柴油溶剂中脂肪酶催化高酸值废油脂酯化制备生物柴油

采用0＃柴油作为反应溶剂,利用固定化脂肪酶催化高酸值废油脂与甲醇酯化反应制备生物柴油。来源于Candida antarctica的固定化脂肪酶Novozym435在0＃柴油溶剂中具有极高的催化活性。以酸价高达157×10-3的废油脂为原料,废油脂质量比10%的Novozym435,甲醇与废油脂初始摩尔比2∶1,0＃柴油与废油脂质量比5∶1,摇床摇速170r/min,50℃下反应2h甲酯化率可达95.10%。0＃柴油作为反应溶剂有效地溶解了高酸值废油脂和甲醇,降低了反应体系的黏度和消除了甲醇对Novozym435的负面影响,提高了Novozym435的稳定性。同时,0＃柴油溶剂对未脱胶废油脂中残留的对脂肪酶有害的磷脂等胶类物质具有一定的稀释作用。该工艺省却了溶剂蒸馏的繁琐工序,直接得到脂肪酸甲酯和石化柴油的混合燃料。     

Structure and properties of partially epoxidized soybean oil

In the present study, the characteric-structure relationship of epoxidized soybean oils (ESO) with various degrees of epoxidation has been investigated. FTIR analysis was used to identify the relative extent of epoxidation of the samples during the epoxidation reaction. The viscosities of ESO were much higher than that of the raw oil, viscosity increased with degree of epoxidation. The viscous-flow activation energy of ESO was determined to be higher than that of the raw oil (20.72 to 77.93% higher). Thermogravimetry analysis (TG) of ESO was used to investigate the thermodynamic behavior of the samples. With increasing degree of epoxidation, the thermal stability of the samples initially decreased, then increased at the final reacting stage. Differential scanning calorimeter (DSC) indicated that the melting point of ESO was higher than that of soybean oil. Gel permeation chromatography (GPC) indicated the molecular mass of the samples increased initially, then decreased, with an increase in the extent of epoxidation.     

Chemo-Enzymatic Epoxidation of <Emphasis Type="Italic">Lallemantia Iberica</Emphasis>Seed Oil: Process Development and Economic-Ecological Evaluation

The chemo-enzymatic epoxidation of Lallemantia iberica seed oil (LISO), a novel plant oil characterized by its exceptional high content of alpha-linolenic acid (>?60%), was developed using an immobilized lipase from Pseudozyma antarctica and hydrogen peroxide as oxidant. A statistical approach was used to study the effect of enzyme amount, temperature, time, and solvent amount on the oxirane oxygen content obtained during epoxidation. An oxirane oxygen content of 8.6 ± 0.2% corresponding to a yield of 82% was obtained under optimized conditions that were identified to be at an enzyme load of 8.2 g/mol of double bonds, a solvent amount of 56.4 wt.%, a temperature of 33 °C, and an incubation time of 17 h. In addition, the experimental investigation was combined with a techno-economic and ecological assessment gaining detailed information regarding cost structure and environmental impact for the chemo-enzymatic epoxidation of the novel plant oil.     

Synthesis and Thermal Properties of Epoxidized Vegetable Oil

Summary: The novel potential epoxy resins, epoxidized soybean oil (ESO) and epoxidized castor oil (ECO), were synthesized and characterized. The cationic polymerization of ESO and ECO with a latent thermal catalyst, N‐benzylpyrazinium hexafluoroantimonate (BPH), was initiated at 80 and 50 °C, respectively. The cured ECO samples showed a higher T_g and lower coefficient of thermal expansion than those of ESO, due to the higher intermolecular interaction in the ECO/BPH system.

Relationships between ESO or ECO conversion and temperature in the polymerization with 1 wt.‐% BPH for 2 h.     

