Maleinization of Soybean Oil Glycerides Obtained from Biodiesel-Derived Crude Glycerol

Glycerides obtained from the glycerolysis of soybean oil with crude glycerol were acylated with maleic anhydride at 80–100 °C. Both uncatalyzed and catalyzed reactions with 2-methylimidazole (2-MI) were evaluated. Formation of maleated glycerides was confirmed by ¹H-NMR and FTIR analyses. Consumption of maleic anhydride as a function of time was followed by acid value titration. High conversion (ca. 95 %) of hydroxyl groups was obtained at 90 °C in 60 min without catalyst. Under these conditions, a product with 1.9 maleate moieties per glyceride molecule was obtained. Catalyzed reactions afforded lower conversions of hydroxyl groups and lower maleate yields compared to uncatalyzed reactions.     

Design of new solid catalysts for the selective conversion of glycerol

Glycerol is now obtained as a co‐product of biodiesel from renewable raw materials with a dramatically increasing production. It follows that one of the most important breakthroughs is to find new catalytic processes for chemical valorizations. The present paper gives a short overview of selective esterification, transesterification or etherification of glycerol via the use of new heterogeneous catalysts. The selectivity control is mainly the result of the synthesis of mesoporous materials for which acidic or basic properties as well as the surface hydrophilic‐lipophilic balance were optimized.     

Improvement of lecithin as an emulsifier for water-in-oil emulsions by thermalization

The various forms (granular, liquid, gum) of lecithin can be heated under certain conditions of time and temperature to greatly improve their properties as emulsifiers for water-in-oil emulsions. Viscosity, discontinuous phase-holding capacity, stability and water retention were greatly enhanced in emulsions containing thermalized lecithins as the emulsifier compared to those prepared with corresponding amounts of nonthermalized lecithins. The improved emulsification properties of the thermalized lecithins appeared to be due, at least in part, to an increase in diglycerides and free fatty acids resulting from the thermal degradation of phosphatides.     

Glycerolysis of Fatty Acid Methyl Esters: 1. Investigations in a Batch Reactor

The present work focused on the glycerolysis of fatty acid methyl esters. The aim was to develop and test a kinetic model that could be used to reliably simulate different process alternatives for this reaction. A prerequisite was the identification and characterization of the factors that affect the reaction kinetics. Experiments were carried out in a batch reactor with and without forced removal of methanol, which is one of the reaction products. Concentrations of all components in the two-phase system were measured. It was found that the methanol concentration has a strong effect on the reaction rate and equilibrium conversion. Near-complete conversions were obtained by stripping methanol with an inert gas. The glycerol concentration in the ester phase was found to increase as the reaction proceeds, which also accelerates the reaction. Effects of mass transfer on the reaction rate were not found to control the reaction rate under well-agitated conditions. A semi-empirical model was used to simulate the reaction. The results from the semi-empirical model show good agreement with experimental results.     

Glycerolysis of Fatty Acid Methyl Esters: 2. Simulation and Experiments in Continuous Reactors

The glycerolysis of methyl ester was investigated in flow reactors. This reaction represents a liquid two-phase reaction with changing reaction rates in a batch reactor. A semi-empirical model tested earlier with batch reactor data was used to simulate different continuous processes for this reaction. Among the processes simulated, a single continuous-flow stirred tank reactor (CSTR) without recycling was considered most appropriate for experimental implementation, although simulations showed that a faster reaction rate is possible with the application of a CSTR followed by a tubular reactor with certain associated residence times. The CSTR simulations were verified experimentally. A good agreement was found between the experimental data and simulation results.     

环氧乙烷催化水合生产乙二醇工艺技术研究

非催化水合生产乙二醇工艺具有能耗大、成本高的缺点。笔者采用树脂类催化剂进行了环氧乙烷化水合生产乙二醇工艺技术研究,并考察了温度、空速、n(H2O)∶n(EO)、压力及进料方式等工艺条件对催化剂性能的影响,催化剂经过了800 h稳定性考察,研究结果表明,在温度100℃、压力1.0MPa、空速1.5 h-1、n(H2O)∶n(EO)=6.5条件下,不仅具有很稳定的性能,而且环氧乙烷(EO)转化率和乙二醇(EG)选择性最高都可以达到100%。     

Behavior of diglycerides and conjugated fatty acid triglycerides in reverse-phase chromatography

The behavior of conjugated fatty acid triglycerides and diglycerides on reverse-phase chromatography was studied. Trieleostearin is a geometric isomer of trilinolenin. The conjugated double bond arrangement in trieleostearin enhances its hydrophobic interaction with the stationary phase and causes it to be eluted later than trilinolenin. In separation of “critical pairs” of tri- and diglycerides, diglycerides elute later than triglycerides due to the longer fatty acid constituent. Position isomers of 1,2- and 1,3-diglycerides can be separated by reverse-phase high-performance liquid chromatography.     

