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In this study, we tested several amino acids as eco-friendly inhibitors against corrosion of mild steel by used cooking oils (UCOs). The corrosion inhibition was studied by immersing mild steel rods in the UCOs and reference fresh rapeseed and olive oils mixed with amino acids. The immersion tests were conducted at room temperature for three days. The roles of water and bio-oil preservatives (formic and propionic acids) in the corrosion were explored. The mild steel surface morphology changes after exposure to the oils were analyzed with a scanning electron microscope coupled with an energy dispersive spectroscope (SEM-EDS). The concentration of iron dissolved in the oils was determined with a spectrophotometer. A thick layer was analyzed on the surfaces of the mild steel rods immersed in the oils containing formic or propionic acid and water. This layer provided a minor barrier against corrosion. According to the Fourier transform infrared spectrometer (FTIR) analytical results, the layer consisted of an acid and iron salt mixture. All the tested amino acids decreased the concentration of dissolved iron in the UCOs; particularly, cationic amino acids, L-lycine and L-arginine showed adequate corrosion inhibition properties at low concentrations. [ABSTRACT FROM AUTHOR]

The first goal of this study was to determine the polysaccharide composition of Pinus brutia wood and how this composition changes during kraft pulping. The second goal was to determine the effect of the stem height on chemical composition. The content of hemicelluloses was about 280 mg/g at a height of 1.3 m, whereas the content was about 300 mg/g at the top of the stem (4.3 m). The main sugars in the wood of P. brutia were mannose (102 mg/g dw), xylose (69 mg/g dw), and glucose (44 mg/g dw). During kraft pulping, 52% of the total hemicelluloses were degraded. Glucose and xylose were more stable than mannose. The total amounts of cellulose in the wood and in the kraft pulp of P. brutia were determined to be 330 mg/g and 661 mg/g, respectively, at 1.3 m. [ABSTRACT FROM AUTHOR]

Background: In the production of biofuels from lignocellulosic material, biocrude plays a key role. The present work deals with the biocrude production through hydrothermal liquefaction (HTL) of birch wood in supercritical ethanol over 5 wt% Fe‐H‐Beta‐150 (SiO2 to Al2O3 ratio of 150) or 5 wt% Fe‐SiO2 catalyst. Results: The liquid and solid products were characterized with various analytical techniques such as gas chromatography mass spectrometry (GC–MS), gas chromatography with a flame ionization detector (GC‐FID), size exclusion chromatography (SEC), inductively‐coupled plasma mass spectrometry (ICP‐MS), powder X‐ray diffraction (p‐XRD), scanning electron microscopy (SEM), and solid‐state carbon‐13 magic angle spinning nuclear magnetic resonance (13C‐MAS‐NMR), respectively. The results revealed that 5 wt% Fe‐H‐Beta‐150, a strongly Brønsted acidic catalyst, enhanced the biocrude formation when compared with a non‐acidic 5 wt% Fe‐SiO2 catalyst. Hemicellulose and lignin degradation occurred resulting in formation of mainly sugars, acids‐esters and phenolic compounds in the liquid phase. The gaseous atmosphere of hydrogen also enhanced the degradation of biomass. The biocrude yield from birch was 25 wt% over 5 wt% Fe‐H‐Beta‐150. The Brønsted acidic catalyst gave higher dissolution efficiency and its clear catalytic effect was observed in comparison to non‐acidic 5 wt% Fe‐SiO2. The degradation level of lignin in the presence of 5 wt% Fe‐H‐Beta‐150 was high 68 wt% aromatic products were formed, while only 38 wt% was obtained with 5 wt% Fe‐SiO2. Conclusions: Hydrogen atmosphere enhances the fractionation of birch wood when compared to argon atmosphere. The 5 wt% Fe‐H‐Beta‐150 catalyst enhanced very strongly the degradation of hemicellulose and lignin in biomass to sugars and acid‐esters as well as phenolic compounds, respectively, compared to the non‐acidic 5 wt% Fe‐SiO2 catalyst. © 2019 Society of Chemical Industry [ABSTRACT FROM AUTHOR]