Carbonyldiimidazole‐accelerated efficient cure of epoxidized soybean oil with dicyandiamide

This study investigates the curing of epoxidized soybean oil (ESO) using dicyandiamide (DICY) and combinations of DICY with several accelerators as curing agents. The differential scanning calorimetry (DSC) results indicated that carbonyldiimidazole (CDI) is a highly efficient accelerator for the ESO‐DICY curing system. CDI accelerated ESO‐DICY curing system can gel within a short period of 13 min at 190 °C. The activation energies of the ESO‐DICY curing systems with and without CDI are 95 and 121 kJ mol^?1, respectively. Similar acceleration effect was observed in the ESO‐diglycidyl ether of biphenyl A (DGEBA) blending formulations. When the molar part of the glycidyl epoxy groups of DGEBA was equal to the internal epoxy groups of ESO in the mixture, gelation of the DICY curing system accelerated by CDI was achieved in 3 min at 160 °C. Furthermore, the DSC results with FTIR analysis suggest that the stoichiometric curing molar ratio was 3 ESO epoxy units per 1 DICY molecule. Two epoxy units reacted with DICY to give secondary alcohols, while the other one linked to the nitrile group. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 375–382     

席夫碱钼(Ⅵ)配合物的制备及催化大豆油环氧化

以水杨醛和邻氨基酚为起始原料, 合成了N-亚水杨醛基-2-氨基苯酚配体(H₂SAP); H₂SAP与乙酰丙酮钼的无水乙醇溶液反应, 制得席夫碱钼(Ⅵ)配合物MoO₂(SAP)(EtOH); 采用元素分析、红外光谱、紫外光谱、¹H NMR及热重分析对配合物进行了表征. 以MoO₂(SAP)(EtOH)为催化剂, 研究了其催化合成环氧大豆油的催化性能, 考察了氧源种类、反应温度、反应时间及溶剂/助剂等因素对环氧化反应的影响. 结果表明, 以65%(质量分数)叔丁基过氧化氢(65% TBHP)为氧源, 在80℃时反应4 h, 转化率和选择性分别为43.0%和67.2%, MoO₂(SAP)(EtOH)在催化体系中表现出强烈的助剂效应, 当加入强给电子配体咪唑时, 环氧产率显著降低. 同时对该配合物催化环氧化机理进行了初步探讨.     

Bio‐based nanocomposites composed of photo‐cured epoxidized soybean oil and supramolecular hydroxystearic acid nanofibers

A mixture of epoxidized soybean oil (ESO), (R)‐12‐hydroxystrearic acid (HSA) and a photoinitiator for cationic polymerization in the ESO/HSA weight ratio 10/1 was heated to 100 °C and gradually cooled to room temperature to give bio‐based gelatinous material. The photo‐curing of the gel afforded a nanocomposite composed of crosslinked ESO and supramolecular HSA nanofibers. The transmission electron microscopy observation of the photo‐cured ESO/HSA revealed that dendritic clusters of HSA nanofibers are formed in the crosslinked ESO matrix. In the differential scanning calorimetry chart of the ESO/HSA, a thermal transition from the mesophase composed of supramolecular nanofibers to isotropic state was observed at 67 °C (ΔH = 22.6 J/g‐HSA), while the T_m of crystalline HSA is 77.7 °C (ΔH_m = 159 J/g‐HSA). Tensile strength at 20 °C of the ESO‐HSA was ～80% higher than that of photo‐cured ESO without HSA. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 669–673, 2009     

"Sweet silicones": biocatalytic reactions to form organosilicon carbohydrate macromers

Immobilized lipase B from Candida antarctica (Novozyme 435) catalyzed the regioselective formation of ester bonds between organosilicon carboxylic diacids and a C1-O-alkylated sugar under mild reaction conditions (i.e., low temperature, neutral pH, solventless). Specifically, the acid-functionalized organosilicones reacted with the primary hydroxyl group at the C6 position of alpha,beta-ethyl glucoside during the regioselective esterification. The pure organosilicon-sugar conjugates were prepared in a one-step reaction without protection-deprotection steps and without activation of the acid groups with the integrity of the siloxane bonds. [reaction: see text]     

Thermal and mechanical properties of epoxy resin toughened with epoxidized soybean oil

A series of new modified epoxy resin (EP) cured products were prepared from epoxidized soybean oil and commercial epoxy resin, with methyl nadic anhydride as curing agent and 1-methylimidazole as promoting agent. The thermal properties of the resins were characterized by DMA and TG; DSC was used to determine the curing process. Fourier transform infrared spectroscopy was utilized to investigate their molecular structures and scanning electron microscopy was used to observe the micro morphology of their impact fracture surfaces. Tensile and impact testing was employed to characterize the mechanical properties of the cured products. The combination of commercial EP with 20 wt% ESO resulted in a bioresin with the optimum set of properties: 130.5 °C T _g, 396.9 °C T _50 %, 74.89 MPa tensile strength, and 48.86 kJ m^?2 impact resistance.     