Catalytic destruction of malathion by metallomicelle layers

Two micellized Cu(II) and Fe(III) ion complexes were synthesized and found to possess good catalytic activity in the cleavage of the malathion/dupric (ferric) complex thionate ester. The complexes form metallomicelles, which bind the substrate by coordinating with the thionate sulfur in the malathion (which is chemically similar to the nerve agent sarin). Possible reasons for the rate acceleration include enhanced electrophilicity of the micellized metals, enhanced surface activity, and the recognized ability of cationic micelles to accelerate the cleavage of the thionate ester. The results of kinetic data (half-life times) for malathion degradation were 13.7 and 8.3 min in the presence of Cu(II) and Fe(III) metallomicelle layers, respectively.     

Polyurethane foams based on crude glycerol-derived biopolyols: One-pot preparation of biopolyols with branched fatty acid ester chains and its effects on foam formation and properties

Environmentally friendly biopolyols have been produced with crude glycerol as the sole feedstock using a one-pot thermochemical conversion process without the addition of extra catalysts and reagents. Structural features of these biopolyols were characterized by rheology analysis. Rigid polyurethane (PU) foams were obtained from these crude glycerol-based biopolyols and the foaming mechanism was explored. Investigations revealed that partial carbonyl groups hydrogen-bonded with N–H were replaced by aromatic rings after the introduction of branched fatty acid ester chains in the “urea rich” phase, and that distinct microphases had formed in the foams. Studies showed that branched fatty acid ester chains in the biopolyols played an important role in reducing the degree of microphase separation and stabilizing bubbles during foaming processes. PU foams with thermal conductivity comparable to commercial products made from petroleum-based polyols were obtained. These studies show the potential for development of PU foams based on crude glycerol, a renewable resource.     

Conversion of oils to monoglycerides by glycerolysis in supercritical carbon dioxide media

Glycerolysis of soybean oil was conducted in a supercritical carbon dioxide (SC-CO₂) atmosphere to produce monoglycerides (MG) in a stirred autoclave at 150–250°C, over a pressure range of 20.7–62.1 MPa, at glycerol/oil molar ratios between 15–25, and water concentrations of 0–8% (wt% of glycerol). MG, di-, triglyceride, and free fatty acid (FFA) composition of the reaction mixture as a function of time was analyzed by supercritical fluid chromatography. Glycerolysis did not occur at 150°C but proceeded to a limited extent at 200°C within 4 h reaction time; however, it did proceed rapidly at 250°C. At 250°C, MG formation decreased significantly (P<0.05) with pressure and increased with glycerol/oil ratio and water concentration. A maximum MG content of 49.2% was achieved at 250°C, 20.7 MPa, a glycerol/oil ratio of 25 and 4% water after 4 h. These conditions also resulted in the formation of 14% FFA. Conversions of other oils (peanut, corn, canola, and cottonseed) were also attempted. Soybean and cottonseed oil yielded the highest and lowest conversion to MG, respectively. Conducting this industrially important reaction in SC-CO₂ atmosphere offered numerous advantages, compared to conventional alkalicatalyzed glycerolysis, including elimination of the alkali catalyst, production of a lighter color and less odor, and ease of separation of the CO₂ from the reaction products.     

Preferential degradation of noncholine phosphatides in soybean lecithin by thermalization

Purified soybean lecithin and the gum derived from soybean oil processing were heated separately in bulk at 125 to 200°C for 60 min, or at 175°C for 30, 60, 90 and 120 min, and the products were analyzed by thin-layer chromatography and high-performance liquid chromatography. It was found that the noncholine phosphatides are preferentially degraded relative to phosphatidylcholine, and that these phosphatides are broken down in the order phosphatidyl-ethanolamine (PE)>phosphatidylinositol (PI)>phosphatidic acid (PA) with increasing temperature. At 175°C, the heating time required to degrade the noncholine phosphatides was between 30 and 60 min. Diglycerides were the principal products of thermalization at 77% of the total material, indicating that the 3-phosphoester linkage is the most heat-labile portion of the noncholine phosphatide molecules. Cleavage of the fatty acids from positions 1 and 2 of the phosphatides was minimal, as indicated by the relatively low amount of free fatty acids (8% of the total) when the lecithin was heated at 180°C for 90 min. The appearance of brown discoloration, characteristic of heated lecithin, coincided mainly with the decomposition of PE.     

