Kinetics of Resorcinol-Formaldehyde Condensation—Comparison of Common Experimental Techniques

Porous carbons, originated from resorcinol-formaldehyde (RF) gels, show high application potential. However, the kinetics and mechanism of RF condensation are still not well described. In this work, different methods (dynamic light scattering–DLS, Fourier transform infrared spectroscopy–FTIR, low field 1H nuclear magnetic resonance relaxometry–1H-NMR, and differential scanning calorimetry–DSC) were used to follow the isothermal RF condensation of mixtures varying in catalyst content (Na2CO3) and reactant concentration. The applicability and results obtained by the methods used differ significantly. The changes in functional groups can be followed by FTIR only at very early stages of the reaction. DLS enables the estimate of the growth of particles in reaction solution, but only before the solution becomes more viscous. Following the relaxation of 1H nuclei in water during RF condensation brings a different view on the system—this technique follows the properties of the present water that is gradually captured in polymeric gel. From this side, the process behaves similarly to the nucleation reaction, which is in contradiction to the n-order mechanism confirmed by other techniques. The widest range of applicability was found for DSC measurement of the freezing/melting behavior of the reaction mixture, which is possible to use without any limitations until full solidification. Furthermore, this approach enables us to follow the gradual formation and development of the gel through the intermediate undergoing glass transition.

Activated Carbon Modification towards Efficient Catalyst for High Value-Added Products Synthesis from Alpha-Pinene

DT0-activated carbons modified with HCl and HNO3 acids, which were used for the first time in the catalytic process of alpha-pinene isomerization, are presented in this study. The carbon materials DT0, DT0_HCl, DT0_HNO3, and DT0_HCl_HNO3 were examined with the following methods: XRF, SEM, EDX, XPS, FT-IR, XRD, and N2 adsorption at −196 °C. It was shown that DT0_HCl_HNO3-activated carbon was the most active material in the alpha-pinene isomerization process. Detailed studies of alpha-pinene isomerization were carried out over this carbon by changing the reaction parameters such as time (5–180 min) and temperature (60–175 °C). The 100% conversion of alpha-pinene was achieved at the temperature of 160 °C and catalyst content of 5 wt% after 3 h over the DT0_HCl_HNO3 catalyst. Camphene and limonene were the main products of the alpha-pinene isomerization reaction.

The Studies on α-Pinene Oxidation over the TS-1. The Influence of the Temperature, Reaction Time, Titanium and Catalyst Content

The work presents the results of studies on α-pinene oxidation over the TS-1 catalysts with different Ti content (in wt%): TS-1_1 (9.92), TS-1_2 (5.42), TS-1_3 (3.39) and TS-1_4 (3.08). No solvent was used in the oxidation studies, and molecular oxygen was used as the oxidizing agent. The effect of titanium content in the TS-1 catalyst, temperature, reaction time and amount of the catalyst in the reaction mixture on the conversion of α-pinene and the selectivities of appropriate products was investigated. It was found that it is most advantageous to carry out the process of α-pinene oxidation in the presence of the TS-1 catalyst with the titanium content of 5.42 wt% (TS-1_2), at the temperature of 85 °C, for 6 h and with the catalyst TS-1 content in the reaction mixture of 1 wt%. Under these conditions the conversion of α-pinene amounted to 34 mol%, and the selectivities of main products of α-pinene oxidation process were: α-pinene oxide (29 mol%), verbenol (15 mol%) and verbenone (12 mol%). In smaller quantities also campholenic aldehyde, trans-pinocarveol, myrtenal, myrtenol, L-carveol, carvone and 1,2-pinanediol were also formed. These products are of great practical importance in food, cosmetics, perfumery and medicine industries. Kinetic studies were also performed for the studied process.