4-Vinylbenzenesulfonic acid adduct of epoxidized soybean oil: Synthesis, free radical and ADMET polymerizations

In this work new radically polymerizable triglyceride based monomers were synthesized by the reaction of epoxidized methyl oleate (EMO) and epoxidized soybean oil (ESO) with 4-vinyl benzene sulfonic acid (4VBSA). The products are 1-(4-vinylbenzene sulfonyl)oxy-2-alkonols of epoxidized soybean oil (SESO) and 1-(4-vinylbenzene sulfonyl)oxy-2-alkonols of epoxidized methyl oleate (SEMO). These adducts were characterized by ¹H NMR, ¹³C NMR, IR and CHNS elemental analysis. SESO was found to contain, on the average, 2.47 4VBSA units per triglyceride. SESO was free radically polymerized and co-polymerized with styrene and the mechanical and thermal properties of the resulting thermosets were determined by DMA, DSC and TGA. SEMO was used as a model compound to determine the efficiency of metathesis catalysts for these fatty acid derivatives. The second generation Hoveyda–Grubbs catalyst was found to give best yields. ADMET polymerization of SESO with this catalyst with and without solvent gave ∼80% yield of a thermoset polymer. Polymers obtained by free radical route swelled in water at room temperature, and hydrolyzed in water at 60 °C.     

Kinetics of epoxidation of poly(trans-1,4-butadiene) crystals in suspension

The kinetics of the epoxidation reaction between metachloroperbenzoic acid (MCPBA) and poly-(trans-1,4-butadiene), (PTBD), crystals in toluene suspension was investigated in the 6–21°C range using infrared spectroscopy. Crystals of PTBD with M?_n = 36,000 grown from heptane and from toluene solutions and crystals of PTBD with M?_n = 5500 grown from heptane were studied. For toluene-grown crystals the total number of double bonds available for reaction increases with reaction temperature. For all preparations studied the epoxidation reaction is initially second-order—first-order with respect to [MCPBA] and first-order with respect to the concentration of the available double bonds. The second-order rate constant is found to be dependent on temperature, on molecular weight, and also on the crystal preparation conditions. The bromination of PTBD crystals was studied in CCl₄ suspension at 0°C; this reaction was found to be complete within 1 hr with the fraction of double bonds brominated consistent with the epoxidation results. The IR spectra for dried mats of brominated and of epoxidized PTBD crystals were obtained: Changes in the amorphous band at 1335 cm^?1 due to reaction of double bonds at crystal surfaces were observed. The results of this investigation are discussed in terms of the amorphous content of the PTBD lamellas.     

Esterification activity and stability of Candida rugosa lipase immobilized into chitosan

Microbial lipase from Candida rugosa immobilized into porous chitosan beads was tested for esterification selectivity with butanol and different organic acids (C2–C12), and butyric acid and different aliphatic alcohols (C2–C10). After 24 h, the acids tested achieved conversions of about 40–45%. Acetic acid was the only exception, and in this case butanol was not consumed. Different alcohols led to butyric acid conversions >40%, except for ethanol, in which case butyric acid was converted only 26%. The system’s butanol and butyric acid were selected for a detailed study by employing an experimental design. The influence of temperature, initial catalyst concentration, and acid:alcohol molar ratio on the formation of butyl butyrate was simultaneously investigated, employing a 2³ full factorial design. The range studied was 37–50°C for temperature (X₁), 1.25–2.5% (w/v) for the catalyst concentration (X₂), and 1 and 2 for the acid:alcohol molar ratio (X₃). Catalyst concentration (X₂) was found to be the most significant factor and its influence was positive. Maximum ester yield (83%) could be obtained when working at the lowest level for temperature (37°C), highest level for lipase concentration (2.5% [w/v]), and center level of acid:alcohol molar ratio (1.5). The immobilized lipase was also used repeatedly in batch esterification reactions of butanol with butyric acid, revealing a half-life of 86 h.     

