Agnieszka Wróblewska

The Epoxidation of Limonene over the TS-1 and Ti-SBA-15 Catalysts

Limonene belongs to a group of very important intermediates used in the production of fine chemicals. This monoterpene compound can be obtained from peels of oranges or lemon which are a (biomass) waste from the orange juice industry. Thus, limonene is a renewable, easy available and a relatively cheap compound. This work presents preliminary studies on the process of limonene epoxidation over zeolite type catalysts such as: TS-1 and Ti-SBA-15. In these studies methanol was used as a solvent and as an oxidizing agent a 60 wt % hydrogen peroxide solution was applied. The activity of each catalyst was investigated for four chosen temperatures (0 °C, 40 °C, 80 °C and 120 °C). The reaction time was changed from 0.5 to 24 h. For each catalyst the most beneficial conditions (the appropriate temperature and the reaction time) have been established. The obtained results were compared and the most active catalyst was chosen. These studies have also shown different possible ways of limonene transformation, not only in the direction of 1,2-epoxylimonene and its corresponding diol, but also in direction of carveol, carvone and perillyl alcohol—compounds with a lot of applications. The possible mechanisms of formation of the allylic oxidation products were proposed.

Epoxidation of allyl alcohol to glycidol over the microporous TS-1 catalyst.

The results of the epoxidation of allyl alcohol with 30% hydrogen peroxide over the TS-1 catalyst have been presented. The studies were carried out under the atmospheric pressure and at the presence of methanol as a solvent. The influence of the following technological parameters on the course of epoxidation was examined: the temperature of 20-60 degrees C, the molar ratio of AA/H(2)O(2) 1:1-5:1, the methanol concentration of 5-90 wt%, the catalyst content of 0.1-5.0 wt% and the reaction time 5-300 min. The main functions describing the process were the selectivity to glycidol in relation to allyl alcohol consumed, the conversion of substrates, and the selectivity of transformation to organic compounds in relation to hydrogen peroxide consumed. The parameters at which the functions describing the process reached the highest values were determined.

The utilization of Ti-SBA-15 catalyst in the epoxidation of allylic alcohols

Ti-SBA-15, one of the latest titanium silicalite catalysts, has been prepared according to the literature by the direct hydrothermal synthesis using Pluronic 123 as structure-directing agent. The characterization of the catalyst was performed by means of the following methods: XRD, IR, UV–Vis, X-ray microanalysis and SEM. The catalytic properties of the Ti-SBA-15 catalyst have been tested in the epoxidation of allyl alcohol, methallyl alcohol, crotyl alcohol and 1-butene-3-ol with hydrogen peroxide. The process has been described by the following main functions: the selectivity to epoxide compound in relation to allylic compound consumed and the conversion of allylic compound.

Epoxidation of allyl alcohol over mesoporous Ti-MCM-41 catalyst

Epoxidation of allyl alcohol with 30 wt% hydrogen peroxide over Ti-MCM-41 catalyst under atmospheric pressure and in the presence of methanol as a solvent has been studied. The influence of the following parameters: temperature (20-60 degrees C), the molar ratio of AA/H(2)O(2) (0.5-5), methanol concentration (5-90 wt%), catalyst concentration (0.1-5.0 wt%) and reaction time (5-180 min) has been investigated. The process has been described by the following functions: the selectivity of transformation to glycidol in relation to allyl alcohol consumed, conversions of the substrates and selectivity of transformation to organic compounds in relation to hydrogen peroxide consumed. The technological parameters, at which the functions describing the process take the optimum values, have been established.

Studies on the deactivation of Ti-MCM-41 catalyst in the process of allyl alcohol epoxidation

Abstract The synthesis of Ti-MCM-41 catalyst was performed. The obtained catalyst was characterized by the following instrumental methods: UV-vis, IR spectroscopy, XRD, and X-ray microanalysis. The activity of the obtained catalyst was tested in the process of allyl alcohol epoxidation with 30 wt.% hydrogen peroxide in methanol as a solvent and under atmospheric pressure. In the next stage, recovery of Ti-MCM-41 catalyst from the post-reaction mixture and its regeneration by washing with appropriate solvents and drying were conducted. In the case of total loss of the activity of the catalyst, calcination of the catalyst was also carried out. The loss of titanium from the structure of Ti-MCM-41 catalyst and a partial collapsing of the structure of this catalyst can be the main reason of the decrease the activity of the catalyst what was manly visible in the decrease of the values of two functions of this process: the allyl alcohol conversion and conversion of hydrogen peroxide to organic compounds.

The oxidation of limonene at raised pressure and over the various titanium-silicate catalysts

Abstract This work presents the studies on the oxidation of limonene with hydrogen peroxide and tert-butyl hydroperoxide (TBHP) in the presence of : TS-2, Ti-Beta, Ti-MCM-41 and Ti-MWW catalysts, at the autogenic pressure and atmospheric pressure. The examination were performed at the following conditions: the temperature of 140°C (studies in the autoclave) and 80°C (studies in glass reactor), the molar ratio of limonene/oxidant (H2O2 or WNTB) = 1:1, the methanol concentration 80 wt%, the catalyst content 3 wt%, the reaction time 3 h and the intensity of stirring 500 rpm. The analysis of the results showed that in process not only 1,2-epoxylimonene was formed but also: 1,2-epoxylimonene diol, carveol, carvone and perillyl alcohol but for 1,2-epoxylimonene obtaining the better method was the method at the autogenic pressure and in the presence of TBHP.