Betulin (90–94%) was extracted from birch with a non-polar solvent and recrystallized from 2-propanol. Liquid-phase oxidation of betulin aimed at obtaining its biologically active oxo-derivatives (betulone, betulonic and betulinic aldehydes), exhibiting e.g. antitumor, anti-inflammatory, antiparasitic, anticancer and anti-HIV properties, was demonstrated for the first time over gold-based catalysts. Gold was deposited on pristine TiO2 and the same support modified with ceria and lanthana, followed by pretreatment with a H2 or O2 atmosphere. The catalysts were characterized by XRD, BET, ICP, TEM, XPS, DRIFT CO, TPD of NH3 and CO2 methods. The nature of the support, type of modification and the pretreatment atmosphere through the metal–support interactions significantly influenced the average particle size of gold, its distribution and the electronic state of gold, as well as the acid–base properties and, thereby, the catalytic performance (activity and selectivity) in betulin oxidation. Au/La2O3/TiO2 pretreated in H2 displayed the highest catalytic activity in betulin oxidation among the studied catalysts with selectivities to betulone, betulonic and betulinic aldehydes of 42, 32 and 27%, respectively, at 69% conversion. Side reactions resulting in oligomerization/polymerization products occurred on the catalyst surface with the participation of strong acid sites, diminishing the yield of the desired compounds. The latter was improved by adding hydrotalcite with the basic properties to the reaction mixture containing the catalyst. Kinetic modelling through numerical data fitting was performed to quantify the impact of such side reactions and determine the values of rate constants. [ABSTRACT FROM AUTHOR]

The aim of the study was to find appropriate non-chlorinated solvent systems for the extraction and separation of pure pinosylvin (PS) and pinosylvin monomethylether (PSMME) from Scots pine/Norway spruce wood residues. The extraction was performed in a pressurized solvent extractor and the purification and isolation of pure substances was done by flash chromatography. More precisely, pure PS was isolated via sequential flash chromatography in two repetitions in the gradient mode of the mobile phase, with cylcohexane (CX) and ethylacetate (EtOAc), beginning with 100% CX and ending up with 100% EtOAc. The extractives were qualitatively and quantitatively analyzed in terms of PS and PSMME contents by gas chromatography-flame ionization detector (GC-FID), gas chromatography-mass spectrometry (GC-MS), high-performance liquid chromatography (HPLC) and proton nuclear magnetic resonance (1H-NMR) spectroscopy. [ABSTRACT FROM AUTHOR]

Abstract: Vanillin hydrodeoxygenation was investigated using Pt/C catalyst in the temperature and total pressure ranges of 80-200 °C and 20-30 bar in several solvents, such as tetrahydrofuran, 2-propanol, water and in solventless conditions using 1:1 mass ratio of vanillin to guaiacol. The results revealed that the rate increased with increasing solvent polarity as follows: tetrahydrofuran < 2-propanol < water. The main product was p-creosol with 66% selectivity at complete vanillin conversion in HDO under 30 bar total pressure at 100 °C after 4 h using water as a solvent. In a solventless experiment with 1:1 mass ratio of vanillin-guaiacol as a feedstock only vanillin was transformed to p-creosol with 91% conversion in 4 h at 200 °C under 30 bar total pressure, while guaiacol did not produce any HDO products. Both thermodynamic analysis and kinetic modelling were performed. Vanillin hydrodeoxygenation resulted in formation of p-creosol over Pt/C catalyst using an optimum vanillin initial concentration in water solution. From the industrial point of view vanillin hydrodeoxygenation proceeded rapidly giving high yields of p-creosol in solventless hydrodeoxygenation of vanillin-guaiacol mixture, while guaiacol was not deoxygenated.Graphical Abstract: [ABSTRACT FROM AUTHOR]