Nutritional improvement of soybean oil via lipase-catalyzed interesterification

In order to decrease the content of linoleoyl moiety in soybean oil, soybean oil that contains 22.8% oleoyl, 54.8% linoleoyl, and 7.1% α-linolenoyl moieties as molar acyl moiety composition was interesterified in hexane with oleic acid or α-linolenic acid, using an immobilized sn-l,3-specific lipase (Lipozyme® IM) fromMucor miehei. The reactions were carried out in a batch reactor at 37°C in the following system: molar ratio of fatty acid to soybean oil = 1.0 ～ 6.0, 5.0 mL of hexane/500 μmol soybean oil, and 10.0 or 15.0 batch interesterification units of enzyme/500 μmol soybean oil. Under these reaction conditions, the rates of interesterification of acyl moieties in soybean oil were of the order: stearoyl > palmitoyl > linoleoyl > oleoyl > α-linolenoyl, and the reaction with oleic acid occurred without a significant loss of α-linolenoyl moiety. At the molar ratio of 3.0 and the reaction time of 6 h, triacylglycerols (TGs), which contain 50.8% oleoyl, 38.8% linoleoyl, and 5.4% α-linolenoyl moieties, were produced in the reaction with oleic acid; TGs that contain 13.5% oleoyl, 40.8% linoleoyl, and 40.4% α-linolenoyl moieties were obtained with α-linolenic acid. Approximately 86-88% of the interesterification of linoleoyl moiety, which occurred in 10 h, took place within 1 h.     

Synthesis of SBA-15 from low cost silica precursor obtained from sugarcane leaf ash and its application as a support matrix for lipase in biodiesel production

Ordered mesoporous silica material was synthesized from a low-cost precursor, sugarcane leaf ash, was used as a support matrix for lipase for the production of biodiesel. The mesoporous samples were characterized using Fourier transform infra red spectroscopy. The surface topography and morphology of the mesoporous materials were studied using scanning electron microscope. The pore diameter, pore volume, Brunauer Emmett and Teller surface area of the mesoporous material were determined by N₂ gas adsorption technique. Different pore size Santa Barbara Acid-15 (SBA-15) samples were synthesized and their lipase immobilization capacity and specific enzyme activity of immobilization lipase were determined and compared. Lipase from Candida Antarctica immobilized on SBA-15 (C) had shown maximum percentage immobilization and specific enzyme activity. The immobilized lipase mesoporous matrix was used for biodiesel production from crude non-edible Calophyllum inophyllum oil. The percentage yield of fatty acid methyl ester, 97.6 % was obtained under optimized conditions: 100 mg of lipase immobilized on SBA-15, 6:1 methanol to oil molar ratio, the reaction of 2 g C. inophyllum oil with methanol.     

脂肪酶 Novozyme 435 选择性催化2,2-二甲基环丙烷甲酸乙酯合成S-(+)-2,2-二甲基环丙烷甲酸

 采用脂肪酶催化外消旋 2,2-二甲基环丙烷甲酸乙酯 (DMCPE) 不对称水解合成西司他丁关键手性中间体 S-(+)-2,2-二甲基环丙烷甲酸 (S-(+)-DMCPA). 比较了 5 种不同来源的脂肪酶, 从中优选出立体选择性较高和催化活性较高的脂肪酶 Novozyme 435, 系统考察了影响该酶催化不对称水解反应的关键因素, 获得了优化的生物催化工艺条件. 结果表明, 当脂肪酶 Novozyme 435 用量为 16 g/L, 底物 DMCPE 浓度为 65 mmol/L 时, 以 pH 值为 7.2 的磷酸缓冲液 (1 mol/L) 为反应介质, 30 oC 反应 64 h, 产物的收率和光学纯度分别为 45.6% 和 99.2%. 脂肪酶 Novozyme 435 催化 DMCPE 不对称水解制备 S-(+)-DMCPA 工艺的产物光学纯度高, 路线可行, 并且酶可重复使用, 具有良好的工业化应用前景.     

Castor oil modified by epoxidation,transesterification, and acrylation processes: Spectroscopic characteristics

In the present study, castor oil (CO) was modified by epoxidation, transesterification, and acrylation processes. In situ epoxidation method was used to prepare epoxidized castor oil (ECO) in acetic acid with hydrogen peroxide in the presence of Seralite SRC-120 catalyst. Transesterified epoxidized castor oil was synthesized from the reaction of methanol in the presence of sodium methoxide catalyst. The acrylated epoxidized castor oil was synthesized from the reaction of ECO with acrylic acid containing hydroquinone. Chemical structures of modified CO were analyzed by Fourier transform infrared spectroscopy and proton nuclear magnetic resonance spectra analysis.     

