted co-synthetic approach based on aerosol processing has been proved by 29Si solid-state NMR experiments revealing a degree of functionalization close to the theoretical value. The successful incorporation of gallium as single sites within the silica framework was confirmed via71Ga solid-state magic-angle-spinning NMR measurements. These materials were tested as catalysts for the synthesis of solketal from glycerol at low temperature and under solventless conditions. A systematic study evidenced the importance of a careful tuning of surface polarity, achievable with surface functionalization as well as with different thermal treatments. The solids functionalized with a low degree of methyl groups (5%) displayed enhanced performances compared to the non-functionalized analogues, highlighting the highly beneficial role of surface hydrophobicity as well as the importance of the careful tuning of the hydrophilic/hydrophobic balance. The best functionalized catalysts proved to be easily reusable for multiple catalytic runs. With such a high-performance catalyst in hand, we propose a process which shows a favorable E-factor, indicating that the production of solketal can be envisaged in a sustainable way.

Solketal Formation in a Continuous Flow Process over Hierarchical Zeolites

Glycerol ketalization with acetone to solketal, an oxygenate fuel additive, was demonstrated over hierarchical zeolites of ZSM5, Beta and Mordenite structure in a continuous flow system. Micro-mesoporous zeolites were prepared in two steps, by means of alkaline treatment with NaOH followed by the ionic exchange with NH4NO3 and a subsequent treatment with citric acid. The presence of mesopores in the applied catalysts was confirmed by N2 adsorption/desorption measurements and TEM microscopy. Hierarchical zeolites showed superior catalytic performance and lifetime over 24 hours under mild conditions (atmospheric pressure, acetone to glycerol molar ratio of 3 : 1, WHSV of 3–8 h?1, reaction temperature of 323 K). Glycerol conversion of about 90 % and selectivity to solketal up to 98 % have been obtained over micro-mesoporous catalysts within 24 h without any drop of performance and the symptoms of clogging. Among all hierarchical catalysts tested in a flow reactor, the very high activity defined as solketal yield (88 %) showed ZSM5 and Beta zeolites.

Method for preparing ketal glycerine and/or acetal glycerine by catalyzing glycerine

The invention relates to a method for preparing ketal glycerine and/or acetal glycerine by catalyzing glycerine. The method comprises the following steps: contacting glycerine and a reaction raw material with a catalyst in a reactor, and reacting to obtain a product containing ketal glycerine and/or acetal glycerine, wherein the reaction raw materials contains aldehyde and/or ketone, the molar ratio of glycerine to aldehyde and/or ketone is 1:(1-10), the reaction temperature is 30-180 DEG C, the reaction time is 1-10 hours, the catalyst contains a tin-silicon molecular sieve, and the weight ratio of glycerine to the tin-silicon molecular sieve based on dry basis weight is (1-40):1, the tin-silicon molecular sieve contains a silicon element, a tin element and an oxygen element, a cavity orcavity structure is formed in all or part of crystal grains, the total specific surface area is larger than or equal to 300 m/g, and the proportion of the external specific surface area to the total specific surface area is larger than or equal to 10%. The method provided by the invention has high aldehyde/ketone conversion rate and high acetal/ketal glycerine selectivity.

Exploring the Br?nsted acidity of UiO-66 (Zr, Ce, Hf) metal-organic frameworks for efficient solketal synthesis from glycerol acetalization

Zr, Ce, Hf-based isostructural UIO-66 MOFs exhibited varying degree of Br?nsted acidity (UiO-66(Hf) > UiO-66(Ce) > UiO-66(Zr)) on their secondary building units owing to the differences in their oxophilicities. UIO-66(Hf) showed remarkable catalytic activity for solketal synthesis with a turnover frequency as high as 13?886 h?1, which is 90 times higher than that of UiO-66(Zr) and several orders of magnitude higher than that of H2SO4 or Zeolites.

