Enhanced Combustion of Bituminous Coal and Semicoke Mixture by Ferric Oxide with Thermographic and Kinetic Analyses

We study the specific catalytic effect of the catalyst on the combustion process of pulverized coal of increasing the proportion of semicoke in the mixture of semicoke and bituminous coal, and reducing the cost of blast-furnace coal injection. A combination of thermogravimetric and kinetic analyses were used to study the catalytic effect of Fe2O3 on semicoke and bituminous coal, and to improve the amount of semicoke in the mixed coal powder of bituminous coal and semicoke. Experimental results showed that Fe2O3 had a catalytic effect on both semicoke and bituminous coal, but there were differences in the catalytic stages of the same catalyst for different pulverized coal types. The addition of 2 wt % Fe2O3 to semicoke and bituminous coal each led to the ignition temperature and maximal burning rate temperature of the semicoke decreasing, indicating that the catalyst promoted the precipitation of a volatile fraction from the semicoke. The maximal burning rate temperature and burnout temperature of the bituminous coal decreased, and maximal weight loss rate increased, indicating that the catalyst promoted the combustion of the fixed carbon of bituminous coal. The optimal proportioning amount of semicoke in the mixed coal powder without the addition of a catalyst was 25%. After adding 2 wt % Fe2O3, the proportional amount of semicoke increased by 10%. The addition of the catalyst resulted in even lower activation energy for the same conversion rate. When the conversion rate was in the ranges of 0.1–0.2 and 0.5–0.7, the activation energy decreased by 22% and 26%, respectively, compared with that without a catalyst. Fe2O3 promoted the combustion of bituminous coal and semicoke. This enhanced the combustion performance of the pulverized coal mix and increased the proportion of semicoke in the mix, which has certain guiding significance in reducing the cost of blast-furnace iron making.

Retrieval of High Added Value Natural Bioactive Coumarins from Mandarin Juice-Making Industrial Byproduct

Cold pressed essential oil (CPEO) of mandarin (Citrus reticulata Blanco), a by-product of the juice-making industrial process known to contain large amounts of polymethoxyflavones, was exploited for its content in high added value natural coumarins. The study herein afforded a method referring to the evaporation of CPEO volatile fraction under mild conditions (reduced pressure and temperature below 35 °C) as azeotrope with isopropanol. This allowed the isolation of high added value coumarins from the non-volatile fragment using preparative High Performance Liquid Chromatography (HPLC). Pilot-scale application of this procedure afforded for each kg of CPEO processed the following natural bioactive coumarins in chemically pure forms: heraclenol (38–55 mg), 8-gerayloxypsoralen (35–51 mg), auraptene (22–33 mg), and bergamottin (14–19 mg). The structures of coumarins were verified by Nuclear Magnetic Resonance (NMR) spectroscopy and HPLC co-injection with authentic standards. Thus, the low market value mandarin CPEO with current value of 17 to 22 EUR/kg can be valorized through the production of four highly bioactive natural compounds worth 3479 to 5057 EUR/kg, indicating the great potentials of this methodology in the terms of the circular economy.

Different Wines from Different Yeasts? “Saccharomyces cerevisiae Intraspecies Differentiation by Metabolomic Signature and Sensory Patterns in Wine”

Alcoholic fermentation is known to be a key stage in the winemaking process that directly impacts the composition and quality of the final product. Twelve wines were obtained from fermentations of Chardonnay must made with twelve different commercial wine yeast strains of Saccharomyces cerevisiae. In our study, FT-ICR-MS, GC-MS, and sensory analysis were combined with multivariate analysis. Ultra-high-resolution mass spectrometry (uHRMS) was able to highlight hundreds of metabolites specific to each strain from the same species, although they are characterized by the same technological performances. Furthermore, the significant involvement of nitrogen metabolism in this differentiation was considered. The modulation of primary metabolism was also noted at the volatilome and sensory levels. Sensory analysis allowed us to classify wines into three groups based on descriptors associated with white wine. Thirty-five of the volatile compounds analyzed, including esters, medium-chain fatty acids, superior alcohols, and terpenes discriminate and give details about differences between wines. Therefore, phenotypic differences within the same species revealed metabolic differences that resulted in the diversity of the volatile fraction that participates in the palette of the sensory pattern. This original combination of metabolomics with the volatilome and sensory approaches provides an integrative vision of the characteristics of a given strain. Metabolomics shine the new light on intraspecific discrimination in the Saccharomyces cerevisiae species.