The lipophilic and hydrophilic extractives in the sapwood (sW) and heartwood (hW) of stems from Pinus halepensis Mill and Eucalyptus camaldulensis Dehnh trees grown in the north of Algeria were analyzed. The extraction of dried samples was carried out in an accelerated solvent extractor (ASE). The lipophilic substances were first extracted with n-hexane and then the hydrophilic ones with acetone/water. The extractives were analyzed by gas chromatography-flame ionization detection (GC-FID), GC-mass spectroscopy (MS) and high-performance size-exclusion chromatography (HPSEC). The largest amount of lipophilic extractives (≈13.4 mg g-1) was observed in the hW of P. halepensis, while the hW of E. camaldulensis contained the largest amount of hydrophilic extractives (≈116.3 mg g-1). Lipophilic extractives are mainly composed of oleoresins (resin acids, terpenes), fats (fatty acids, glycerides, steryl esters, sterols) and waxes (fatty alcohols). Hydrophilic extractives are composed of polyphenols (stilbenes, flavanols), sugars (monosaccharides) and sugar alcohols (cyclic polyols). The main identified lipophilic extractives are resin acids in pine and glycerides in eucalypt. The main identified hydrophilic extractives are cyclic polyols in pine and flavanols and monosaccharides in eucalypt. The total content of extractives is higher in hW than in sW. [ABSTRACT FROM AUTHOR]

Sugarcane bagasse is abundant agro-industrial waste that can be potentially utilized as a source of valuable compounds and biopolymers. In the present study, sugarcane bagasse from Brazil was fractionated employing an environmentally friendly hydrotropic process. Several treatments were carried out at 150 and 170 °C and dwell times of 60 and 120 min using unmodified 30% hydrotropic solutions as well as the solutions acidified with formic acid. The major produced fraction was cellulose pulp obtained with the yield of 44–67% (bagasse based) and the cellulose content of 60–92%. Lignins dissolved during the treatments were isolated from the spent solutions by dilution with water and filtration. The yields of the lignins were 11.8–14.7% (bagasse based) and their purity ranged from 88 to 94%. Generally, the purity of both fractions and the yield of lignin were higher at more severe process conditions. However, the more severe conditions resulted in lower average molar masses of the lignins and lower intrinsic viscosity values of the cellulose fractions. The composition of the spent solutions also varied with the treatment conditions, and, besides the lignins, they contained different amounts of dissolved hemicelluloses, sugar monomers, furfural and acetic and formic acids. The results of the present study showed that the hydrotropic process could be successfully applied for the valorization of sugarcane bagasse by its fractionation into lignin, cellulose and other products. [ABSTRACT FROM AUTHOR]

BACKGROUND Hydrodeoxygenation ( HDO) of Chlorella algal oil extracted with supercritical hexane and stearic acid as a model compound was investigated over several supported Ni and Mo2N-MoO2 catalysts in a semibatch reactor at 300 °C under 30 bar in the presence of hydrogen. RESULTS The results showed that all catalysts were very active in HDO of stearic acid. With crude algal oil, a maximum conversion of lipids of 35% was found with an acidic Ni- HY-80 zeolite catalyst after 360 min. The main products in algal oil HDO were fatty acids; whereas maximally only 7% hydrocarbons were formed with Ni- HY-80. The main hydrocarbon products were formed via decarbonylation, as the hydrogenation/dehydration route was suppressed. CONCLUSIONS Hydrodeoxygenation of crude Chlorella algal oil was demonstrated over nickel supported on beta zeolite and with a molybdenum oxide-nitride catalyst. Strong catalyst deactivation occurred for the former catalyst, whereas the latter retained its activity. © 2016 Society of Chemical Industry [ABSTRACT FROM AUTHOR]

