A continuous process for the glycerolysis of soybean oil

A continuous process for the glycerolysis of soybean oil with pure and crude glycerol, the co-product from the transesterification of soybean oil, was investigated in a pilot plant. The process was equipped with a static and a high-shear mixer. The experimental studies explored the effects of variations in mixing intensity, temperature, reactant flow rates, and reactant stoichiometry on the formation of MG and DG. The developed process resulted in high conversion of TG to MG. The most favorable conditions were 230°C, 40 mL/min total flow, 25 min of reaction time, 2.5∶1 molar ratio of glycerol/soybean oil, and 3600 rpm for the reactions involving crude glycerol where the concentrations of MG and DG in the product were about 56 and 36 wt%, respectively. Under similar conditions, glycerolysis of pure glycerol resulted in 58% MG and 33% DG. In general, higher temperatures and mixing intensities favored the conversion of TG to MG and DG. Reaction temperature had a greater influence on the extent of the reaction than mixing. The formation of MG approached equilibrium for nearly all cases under investigation.     

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.     

铜绿假单胞菌脂肪酶无溶剂催化棕榈油甘油解Ⅰ.单甘酯酶促合成工艺的研究

以自产铜绿假单胞菌脂肪酶为催化剂 ,通过无溶剂法棕榈油甘油解反应催化合成了单脂肪酸甘油酯。实验结果表明 :适宜加酶量为 50 0u g棕榈油 ,甘油相适宜水质量分数为w (H2 O)=3%～ 4 5% ,反应物量比宜设定为 n(甘油 )∶n(棕榈油 ) =( 2 0～ 2 5)∶1。反应器材质对单甘酯产率有影响 ,31 6L型不锈钢为适宜材质。最佳反应温度为 38～ 42℃ ,在此温度区间内适宜反应时间为 2 4h。临界反应温度为 44℃。     

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.     

Zn-Mg复合氧化物催化大豆油甘油解合成单甘酯

采用共沉淀法制备了一系列不同Zn、Mg物质的量比的Zn-Mg复合氧化物,将其用于催化大豆油甘油解合成单甘酯(MG),采用XRD、氮气吸附-脱附仪、SEM、TEM对Zn-Mg复合氧化物结构与性能进行了表征,并测定了催化剂的表面碱强和碱量。优化了合成单甘酯的工艺条件,并考察了Zn-Mg复合氧化物的重复使用性能。结果表明,改变Zn、Mg物质的量比不仅可以调控Zn-Mg复合氧化物的碱强与碱量,还可以调控其比表面积、孔容等结构参数;不同Zn、Mg物质的量比复合氧化物的催化活性变化趋势与其碱强度(H)在15.0H17.2间碱量变化趋势相一致;n(Zn)/n(Mg)=0.1时,复合氧化物(ZM0.1)具有最好的催化甘油解反应活性;使用该催化剂合成单甘酯的适宜条件为:n(甘油)∶n(大豆油)=3∶1,反应温度210℃,反应时间2 h,催化剂用量为大豆油质量的0.6%,该条件下大豆油转化率达95.6%,单甘酯收率为58.5%。ZM0.1催化剂重复使用4次时大豆油转化率仍达80.9%。     

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.     

Selective hydrogenation of soybean oil: VII. Poisons and inhibitors for copper catalysts

Hydrogenation rates for the catalytic reduction of soybean oil with a copper-on-silica catalyst increased when the oil was re-refined and bleached in the laboratory. Purification of the re-refined and bleached oil by passage through alumina further enhanced hydrogenation rates. Since these observations suggested that poisons were present in the oil, the effect of minor components of soybean oil upon the activity of copper catalysts was investigated. Free fatty acids, monoglycerides, β-carotene, phosphoric acid, sodium soaps, phosphatides, glycerine, choline, ethanolamine, water, pheophytin, and pyrrole all reduced hydrogenation rates when added to the oil. Organic sulfur added to the oil was a more effective catalyst inhibitor than inorganic sulfur added to the gas. Catalyst activity was affected adversely when iron was added to the oil as a soap or when deposited on the catalyst during its preparation. Squalene, copper soaps, and carbon monoxide had no influence on the activity of the catalyst. Aging of soybean oil also had no effect. There was no significant change in either selectivity or formation oftrans or conjugated diene isomer when these additives were added to the oil.     

