Yuanlin Li

Pressure and temperature behavior of the cinnamaldehyde oxidation process was determined using a custom-designed mini closed pressure vessel test (MCPVT), which is a new method to investigate the stability and hazard assesment of the cinnamaldehyde oxidation reaction. The oxidation products were analyzed by gas chromatography-mass spectrometry (GC-MS). The results showed that cinnamaldehyde was stable under nitrogen atmosphere but very unstable under oxygen atmosphere. The initial oxidation products were analyzed by iodimetry and the cinnamaldehyde peroxide value could reach 139.44 mmol kg⁻¹ when the oxidation temperature was 308 K. The oxidation kinetics of cinnamaldehyde were studied by using the pressure versus time (P–t) curves obtained from the MCPVT process. The reaction is a second-order reaction, the kinetic equation is ln k = −2233.66 × (1/T) + 11.19, and the activation energy E_a is 18.57 kJ mol⁻¹ at 308–338 K. The explosion of the cinnamaldehyde oxidation reaction was observed by MCPVT, in which the onset temperature was 373 K. The main products of cinnamaldehyde oxidation are acetaldehyde, benzaldehyde, phenylacetaldehyde, acetophenone, 2-hydroxyphenyl acetone, cinnamaldehyde epoxide, benzoic acid, and cinnamic acid. Oxidation is a three-step process: (1) cinnamaldehyde reacts with oxygen to form peroxides; (2) complex oxidation reactions are caused by the thermal decomposition of peroxides; (3) rapid oxidation and thermal decomposition lead to explosion hazard.

Carbon-based solid acid catalysts were prepared using rice straw (RS) waste, and the effects of carbonization temperature and sulfonation temperature on the catalytic activity were investigated. The properties of the catalysts were characterized using thermo gravimetric (TG), scanning electron microscope (SEM), Brunauer–Emmet–Teller (BET), Fourier transform infrared spectroscopy (FT-IR), temperature-programmed desorption (TPD), and X-ray photoelectron spectroscopy (XPS), and their activities were investigated through the hydration of α-pinene. The conversion of α-pinene and the selectivity of α-terpineol reached 67.60% and 57.07% at 80 °C and atmospheric pressure in 24 h, respectively. The high catalytic capacity of the catalyst is attributed to the high acid site density and high porosity of the catalyst. TPD analysis and FT-IR spectroscopy showed that the catalyst produced by low-temperature carbonization at 300 °C followed by low-temperature sulfonation at 80 °C had abundant strong acid sites (0.82 mmol/g), which can effectively inhibit the side reactions of hydrated α-pinene. The total acidity reached 2.87 mmol/g. N₂-physisorption analysis clearly indicated that the obtained catalysts were mesopore-predominant materials, and the S_BET and V_Total of catalysts reached 420.9 m²/g and 4.048 cm³/g, respectively. Preparation of the catalyst involves low energy consumption, and its cheap raw materials make the whole process simple, economical, and environmentally friendly.

A self-designed mini gas–solid reaction device was applied as promising equipment to investigate the oxidation characteristics and kinetics of the glycerol ester of rosin (GER) under 254 nm UV irradiation in air. Peroxide formation during the photo-oxidation process was analyzed by iodimetry. The peroxide concentration is related to the light intensity (I) and the temperature (T), and increasing I and T would destabilize the GER by accelerating peroxide generation. The photo-oxidation of GER followed pseudo-first-order reaction kinetics under a given hypothesis. A linear relationship was observed between activation energy and the logarithm of light intensity (ln I), which can be expressed as E_a = −3.575 ln I + 34.943 under the experimental conditions. This research indicated that under 254 nm UV irradiation GER could be easily oxidized even at room temperature.

A self-designed reaction device was used as a promising equipment to investigate the oxidation characteristics and kinetics of rosin pentaerythritol ester (RPE) under UV irradiation. Photo-oxidation kinetics and the initial quantum yield (Φ) of RPE were calculated. The initial oxidation product of the photo-oxidation reaction—peroxide was analyzed by iodimetry. The peroxide concentration is related to the light intensity (I) and the temperature (T), and the increasing T and I would destabilize the RPE by accelerating peroxide forming. Photo-oxidation of RPE follows the pseudo first-order reaction kinetics. The relationship between activation energy and logarithm of light intensity (ln I) is linear, and it is expressed as Ea = −4.937ln I + 45.565. Φ was calculated by the photo-oxidation kinetics, and the average value of Φ was 7.19% in the light intensity range of 200–800 μW cm⁻². This research can provide fundamental information for application of RPE, and help obtain a better understanding of the stability of rosin esters.