Limonene oxidation over Ti-MCM-41 and Ti-MWW catalysts with t-butyl hydroperoxide as the oxidant

This paper presents the method of limonene epoxidation over Ti-MCM-41 and Ti-MWW catalysts in the presence of t-butyl hydroperoxide as an oxidant. Natural limonene used in the epoxidation process was obtained via steam distillation (97% purity). The purpose of the research was to obtain the highest yield of 1,2-epoxylimonene, but the performed studies showed that the process of limonene epoxidation is more complex because in addition to epoxidation products (1,2-epoxylimonene and its diol which were formed usually in small amount) also the following oxygenated derivatives of limonene are formed: carvone, carveol, and perillyl alcohol (products of allylic oxidation (hydroxylation) at positions 6 and 7 in limonene molecule). Therefore, ultimately, the most favorable conditions for the limonene oxidation process were selected at the highest conversion of limonene and at high values of perillyl alcohol and carveol or one of these two products. Perillyl alcohol and carveol have found numerous applications in medicine, among others, therefore this direction seems to be the most beneficial. This also work presents the short characteristization of the titanium silicate Ti-MCM-41 and Ti-MWW catalysts used in the research, taking into account their structure, properties and applications are presented.

Epoxidation of allyl-glycidyl ether with hydrogen peroxide over Ti-SBA-15 catalyst and in methanol medium

Abstract This work presents the studies on the epoxidation of allyl-glycidyl ether (AGE) over the Ti-SBA-15 catalyst. In these studies an aqueous hydrogen peroxide was used as an oxidizing agent and as a solvent methanol was applied. The studies on the influence the following parameters: temperature (20–80°C), molar ratio of AGE/H2O2 (1:1.5–5:1), methanol concentration (10–90 wt%), catalyst content (1–9 wt%) and reaction time (15–240 min.) were carried out and the most favourable values of these parameters were chosen (temperature 80°C, molar ratio of AGE/H2O2 = 5:1, methanol concentration 30 wt%, catalyst content 3 wt% and the reaction time 240 min.). At these conditions the functions describing the process reached the following values: the selectivity of diglycidyl ether (DGE) 9.2 mol%, the conversion of AGE 13.9 mol% and the efficiency of H2O2 conversion 89.9 mol%.

The utilization of the mesoporous Ti-SBA-15 catalyst in the epoxidation of allyl alcohol to glycidol and diglycidyl ether in the water medium

Abstract This work presents the studies on the optimization the process of allyl alcohol epoxidation over the Ti-SBA-15 catalyst. The optimization was carried out in an aqueous medium, wherein water was introduced into the reaction medium with an oxidizing agent (30 wt% aqueous solution of hydrogen peroxide) and it was formed in the reaction medium during the processes. The main investigated technological parameters were: the temperature, the molar ratio of allyl alcohol/hydrogen peroxide, the catalyst content and the reaction time. The main functions the process were: the selectivity of transformation to glycidol in relation to allyl alcohol consumed, the selectivity of transformation to diglycidyl ether in relation to allyl alcohol consumed, the conversion of allyl alcohol and the selectivity of transformation to organic compounds in relation to hydrogen peroxide consumed. The analysis of the layer drawings showed that in water solution it is best to conduct allyl alcohol epoxidation in direction of glycidol (selectivity of glycidol 54 mol%) at: the temperature of 10–17°C, the molar ratio of reactants 0.5–1.9, the catalyst content 2.9–4.0 wt%, the reaction time 2.7–3.0 h and in direction of diglycidyl ether (selectivity of diglycidyl ether 16 mol%) at: the temperature of 18–33°C, the molar ratio of reactants 0.9–1.65, the catalyst content 2.0–3.4 wt%, the reaction time 1.7–2.6 h. The presented method allows to obtain two very valuable intermediates for the organic industry.

The Role of the Additive in the Form of Na2SO4 in the Epoxidation of Dialllyl Ether

This work presents the research on the influence of the addition of the appropriate amounts of the inorganic salt (Na2SO4) on the reduction of the ineffective decomposition of hydrogen peroxide (H2O2) and simultaneously on the increase of the efficiency of hydrogen peroxide conversion. The studies were carried out for the epoxidation of diallyl ether to allyl-glycidyl ether with 30 wt% hydrogen peroxide on the TS-1 catalyst and in the presence of acetonitrile as the solvent. The studies were conducted in the following conditions: the temperature of 70°C, the molar ratio of diallyl ether/hydrogen peroxide = 3:1, the acetonitrile concentration of 50 wt%, the TS-1 content of 9 wt%, the reaction time of 3 hours, the intensity of stirring of 500 rpm and the molar ratio of hydrogen peroxide/Na2SO4 2:1 to 14:1 (also the results for epoxidation of diallyl ether without Na2SO4 were presented)