High yield of monoacylglycerols production through low‐temperature chemical and enzymatic glycerolysis

The present study aimed to produce MAG through low‐temperature chemical glycerolysis. Over 80% MAG yield with 97% TAG conversion was obtained within short reaction times at temperature of 35–55°C, when tert‐butanol (TB) or tert‐pentanol (TP) was used as reaction medium and sodium hydroxide (NaOH) as catalyst. TB gave a faster reaction rate than TP. Catalysts were important for the low‐temperature chemical glycerolysis reaction. Of the eight common base catalysts evaluated, only NaOH and potassium hydroxide (KOH) were effective, and NaOH was better than KOH. Reaction parameters were studied and optimized. The optimum conditions were TB dosage 3:1 (TB to oil in weight ratio), NaOH concentration 0.45 wt% based on oil, molar ratio of glycerol to oil 5:1. Under these conditions, similar MAG yield and TAG conversion was also observed by Novozym 435 catalyzed glycerolysis, however, a 4 h reaction was required. Practical applications: The process of NaOH catalyzed chemical glycerolysis for MAG production in TB solvent system described in this study provides several advantages including short reaction time and high product yield, which is potential for industrial considerations.     

Glycerolysis of coconut,sesame, and linseed oils. Fractionation of the products with alcohol and urea

Summary This study of the glycerolysis of linseed, coconut, and sesame oil at 200°C., 225°C., and 250°C. shows that coconut oil, because of its low-average-molecular weight, is esterified more easily than sesame and linseed oils. Comparison of the reactions of sesame and linseed oils indicates that saturated acids are trans-esterified more easily than the unsaturated ones. The amount of glycerol to be used is determined by its miscibility at the particular reaction temperature. Results of alcohol extraction of the crude monoglycerides from linseed and coconut oil indicate that the glycerides separate on the basis of degree of esterification rather than on unsaturation. Urea adduct fractionals of the technical monoglycerides of sesame oil and lauric acid show that diglycerides form urea adducts more easily than do monoglycerides. In this case, also, the fractionation is related to the degree of esterification rather than unsaturation.     

Kinetics of hydroxide‐catalyzed methanolysis of crude sunflower oil for the production of fuel‐grade methyl esters

Methyl esters from crude sunflower oil were produced via methanolysis reaction using sodium hydroxide catalyst. Methanolysis was carried out at different agitation speeds (200–600 rpm), temperatures (25–60 °C), catalyst loadings (0.25–1.00% by weight of oil), and methanol:oil mole ratios (6:1–20:1). Mass‐transfer limitation was effectively minimized at agitation speeds of 400–600 rpm with no apparent lag period. Lowering the temperature resulted in a fall in the rate of reaction prolonging the reaction time necessary to achieve maximum production of methyl ester. Using 0.50% hydroxide catalyst was found to be adequate, resulting in 97–98% conversion without compromising recovery due to soap formation. Increasing the methanol:oil mole ratio beyond the usual amount of 6:1 tended to speed up the initial rate of methanolysis and was found to lower the bonded glycerol content, especially the amount of diglyceride in the sample. Kinetic rate constants were derived from experimental results using second‐order rate expressions, and values of activation energy for glyceride methanolysis have been established. Copyright © 2007 Society of Chemical Industry     

Enzymatic Glycerolysis of Palm and Palm Kernel Oils

Glycerolysis of palm and palm kernel oils were carried out using commercial lipases from Candida antarctica (Novozym 435) and Mucor miehei (Novozym 388) as catalyst (500 units lipase/g oil) at 40°C and with an oil:glycerol molar ratio of 1:2 in a solvent-free system. Novozym 435 catalyzed the glycerolysis of palm and palm kernel oils giving reaction products in similar compositions. Partial acylglycerols contents of the glycerolysis products obtained from palm and palm kernel oils were 64% (wt) and 66% (wt), respectively. However, partial acylglycerols contents of the glycerolysis products obtained from palm and palm kernel oils conducted with Novozym 388 as catalyst at the same conditions were 44% (wt) and 56% (wt), respectively. On the other hand, free fatty acid contents of the glycerolysis products of palm and palm kernel oils obtained using Novozym 388 were higher, 25–30% (wt), than those obtained by Novozym 435, 4–5% (wt). The monoacylglycerols fraction with the highest content of oleic acid, 62.7% (wt), was obtained from the palm kernel oil glycerolysis reaction catalyzed by Novozym 435.     