Hemicellulose O-acetyl-galactoglucomannan (GGM) is the main noncellulosic water-soluble polysaccharide in the coniferous softwood Norway spruce, consisting of anhydro-galactose, -glucose, and -mannose. Acid hydrolysis of GGM has been studied in a continuous tube reactor to obtain these sugars under industrially relevant conditions. The reaction was performed under atmospheric pressure at 90°C and 95°C, and hydrochloric acid (HCl) served as catalyst. The influence of the reaction parameters, such as acid concentration (pH), temperature, concentration of the substrate, as well as catalyst and reactant flow rates, has been studied on the conversion efficiency and product distribution. Continuous production of monomeric sugars was achieved without formation of low-molecular by-products. The GGM conversion was high with HCl as catalyst, at 95°C, and a pH of 0.3. The main hydrolysis products were mannose, glucose, and galactose monomers. Minor amounts of sugar dimers were detected among the products. The experimental results are described with a laminar flow model for the continuous reactor. [ABSTRACT FROM AUTHOR]

Arbutus andrachne and Platanus orientalis grow naturally in Turkey. They do not occur in stands but can be seen as solitary trees. A. andrachne is seen in coastal parts of Anatolia, whereas P. orientalis can be found from west to the east of Turkey, mostly in river banks. Lipophilic extractives, hydrophilic extractives, and suberin monomers from Arbutus andrachne and Platanus orientalis bark was analyzed by chromatography. The total amount of lipophilic extractives was higher in P. orientalis (8.55 mg/g). However, the total amount of hydrophilic extractives had a bigger proportion, 100.86 mg/g, in A. andrachne bark. Dioic and hydroxy acids were the dominant group in the suberin monomers of both species of bark. Acid 1,18-dioic-18:0 and acid 18-hydroxy-18:1 were determined as the main compounds of suberin monomers in both samples. In addition, total amount of suberin monomers was determined to be 11.36 mg/g in A. andrachne and 15.95 mg/g in P. orientalis bark. [ABSTRACT FROM AUTHOR]

In this work, the brown algae Macrocystis pyrifera were pretreated with dilute sulfuric acid, water and three different types of ionic liquids (ILs): 1-ethyl-3-methylimidazolium acetate ([EMIM][OAc]), 1,5-diazabicyclo[4.3.0]non-5-ene acetate ([DBNH][OAc]) and 1,8-diazabicyclo-[5.4.0]–undec-7-ene–sulfurdioxide–monoethanolamine (DBU–MEA–SO 2 –SIL), to disassemble the complex polysaccharide structure. After each pretreatment procedure, enzymatic saccharification was performed to release the monosaccharides. The main building blocks of M. pyrifera were processed by derivatization via acid methanolysis and subjected to gas chromatographic analysis. It was found that the main constituents were alginate (60.6 wt.%) and cellulose (22.6 wt.%) of total carbohydrate content. The degradation of alginate requires the action of alginate lyase and oligoalginate lyase, which hydrolyze the main chain in a synergistic mechanism releasing uronic acid (unsaturated uronate). Upon saccharification of cellulose, cellulases and β-glucosidase were used allowing the release of glucose. It was found that the best pretreatment strategy for M. pyrifera consisted of a pretreatment with 2 vol.% sulfuric acid, followed by saccharification of cellulose with a mixture of cellulases at pH 5.2 for 4 h at 50 °C or by saccharification of alginate with the enzyme lyase/oligoalginate lyase at pH 7.5 for 2 h at 37 °C. The process resulted in a release of 68.4 wt.% of glucose (55.74 ± 0.05 mg glucose/g algae) whereas in the case of alginate 85.8 wt.% of uronic acid (193.7 ± 10.6 mg uronic acid/g algae) was released. To the best of our knowledge this is the first time that saccharification of both cellulose and alginate from brown algae is reported. [ABSTRACT FROM AUTHOR]