Efficient Synthesis of α-Monoglycerides via Solventless Condensation of Fatty Acids with Glycerol Carbonate

Highly pure α-monoglycerides (5a–e) were successfully prepared in high yields by the condensation of fatty acids such as lauric, myristic, palmitic, stearic and oleic (2a–e) with glycerol carbonate (4-hydroxymethyl-1,3-dioxolan-2-one) (1) in the presence of triethylamine as catalyst. Reaction conditions and spectroscopic identification of products will be presented in this article.     

环氧乙烷催化水合生产乙二醇动力学研究

在温度为70~105℃,压力为0.7~1.5 MPa,n(H2O)∶n(环氧乙烷)=6~8的条件下,以阴离子交换树脂为催化剂,研究了环氧乙烷(EO)催化水合生产乙二醇(EG)反应动力学特性,建立了动力学模型.研究结果表明,EG的生成速率对EO浓度具有一级反应特征.对试验数据进行了回归,得到了动力学模型参数,其反应活化能为42.4 kJ/mol,指前因子为5.48×106h-1。回归数据的线性相关系数均大于0.96,说明该模型能够充分体现反应特征。     

Enzymatic glycerolysis of soybean oil

Enzymatic glycerolysis of soybean oil was studied. Of the nine lipases that were tested in the initial screening, Pseudomonas sp. resulted in the highest yield of monoglycerides. Lipase from Pseudomonas sp. was further studied for the influence of temperature, thermal stability, enzyme/oil ratio, and glycerol/oil ratio. A full factorial optimization approach was performed. The following conditions were tested over the specified ranges: temperature (30–70°C), thermal stability (30–70°C), enzyme/oil ratio (0.05–0.2 g enzyme/10 g oil), glycerol/oil ratio (1:1–3:1 glycerol/oil molar ratio) and 1 h reaction time. The stability of the enzyme at the reaction temperature was also incorporated as a separate variable. At temperatures above 40°C enzyme denaturation offset the higher activity. The optimal conditions were selected to be the basis for a continuous process: 40°C, a glycerol/oil molar ratio of 2:1, and an enzyme/oil ratio of 0.1 g enzyme/10 g oil. A definition for glycerolysis activity was adopted. The glycerolysis activity (1 GU) was defined as the amount of enzyme necessary to consume 1 μmol of substrate (glycerol and oil) per minute. This research is intended to explore the reaction parameters that are important in a continuous enzymatic glycerolysis process.     

Glycerolysis of Crude Methyl Esters with Crude Glycerol from Biodiesel Production

Glycerolysis of crude fatty acid methyl esters (FAME) with crude glycerol derived from biodiesel production was performed. The reaction was accomplished at temperatures ranging between 160 and 200 °C and molar ratios of FAME to glycerol ranging between 1.5 and 3.0. Increasing the temperature improved the formation rate of monoglycerides (MG) and diglycerides (DG). However, increasing both the temperature and the molar ratio of glycerol to FAME diminished the formation of MG. Best results (43 % MG and 26 % DG in 10 min) were obtained at 200 °C using the lowest concentration of glycerol. The effects of soap and NaOH present in crude glycerol were controlled by carrying out the reaction with pure glycerol. In comparison with NaOH-catalyzed reactions, soap-catalyzed reactions resulted in a slower formation rate of products. However, soap-catalyzed reactions were less prone to secondary reactions, affording maximum yields of MG and DG, which were higher than those obtained with NaOH-catalyzed reactions at 180 and 200 °C.     

Micro-fiber elements as perfusive catalysts or in catalytic mixers: Flow, mixing and mass transfer

The flow, mixing and mass transfer in a catalytic stirrer containing catalyst coated porous micro-fiber elements, based on a concept introduced by Moulijn, were studied in a lab-scale reactor with 13 samples of materials with fiber diameters from 8 to 35 μm and porosity values between 0.60 and 0.90. Pressure drop in these sintered metallic fiber materials was shown to follow a modified Kozeny–Carman equation:

When rotating in the reactor, the flow through the fiber mats can be estimated from

where α_D is a drag coefficient of around 2.5. Flow through the catalyst in an operational stirrer can be adjusted over several orders of magnitude by manipulating parameters, such as rotational speed, dimension of the fiber stack and its material characteristics.Mass transport between fibers and the liquid flow through fiber stacks follows:

εSh=0.47Re^1/2Sc^1/3