脂肪酶促乌桕脂组分甘油解及其反应机理研究

Glycerolysis of Chinese vegetable tallow （CVT） fraction was investigated using a 1,3-specific lipase from Rhizopus arrhizus as catalyst. Based upon a binary gradient HPLC with an evaporative light-scattering detector （ELSD）, the contents of free fatty acids （FFA）, monoglycerides （MG）, diglycerides（DG） and triglycerides （TG） with their positional isomers during the glycerolysis were determined. The effects of water content and the ratio of glycerol to oil on the product distribution of glycerolysis were studied. Under the optimum reactant conditions： 250 units lipase per gram oil at 37℃ with 1：2 molar ratio of oil to glycerol in a solvent-free system, after 24 h reaction, the product consisted of 7.2% TG, 25.6% MG, 56.1% DG and 4.9% FFA （all by mass）. Furthermore, the mechanism of glycerolysis was discussed in detail.     

Selective distribution of saturated fatty acids into the monoglyceride fraction during enzymatic glycerolysis

Four triglyceride fats and oils (beef tallow, lard, rapeseed oil and soybean oil) were reacted with glycerol while using lipase as the catalyst. For all fats examined, at reaction temperatures above the critical temperature (T_c), the fatty acid compositions of the monoglyceride (MG) and diglyceride (DG) fractions and of the original fat were similar. A relatively low yield of MG was obtained (20–30 wt%). When the reaction was carried out with beef tallow or lard at a temperature below the T_c (40°C), the concentration of saturated fatty acids in the MG fraction was 2 to 4 times greater than that in the DG fraction. Correspondingly, the concentration of unsaturated fatty acids in the DG fraction was more than two times greater than that in the MG fraction. At 5°C, a similar trend was observed for rapeseed oil and soybean oil. Direct analysis of partial glycerides during glycerolysis by high-temperature gas-liquid chromatography showed that below T_c the content of C16 MG increased relatively more than C18 MG. C36 DG and C54 TG were apparently resistant to glycerolysis. Preferential distribution of saturated fatty acids into the MG fraction was accompanied by a high yield of monoglyceride (45–70 wt%) and solidification of the reaction mixture. It is concluded that during glycerolysis below T_c, preferential crystallization occurs for MGs that contain a saturated fatty acid.     

铜绿假单胞菌脂肪酶无溶剂催化棕榈油甘油解Ⅱ.进一步提高单甘酯产率的研究

以自产铜绿假单胞菌脂肪酶为催化剂 ,通过无溶剂法棕榈油甘油解反应催化合成了单脂肪酸甘油酯。考察了反应温度程序以及加酶方式对最终产物中单甘酯质量分数的影响。结果表明程序降温和批次加酶更有利于反应 ,产物中单甘酯质量分数可增大 1 0 %～ 2 0 % ,实验条件下反应 48h后单甘酯质量分数可达 65 % ,脱酶后达 77%。     

Biodiesel Production from Soybean Oil Catalyzed by Li<Subscript>2</Subscript>CO<Subscript>3</Subscript>

In the present study, we synthesized biodiesel from soybean oil through a transesterification reaction catalyzed by lithium carbonate. Under the optimal reaction conditions of methanol/oil molar ratio 32:1, 12 % (wt/wt oil) catalyst amount, and a reaction temperature of 65 °C for 2 h, there was a 97.2 % conversion to biodiesel from soybean oil. The present study also evaluated the effects of methanol/oil ratio, catalyst amount, and reaction time on conversion. The catalytic activity of solid base catalysts was insensitive to exposure to air prior to use in the transesterification reaction. Results from ICP-OES exhibited non-significant leaching of the Li₂CO₃ active species into the reaction medium, and reusability of the catalyst was tested successfully in ten subsequent cycles. Free fatty acid in the feedstock for biodiesel production should not be higher than 0.12 % to afford a product that passes the EN biodiesel standard. Product quality, ester content, free glycerol, total glycerol, density, flash point, sulfur content, kinematic viscosity, copper corrosion, cetane number, iodine value, and acid value fulfilled ASTM and EN standards. Commercially available Li₂CO₃ is suitable for direct use in biodiesel production without further drying or thermal pretreatment, avoiding the usual solid catalyst need for activation at high temperature.     

A monoglyceride-rich tung oil product

A method for preparing tung monoglycerides (1) by the reaction of tung oil with an excess of glycerol in the presence of sodium methoxide as the catalyst has been adapted to the preparation of large batches of material. Laboratory scale studies have shown that a product analyzing as containing up to 50% of tung monoglycerides is produced when the reaction is carried out at 150°C. for one hour with an excess of 1 mole of glycerol and 1% of sodium methoxide (based on oil weight). The data were applied successfully to three batchwise pilotplant preparations using from 30 to 47 pounds of tung oil to produce a product containing from 32% to 45% tung monoglycerides. Unreated glycerol was successfully separated from the product by centrifugation, with no water or salt solution washing, to give a product containing 1.5% to 3.5% free glycerol. Difficulties were encountered in analyzing the product for monoglyceride, and it was found that the triene conjugation contributed to high results, However, there also appear to be components other than simple monoglycerides in the product which analyze as monoglycerides to give a falsely high value, as evidenced by differences found by analyses of the products before and after essentially complete hydrogenation.     