Microwave-Assisted Hydrodistillation of Hop (Humulus lupulus L.) Terpenes: A Pilot-Scale Study

Interest in essential oils has consistently increased in recent years. Essential oils have a large variety of applications in multiple fields, including in the food, cosmetics and pharmaceutical industries. The volatile fraction (VF) in hops (Humulus lupulus L.) fits within this domain as it is primarily used in the brewery industry for the aromatization of beer, and is responsible for the floral and fruity tones. This work aims to design an optimized extraction protocol of the VF from hops, using microwaves. Microwave-assisted hydrodistillation (MAHD) has been developed to reduce energy and time consumption in lab-scale reactors up to industrial-scale systems. Hops are principally available in three forms, according to a brewery’s applications: (i) fresh (FH); (ii) dried (DH) and (iii) pelletized (PH). In this work, all three forms have therefore been studied and the recovered volatiles characterized by means of GC-MS. The optimized lab-scale MAHD protocol gave the best extraction yield of 20.5 mLVF/kgdry matrix for FH. This value underwent a slight contraction when working at the highest matrix amount (3 kg), with 17.3 mLVF/kgdry matrix being achieved. Further tests were then performed in a pilot reactor that is able to process 30 kg of material. In this case, high yield increases were observed for PH and DH; quadruple and double the lab-scale yields, respectively. In addition, this industrial-scale system also provided marked energy savings, practically halving the absorbed kJ/mLVF.

Py-GC-MS Study on Catalytic Pyrolysis of Biocrude Obtained via HTL of Fruit Pomace

Herein, we proposed new two-stage processing of blackcurrant pomace toward a value-added, hydrocarbon-rich biocrude fraction. The approach consisted of thermochemical liquefaction of a wet-type organic matter into liquid biocrude followed by its upgrade by thermal and catalytic pyrolysis. Particularly, we put effort into investigating the effect of selected catalysts (ZSM-5 and HY zeolite) on the composition of the volatiles released during the pyrolysis of the biocrude. The latter was obtained through liquefaction of the raw material in the binary solvent system of water and isopropanol. The biocrude yield accounted for ca. 45 wt.% of the initial dry biomass. It was a complex mixture of various component groups with an abundant share of oxygenates, especially carboxylic acids and esters. Thereafter, the biocrude was subjected to a pyrolysis study performed by means of the microscale coupled pyrolysis-gas chromatography-mass spectrometry technique (Py-GC-MS). The dominant components identified in the catalytic pyrolytic volatiles were unsaturated hydrocarbons (both cyclic and aliphatic ones) and, to a lesser extent, oxygen and nitrogen compounds. The addition of the ZSM-5 and HY zeolite allowed us to attain the relative total share of hydrocarbons in the volatile fraction equal to 66% and 73%, respectively (in relation to identified compounds). Thus, catalytic pyrolysis over zeolites seems to be particularly prospective due to the promotion of the deoxygenation reactions, which manifested in the noticeable decrease in the share of oxygen compounds in the evolved volatiles. The developed innovative two-stage processing of blackcurrant pomaces allows for obtaining value-added products that could serve as chemicals, biocomponents, and self-contained biofuels as well as bioplastic precursors. The presented contribution brings some new insights into the field of valorization of residuals generated by the food industry sector.

Seasonal Changes in Essential Oil Constituents of Cystoseira compressa: First Report

Marine macroalgae are well known to release a wide spectrum of volatile organic components, the release of which is affected by environmental factors. This paper aimed to identify the essential oil (EO) compounds of the brown algae Cystoseira compressa collected in the Adriatic Sea monthly, from May until August. EOs were isolated by hydrodistillation using a Clavenger-type apparatus and analyzed by gas chromatography coupled with mass spectrometry (GC–MS). One hundred four compounds were identified in the volatile fraction of C. compressa, accounting for 84.37–89.43% of the total oil. Samples from May, June, and July were characterized by a high share of fatty acids (56, 69, and 34% respectively) with palmitic acid being the dominant one, while in the August sample, a high content of alcohols (mainly phytol and oleyl alcohol) was found. Changes in the other minor components, which could be important for the overall aroma and biological activities of the algal samples, have also been noted during the vegetation periods. The results of this paper contribute to studies of algal EOs and present the first report on C. compressa EOs.