Epoxidation of 1,5,9-Cyclododecatriene with Hydrogen Peroxide over Ti-MCM-41 Catalyst

This work presents the results of our research on the epoxidation of 1,5,9-cyclododecatriene (CDT) with hydrogen peroxide over the Ti-MCM-41 catalyst. The influence of the following parameters on the course of the process was investigated: temperature, CDT:H2O2 molar ratio, solvent composition and its type, and catalyst content. The highest selectivity of CDT transformation to 1,2-epoxy-5,9-cyclododecadiene (ECDD)—approximately 100 mol%, the highest yet reported—was obtained at the CDT conversion of 13 mol% and with the following parameter values: a catalyst content of 5 wt%; a molar ratio of CDT:H2O2 = 2; isopropyl alcohol (i-PrOH) as the solvent, with a composition of 80 wt% in the reaction mixture; a temperature of 80 °C; and a reaction time of 240 min. The highest conversion of CDT (37 mol%) was obtained at the ECDD selectivity of 56 mol% and using the following process parameters: a catalyst content of 5 wt%; a molar ratio of CDT:H2O2 = 0.5; i-PrOH used as the solvent, with solvent composition of 80 wt%; a temperature of 80 °C; and a reaction time of 60 min. It should be emphasized that the CDT conversion obtained in the current study is higher (by 9 mol%) than that described in the literature on heterogeneous catalysts.

The Influence of Acid Hardener on the Strength and Hot-Distortion Properties of No-Bake Sand Cores

In this research work, the effects of different amounts of acid hardener (30%, 40%, 60%, 80% weighted to the resin) on the hardening characteristics and hot-distortion properties of no-bake furan and no-bake phenolic bonded sand cores were studied. Bending tests were conducted on test bars with storage times of 1, 2, 3, 5, 7, 24h. Hot-distortion tests were carried out on specimens with storage times of 4h and 24h. The bending tests revealed that in the case of the furan binder system, the acid hardener is best utilized in terms of higher bending strength, in an amount of 40–60%, while in the case of the phenolic binder system, the amount of 60–80% acid hardener resulted in higher bending strength of the sand specimens. Too low (30%) acid hardener (catalyst) level produced low bending strength. Too high (80%) amount of acid hardener decreased the strength of the no-bake furan sand samples, and as can be seen from the SEM analysis, it damaged the binder bridges between the sand grains. The hot-distortion tests showed that there is a correlation between the catalyst content and the max. Deformation of the samples both in the furan and in the phenolic no-bake sand cores, which can be described with a maximum curve. Increasing the acid hardener changes the thermoplastic behavior of the phenolic resin, thus the binder bridges become more rigid and brittle. The acid hardener above 40% decreased the thermal stability of the furan and phenolic bonded test pieces. The research work also revealed significant differences between the specimens made with furan and phenolic binder and the effect of the storage time in terms of the bending strength and hot-distortion properties.

Magnetic silica particles functionalized with guanidine derivatives for microwave-assisted transesterification of waste oil

This study aimed to develop a facile synthesis procedure for heterogeneous catalysts based on organic guanidine derivatives superbases chemically grafted on silica-coated Fe3O4 magnetic nanoparticles. Thus, the three organosilanes that were obtained by reacting the selected carbodiimides (N,N′-dicyclohexylcarbodiimide (DCC), N,N′-diisopropylcarbodiimide (DIC), respectively 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) with 3-aminopropyltriethoxysilane (APTES) were used in a one-pot synthesis stage for the generation of a catalytic active protective shell through the simultaneous hydrolysis/condensation reaction with tetraethyl orthosilicate (TEOS). The catalysts were characterized by FTIR, TGA, SEM, BET and XRD analysis confirming the successful covalent attachment of the organic derivatives in the silica shell. The second aim was to highlight the capacity of microwaves (MW) to intensify the transesterification process and to evaluate the activity, stability, and reusability characteristics of the catalysts. Thus, in MW-assisted transesterification reactions, all catalysts displayed FAME yields of over 80% even after 5 reactions/activation cycles. Additionally, the influence of FFA content on the catalytic activity was investigated. As a result, in the case of Fe3O4@SiO2-EDG, a higher tolerance towards the FFA content can be noticed with a FAME yield of over 90% (for a 5% (weight) vs oil catalyst content) and 5% weight FFA content.