Preparation of 1,3‐Diolein by Irreversible Acylation

Earlier findings on the nutritional benefits of diacylglycerols (DAGs) have attracted much attention on the synthesis of DAGs. In this study, we reported an improved method for the lipase‐catalyzed synthesis of 1,3‐diolein by the irreversible glycerolysis of vinyl oleate with glycerol. The effects of reaction system, lipase loading, molar ratio of vinyl oleate to glycerol, reaction temperature and time on 1,3‐diolein content in crude reaction mixture were investigated. When the reaction was conducted in a solvent‐free system at 30 °C for 8 h by reacting 2 mmol vinyl oleate with 1 mmol glycerol with 8 % (w/w, relative to total reactants) Lipozyme RM IM (Novozymes, Beijing, China) as catalyst, there were 90.5 ± 2.9 % (area/area) 1,3‐diolein and (3.3 ± 0.3) % 1,2‐diolein produced. After purification, 1,3‐diolein was obtained at 81.4 % yield with 98.2 % purity. The lipase‐catalyzed synthesis of 1,3‐diolein using vinyl oleate as acyl donor by glycerolysis was also conducted using a medium with 50 mmol of glycerol and 100 mmol vinyl oleate. Compared to enzymatic esterification in a solvent, enzymatic glycerolysis for the synthesis 1,3‐diolein is more effective due to the irreversible reaction, mild due to the low reaction temperature, and environmentally benign due to the use of solvent‐free reaction system.     

Kinetic study of liquid lipase-catalyzed glycerolysis of olive oil using Lipozyme TL 100L

Monoacylglycerol (MAG) and diacylglycerol (DAG) are two natural components found in most edible oils and fats. Conventional synthesis of MAG and DAG is usually conducted by glycerolysis of triacylglycerol (TAG) at high temperatures (above 200°C) in the presence of an alkaline catalyst. In this work, the synthesis of MAG and DAG using enzymatic glycerolysis of olive oil was investigated using Tween 80 as surfactant, n-butanol as co-surfactant and the novel lipase in free/liquid formulation Lipozyme TL 100L as catalyst. Experimental design was used to evaluate the effect of enzyme load and reaction temperature on the feedstock conversion. Enzyme load and system temperature were significant variables in the statistical design and the best condition was found at 35°C, 7.5 vol% of Lipozyme TL 100L and glycerol to oil volumetric ratio of 2:1 with conversion of TAG at approximately 98% after 2 h of process. A mathematical model based on the Ping-Pong Bi-Bi mechanism was used to describe the reaction kinetics. The model adequately described the behavior of the system and can be a useful tool for the design of reactors in larger scales.     

Synthesis of biodiesel from soybean oil using supercritical methanol in a one-step catalyst-free process in batch reactor

The transesterification of soybean oil with supercritical methanol in a batch reactor with no added catalyst was investigated, studying the evolution of intermediate products (monoglycerides and diglycerides) as well as the conversion of triglycerides and the yield of fatty acid methyl esters and glycerol. Experiments were carried out in a temperature range of 250–350 °C (12–43 MPa) at reaction times of between 15 and 90 min for a methanol-to-oil molar ratio of 43:1. The best reaction conditions in this one-step supercritical process (325 °C/35 MPa and 60 min), in which triglyceride conversion was practically total, led to a maximum yield of fatty acid methyl esters of 84%. In these conditions an 8.1 wt% of monoglycerides and diglycerides remained in the medium. Although the use of more severe reaction conditions (longer reaction times and higher temperatures) reduced the content of these glycerides, the yield of methyl esters decreased due to their thermal decomposition.     

Biodiesel synthesis: A study of the triglyceride methanolysis reaction with alkaline catalysts

The rates of soybean oil methanolysis under NaOCH₃, KOCH₃, NaOH and KOH catalysis were determined at 30.0, 40.0, 50.0 and 60.0 °C using a refractometric method for online monitoring of this reaction. The influences of the metallic cations and anions on the catalysis were studied. Potassium promotes faster reactions than sodium. For the reactions catalyzed by hydroxides, the rate constants are less sensitive to temperature than those catalyzed by methoxides. The proposed reaction mechanism was based on the formation of ionic pairs at the interface of the methanol and oil phases and in the methanol phase.