BACKGROUND In the lube oil re-refining industry silicon, coming mainly from antifoaming agents, is recognized to be a contaminant generating undesired solid deposits. The behavior of the hydrogen-terminated model compound, tetramethyldisiloxane, under base-catalyzed conditions was investigated at 100 °C in dodecane as the solvent with sodium siloxanolate as an alkali agent. RESULTS The use of sodium siloxanolates led to high reaction rates and selectivity to the liquid products. Experiments with an industrially relevant silicon-containing substrate, namely silicone-based antifoam agent showed that its transformation in the presence of 33 wt% aqueous solution of sodium hydroxide resulted in 80% yield of solid sodium siloxanolates, whereas, when sodium siloxanolate was used as an initial alkali agent, no solid products were formed. CONCLUSIONS Experimental results demonstrated that under alkali treatment conditions silicon-containing species existing in real industrial feedstock undergo transformation reactions, with formation of solid sodium siloxanolates. It was found that the use of sodium siloxanolate as an alkali agent could significantly increase the rate of polydimethylsiloxane depolymerization reaction and completely eliminate formation of the undesired solids under industrially relevant conditions. © 2014 Society of Chemical Industry [ABSTRACT FROM AUTHOR]

Amidation of renewable feedstocks, such as fatty acids, esters, and Chlorella alga based biodiesel, was demonstrated with zeolites and mesoporous materials as catalysts and ethanolamine, alaninol, and leucinol. The last two can be derived from amino acids present in alga. The main products were fatty alkanol amides and the corresponding ester amines, as confirmed by NMR and IR spectroscopy. Thermal amidation of technical-grade oleic acid and stearic acid at 180 °C with ethanolamine were non-negligible; both gave 61 % conversion. In the amidation of stearic acid with ethanolamine, the conversion over H-Beta-150 was 80 % after 3 h, whereas only 63 % conversion was achieved for oleic acid; this shows that a microporous catalyst is not suitable for this acid and exhibits a wrinkled conformation. The highest selectivity to stearoyl ethanolamide of 92 % was achieved with mildly acidic H-MCM-41 at 70 % conversion in 3 h at 180 °C. Highly acidic catalysts favored the formation of the ester amine, whereas the amide was obtained with a catalyst that exhibited an optimum acidity. The conversion levels achieved with different fatty acids in the range C12-C18 were similar; this shows that the fatty acid length does not affect the amidation rate. The amidation of methyl palmitate and biodiesel gave low conversions over an acidic catalyst, which suggested that the reaction mechanism in the amidation of esters was different. [ABSTRACT FROM AUTHOR]

The extraction of oils based on animal fat and vegetable oil from two types of spent bleaching earths, namely from the acidic sepiolite and the nonacidic palygorskite, was investigated by the Soxhlet method with hexane as a solvent. The yields of oil were independent of the feedstock, whereas a much lower oil yield was obtained with palygorskite exhibiting also a smaller surface area as compared to sepiolite which provided a higher yield. The glyceride compositions were very similar in bleached and extracted oils, while slightly lower melting and crystallization energies were determined by differential scanning calorimetry for the extracted oils bleached with acidic clay indicating minor hydrolysis of triglycerides. [ABSTRACT FROM AUTHOR]

Various lignin determination methods have been applied to hemicellulose-rich wood extracts obtained after pressurized hot-water extraction (PHWE) and membrane ultrafiltration (UF). In focus were the chlorine number (Cl no.) method, the acetyl bromide method, and the four modifications of the Klason lignin determination, such as the KCL, TAPPI, LAP, and Goldschmid methods. The furfural (F) and hydroxymethylfurfural (HMF) concentrations in the acid hydrolysates were also determined. The mass balances of the fraction were calculated with respect to the contents of dry solids and lignin, including the acid-soluble lignin. The reliability of the methods was evaluated based on the lignin mass balances and the gross chemical composition of the extracts. Although the results were dependent on the method applied, the lignin mass balance calculations yielded similar results in general. [ABSTRACT FROM AUTHOR]