Ternary liquid-liquid equilibria measurement for epoxidized soybean oil + acetic acid + water

Liquid-liquid equilibria (LLE) data were measured for ternary system epoxidized soybean oil (ESO) + acetic acid + water at 313.15, 323.15 and 333.15 K, respectively. The consistency of the measured LLE data was tested, using Othmer-Tobias correlation and root-mean-square deviation (sigma) in mass fraction of water in the lower phase and average value of the absolute difference (AAD) between experimental mass fraction of epoxidized soybean oil in the upper phase and that calculated using Othmer-Tobias correlation.     

Lipase-catalyzed interesterification of soybean oil with an omega-3 polyunsaturated fatty acid concentrate prepared from sardine oil

To reduce the content of linoleoyl moiety in soybean oil, soybean oil that contains 53.0% linoleoyl moiety as molar acyl moiety composition was interesterified with an omega-3 polyunsaturated fatty acid (PUFA) concentrate (24.0 mol% eicosapentaenoic acid [EPA], 40.4 mol% docosahexaenoic acid [DHA]) prepared from sardine oil, using an immobilized sn-1,3-specific lipase from Rhizomucor miehei (Lipozyme IM). The reaction was carried out in a batch reactor at 37 degrees C under the following conditions: 500 micromol of soybean oil, molar ratio of omega-3 PUFA concentrate to soybean oil = 1.0-6.0,5.0 mL of heptane, and 30 batch interesterification units of enzyme. After the reaction time of 72 h, modified soybean oil, which contains 34.9% linoleoyl, 10.1% eicosapentaenoyl, and 14.2% docosahexaenoyl moieties, was produced at the molar reactant ratio of 6.0. In this oil, the total omega-3 acyl moiety composition reached 34.1%; the molar ratio of omega-3 to omega-6 acyl moieties was enhanced by five times compared with soybean oil. Compared with palmitic acid, DHA was kinetically six times less reactive, although the EPA was by 16% more reactive.     

Synthesis and Characterization of a Bio-Based Resin from Linseed Oil

Summary: The use of renewable raw materials in the polymer industries is becoming increasingly popular because of environmental concerns and the need to substitute fossil resources. Plant oils with triglyceride backbones can be chemically modified and used to synthesize polymers from renewable resources (biopolymers). In the present study, linseed oil was epoxidized using a chemo-enzymatic method based on Candida Antarctica lipase B (CALB) as a biocatalyst and the modified linseed oil was cured using maleinated linseed oil and a commercial polyamide resin. The amount of epoxidation achieved depended on the amount of lipase used and was determined by infrared (IR) and nuclear magnetic resonance (NMR) spectroscopies. With 20% (weight per weight) catalyst concentration based on the wt % of oil a degree of epoxidation of > 90% was achieved. The cross-linking reaction of epoxidized linseed oil with the maleinated linseed oil and the polyamide resin was studied using differential scanning calorimetry (DSC). DSC traces showed that an increase in epoxidation degree lead to larger values for the exothermic enthalpy integrals of the curing reactions and hence to a higher reactivity of the linseed oil towards the cross-linking agents.     

Epoxidized HTPB‐based Polyurethane Membranes for Pervaporation Separation

Polyurethane (PU) solutions were synthesized with hydroxyl‐terminated polybutadiene (HTPB), 4,4′‐dicyclohexylmethane diisocyanate (H₁₂MDI) and 1,4‐butanediol (1,4‐BD). PU membranes were prepared by dry/wet method from PU solutions, while epoxidized membranes were prepared by dipping the dried PU membranes into a mixture of formic acid and hydrogen peroxide for the reaction with C=C double bonds of HTPB soft segments. The extent of epoxidized reaction, which forms epoxide or ether groups, on the PU membranes was quantified by the absorbance ratio of the epoxide group to the butadiene group (A_epoxide/A_C=C ratio). Effect of epoxidized time on the polymer composition, morphology, and polarity of these HTPB‐based PUs was investigated by FTIR‐ATR, DMA and contact angle meter. Both permeabilities and permselectivity of a water/ethanol mixture, which is measured by pervaporation method, were improved through the epoxidation of PU membranes.