Unifloral Autumn Heather Honey from Indigenous Greek Erica manipuliflora Salisb.: SPME/GC-MS Characterization of the Volatile Fraction and Optimization of the Isolation Parameters

For long heather honey has been a special variety due to its unique organoleptic characteristics. This study aimed to characterize and optimize the isolation of the dominant volatile fraction of Greek autumn heather honey using solid-phase microextraction (SPME) followed by gas chromatography-mass spectrometry (GC-MS). The described approach pointed out 13 main volatile components more closely related to honey botanical origin, in terms of occurrence and relative abundance. These volatiles include phenolic compounds and norisoprenoids, with benzaldehyde, safranal and p-anisaldehyde present in higher amounts, while ethyl 4-methoxybenzoate is reported for the first time in honey. Then, an experimental design was developed based on five numeric factors and one categorical factor and evaluated the optimum conditions (temperature: 60 °C, equilibration time: 30 min extraction time: 15 min magnetic stirrer velocity: 100 rpm sample volume: 6 mL water: honey ratio: 1:3 (v/w)). Additionally, a validation test set reinforces the above methodology investigation. Honey is very complex and variable with respect to its volatile components given the high diversity of the floral source. As a result, customizing the isolation parameters for each honey is a good approach for streamlining the isolation volatile compounds. This study could provide a good basis for future recognition of monofloral autumn heather honey.

A New Sesquiterpene Essential Oil from the Native Andean Species Jungia rugosa Less (Asteraceae): Chemical Analysis, Enantiomeric Evaluation, and Cholinergic Activity

As part of a project devoted to the phytochemical study of Ecuadorian biodiversity, new essential oils are systematically distilled and analysed. In the present work, Jungia rugosa Less (Asteraceae) has been selected and some wild specimens collected to investigate the volatile fraction. The essential oil, obtained from fresh leaves, was analysed for the first time in the present study. The chemical composition was determined by gas chromatography, coupled to mass spectrometry (GC-MS) for qualitative analysis, and to flame ionization detector (GC-FID) for quantitation. The calculation of relative response factors (RRF), based on combustion enthalpy, was carried out for each quantified component. Fifty-six compounds were identified and quantified in a 5% phenyl-polydimethylsiloxane non-polar column and 53 compounds in a polyethylene glycol polar column, including four undetermined compounds. The main feature of this essential oil was the exclusive sesquiterpenes content, both hydrocarbons (74.7% and 80.4%) and oxygenated (8.3% and 9.6%). Major constituents were: γ-curcumene (47.1% and 49.7%) and β-sesquiphellandrene (17.0% and 17.9%), together with two abundant undetermined oxygenated sesquiterpenes, whose abundance was 6.7–7.2% and 4.7–3.3%, respectively. In addition, the essential oil was submitted to enantioselective evaluation in two β-cyclodextrin-based enantioselective columns, determining the enantiomeric purity of a minor component (1S,2R,6R,7R,8R)-(+)-α-copaene. Finally, the AChE inhibition activity of the EO was evaluated in vitro. In conclusion, this volatile fraction is suitable for further investigation, according to two main lines: (a) the purification and structure elucidation of the major undetermined compounds, (b) a bio-guided fractionation, intended to investigate the presence of new sesquiterpene AChE inhibitors among the minor components.

Antioxidant Activity of Non-Volatile Lime (Citrus aurantifolia Swingle) Extract

The paper reports the antioxidant activity of a non-volatile fraction of lime processing byproducts from the lime syrup home industry. The activity was measured by spectrophotometry to obtain the 50% inhibition concentration (IC50) using the 2,2- diphenyl-1-picrylhydrazyl (DPPH) method. The sample was extracted by the maceration method with n-hexane, ethyl-acetate, and ethyl-ethanol. The IC50 values of 681 ppm, 458 ppm, and 2,775 ppm were n-hexane, ethyl-acetate, and ethyl-ethanol. The experiments concluded that the ethyl-acetate extract provides the best inhibition value to scavenge free-radicals DPPH. The HPLC and mass spectroscopy were measured to find out the content and group of active compounds. The significant compounds consisted of naringin, poncirin, or neoponcirin, which are known as antioxidant substances. The result shows the potential application of the lime by-products, its volatile fraction, and the nonvolatile fraction, which is the production residue of lime peel. This work can be applied as an alternative to zero-waste lime production, which may benefit the industry and the environment.