The extraction conditions have been evaluated concerning the recovery of specific polyphenols from Scots pine (Pinus sylvestris) knots by means of an accelerated solvent extractor. The composition of the extracts was determined by gas chromatography, gas chromatographymass spectrometry, and high-performance size-exclusion chromatography. The main phenolic compounds are the stilbenes pinosylvin and its monomethyl ether and the lignan nortrachelogenin (NTG), and their amounts vary a lot from sample to sample. The sequential extraction with a nonpolar solvent as a first step for removing the lipophilic compounds was the most efficient approach for the recovery of both pinosylvins and NTG. For food applications, hot water and 85% aqueous ethanol were good solvents for the production of the substances in focus. An industrial knotwood sample from a pulp mill was sequentially extracted with cyclohexane and ethanol/water (95:5) in a large-scale Soxhlet equipment. The results show that the industrial production of pinosylvins and NTG from knots is feasible. [ABSTRACT FROM AUTHOR]

ABSTRACT Polysaccharides are biorenewable and biodegradable starting materials for the development of functional materials. The synthesis of a monofunctional macroinitiator for single electron transfer-living radical polymerization was successfully developed from a wood polysaccharide- O-acetyl galactoglucomannan (GGM) using a beforehand synthesized amino-functional α-bromoisobutyryl derivative applying reductive amination. The GGM macroinitiator was employed to initiate a controlled radical polymerization of [2-(methacryloyloxy)ethyl]trimethylammonium chloride (MeDMA), methyl methacrylate (MMA), and N-isopropylacrylamide (NIPAM) using Cu0/Me6-Tren as a catalyst. The either charged or amphiphilic GGM- b-copolymers with different chain lengths of the synthetic block were successfully synthesized without prior hydrophobization of the GGM chain and dimethyl sulfoxide (DMSO) or DMSO/water mixtures were used as solvents. This novel synthetic approach may find untapped potentials particularly for the development of polysaccharide-based amphiphilic additives for cosmetics or paints and for the design of novel temperature or pH responsive polymers with such potential applications as in drug delivery systems or in biocomposites. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 5100-5110 [ABSTRACT FROM AUTHOR]

Highlights: [⿢] Pinus pinaster wood samples were extracted with near and supercritical CO2. [⿢] The effect of pressure (10⿿25MPa), temperature (30⿿50°C) and ethanol as co-solvent was assessed. [⿢] Under selected conditions (25MPa, 50°C, 10% ethanol), 4wt% was extracted. [⿢] One gram of extract contained 76mg of GAE and was equivalent to 0.3g Trolox. [⿢] Selected extracts contained 30% resin acids and 10% of the sum of flavonoids, lignans, stilbenes and juvabiones. [ABSTRACT FROM AUTHOR]

Used cooking oils (UCOs) have a high potential as renewable fuels for the maritime shipping industry. However, their corrosiveness during storage and usage are some of the concerns yet to be investigated for addressing compatibility issues. Thus, the corrosion of steels and copper exposed to the UCOs was studied through the immersion of metal rods for different periods. The changes on the rod surfaces were analyzed with a scanning electron microscope (SEM). After the immersion, the copper concentration dissolved in the bio-oils was measured using inductively coupled plasma-optical emission spectrometry (ICP-OES). The free fatty acids and glycerides were analyzed using gas chromatography with flame ionization detection (GC-FID). The acid number (AN), water concentration, as well as density and kinematic viscosity of the bio-oils were determined with standard methods. The UCOs with the highest water content were corrosive, while the oils with lower water concentrations but higher ANs induced lower corrosion. After mixing two different UCOs, the metal corrosion decreased with an increasing concentration of the oil with lower corrosive properties. The lower corrosion properties were most likely due to the monounsaturated fatty acids, e.g., oleic acid in oils. These acids formed a barrier layer on the rod surfaces, thereby inhibiting the permeation of oxygen and water to the surface. Even adding 0.025 wt% of tert-butylamine decreased the corrosivity of UCO against polished steel rod. The results suggested that mixing several oil batches and adding a suitable inhibitor reduces the potential corrosive properties of UCOs. [ABSTRACT FROM AUTHOR]