Mesoporous tin oxide: An efficient catalyst with versatile applications in acid and oxidation catalysis

Mesoporous tin oxide was prepared by template assisted and template-free methods. As-prepared materials were calcined at various temperatures to generate different nature (Br?nsted and Lewis), amount and strength of acidic sites. The physico-chemical properties of the catalysts were studied by XRD, N2 sorption, pyridine-FTIR, NH3-TPD, DRS UV-vis, TGA, SEM, TEM, 1H MAS and 119Sn MAS NMR analyses. The catalytic behavior of mesoporous tin oxide catalysts was evaluated for acetalization and ketalization of glycerol with benzaldehyde and acetone respectively under solvent free conditions. The catalytic performance of mesoporous tin oxide was compared with that of other conventional solid acid catalysts namely H-ZSM-5, H-mordenite, H-beta, Al-MCM-41, Al-SBA-15 and Al-TUD-1. The efficiency of mesoporous tin oxide was also tested for cyclohexene epoxidation reaction. The catalyst prepared by template assisted method showed excellent catalytic performance compared to other catalysts due the difference in nature and amount of acidic sites in the catalyst. Meso-SnO2-T-350 was stable and reusable catalyst for four cycles without any appreciable loss in activity, and therefore it offers a good catalyst for potentially wide applications.

Highly Efficient Glycerol Acetalization over Supported Heteropoly Acid Catalysts

The acetalization of glycerol with acetone to yield solketal was catalyzed by Cs2.5H0.5PW12O40 (Cs2.5) supported on mesoporous silica under mild conditions. It gave a high glycerol conversion and selectivity to the targeted product even at room temperature (23 °C). We studied the use of both bulk and supported Cs2.5 as catalysts in another highly efficient glycerol acetalization reaction with paraformaldehyde, which gave much higher activity than with formaldehyde solution. For the reaction with acetone, the supported Cs2.5 showed a higher activity than the bulk material because of the high surface area of the mesoporous support. Interestingly, the supported Cs2.5 gave a lower conversion than the bulk for the reaction with paraformaldehyde. This is probably because of the high viscosity of the reaction system with the solid reagent paraformaldehyde. Overall, there is a complex relationship between catalyst, reaction conditions, which include the molar ratio of reactants and temperature, reaction mechanism and thermodynamics that affects the achieved activity and byproduct formation. A discussion about these interactions is included for each reaction.

Kinetics of the Formation of Solketal in the Presence of Sulfuric Acid

The kinetics of reversible solketal synthesis in the presence of sulfuric acid as a catalyst is studied. The parameters of kinetic equations describing direct and reverse reactions are found.

Technologies for Processing of Crude Glycerol from Biodiesel Production: Synthesis of Solketal and Its Hydrolysis to Obtain Pure Glycerol

Information on the volume of production of biodiesel and crude glycerol is discussed. The possibility of using crude glycerol as a feedstock for preparing solketal is demonstrated. The specific features of the solketal synthesis from crude glycerol and of separation of the reaction products are described. A catalytic process is suggested for selective decomposition of solketal to glycerol to obtain purified glycerol of any required concentration up to 99.8 wt.%. A flowsheet is provided for processing of crude glycerol to obtain solketal and subsequently converting it to obtain pure glycerol.

Solketal formation from glycerol and acetone over hierarchical zeolites of different structure as catalysts

Glycerol acetalization reaction with acetone was performed at 343?K and using a 1:1 molar ratio of glycerol to acetone in the feed over hierarchical zeolites comprising pores of different diameters (MFI, BEA, and MOR). The best catalytic performance for glycerol acetalization was exhibited by hierarchical (micro-mesoporous) MFI zeolites. Glycerol conversion over MFI zeolites exceeded 80%, with almost 100% selectivity to the desired product (4-hydroxymethyl-2,2-dimethyl-1,3-dioxolane known as solketal). A significant increase in glycerol conversion and also selectivity to solketal in the studied reaction resulted from the easier accessibility of the active sites to reagents due to the formation of mesopores by means of desilication of the microporous zeolites.