Clinoptilolite as a natural, active zeolite catalyst for the chemical transformations of geraniol

This work presented the studies with the natural zeolite—clinoptilolite as the catalyst for the isomerization of geraniol. During the research, it turned out that the studied process is much more complicated, and not only isomerization takes place in it, but also dehydration, oxidation, dimerization, cyclization and fragmentation of the carbon chain. Geraniol is an organic raw material which can be obtained not only by a chemical synthesis but also from plants (renewable biomass) by distillation or extraction method, for example a source of geraniol can be a plant—geranium. Before catalytic tests clinoptilolite was characterized by the instrumental methods, such as: XRD, porosity studies—nitrogen adsorption at 77 K, SEM, EDXRF, and FT-IR. Gas chromatography analyses showed that the main products of geraniol isomerization process were 6,11-dimethyl-2,6,10-dodecatrien-1-ol and thumbergol. The selectivity of 6,11-dimethyl-2,6,10-dodecatrien-1-ol and thumbergol depended on the temperature, catalyst content and reaction time. These parameters were changed in the following ranges: 80–150 °C (temperature), 5–15 wt% (catalyst content) and 15–1440 min. (reaction time). The most favorable conditions for 6,11-dimethyl-2,6,10-dodecatrien-1-ol and thumbergol obtaining were: temperature 140 ºC, catalyst content 12.5 wt% and reaction time 180 min. At these conditions, the conversion of geraniol amounted to 98 mol%, and the selectivities of 6,11-dimethyl-2,6,10-dodecatrien-1-ol and thumbergol amounted to 14 and 47 mol%, respectively.

Epoxidation of 1,5,9-cyclododecatriene with hydrogen peroxide under phase-transfer catalysis conditions: influence of selected parameters on the course of epoxidation

This work presents the studies on the epoxidation of 1,5,9-cyclododecatriene (CDT) with hydrogen peroxide as the oxidizing agent, under conditions of the phase transfer catalysis (PTC), and with the following catalytic system: H2WO4/H3PO4/[CH3(CH2)7]3CH3N+HSO4− (compounds were mixed at the ratio of 2:1:1). The influence of the following parameters on the course of this process was investigated: catalyst content, molar ratio of H2O2:CDT, temperature and type of solvent. The highest yield of 1,2-epoxy-5,9-cyclododecadiene (ECDD) (54.9 mol%), at the conversion of CDT reached 72.3 mol%, was obtained at the temperature of 50 °C, for the catalyst content of 0.45 mol% (in relation to the introduced CDT), for the molar ratio of H2O2:CDT 1.5:1, with toluene as the solvent and after the reaction time of 30 min. Considering the he obtained results and numerous applications of ECDD, further research should be developed to provide a more efficient and environmentally friendly way of obtaining this compound. Graphic abstract

Synthesis, Characterization, and Catalytic Applications of the Ti-SBA-16 Porous Material in the Selective and Green Isomerizations of Limonene and S-Carvone

This work presents studies on the activity of the Ti-SBA-16 (SBA—Santa Barbara Amorphous) catalyst in the isomerization of limonene and S-carvone. The Ti-SBA-16 catalyst was synthesized by a two-step method: first, the SBA-16 material was produced, and then it was impregnated with the titanium source. The Ti-SBA-16 catalyst was subjected to detailed characterizations by means of instrumental methods: XRD (X-ray Diffraction), UV-Vis (Ultraviolet–Visible) spectroscopy, FTIR (Fourier-Transform Infrared) spectroscopy, SEM (Scanning Electron Microscopy) with EDX (Energy Dispersive X-ray) spectroscopy, and EDXRF (Energy Dispersive X-ray Fluorescence). Both limonene and S-carvone underwent isomerization over the Ti-SBA-16 catalyst. In the isomerization of limonene, the main product was terpinolene, and its highest yield amounted to 39 mol% after 300 min at 170 °C with a catalyst content of 15 wt%. Under these conditions, the conversion of limonene reached 78 mol%. In contrast, the highest yield of carvacrol (65 mol%) was obtained with the catalyst content of 15 wt%, at 200 °C, and with the conversion of S-carvone reaching 79 mol%.

Furfural preparation using KHSO4 as the catalyst and its recovery and reuse

KHSO4 was used for furfural production, and the catalyst was recovered. The wet solid mixture after reaction was subjected to hot water washing and solid-liquid separation to recover the catalyst into the filtrate. Methods for determination of the catalyst content in both liquid and solid phases were invented. The effect of the mass ratio of hot water to the wet solid mixture, washing time, and number of washing times on the catalyst recovery were investigated. The total recovery of the catalyst into the filtrate was up to 87.7% when using the optimum conditions. The catalyst was reused in laboratory experiments up to 5 successive times. The recovered catalyst had the same activity for furfural production as the fresh catalyst on the same dosage level. Thermal gravimetric and X-ray diffractometer analyses of the catalyst showed that the catalyst was stable and reusable.