超临界甲醇法制备生物柴油

研究了超临界甲醇法制备生物柴油中温度、醇油摩尔比、反应时间和助溶剂对甲酯生成率的影响,同时研究了加入少量的KOH以降低反应的苛刻条件.在超临界甲醇反应温度350℃,醇油摩尔比为421的优化反应条件下,10min后脂肪酸甲酯的产率达到95.0%以上;300℃时加入CO2和正己烷可以提高甲基酯的转化率;在160℃的亚临界状态下、醇油摩尔比为241时,加入质量分数为0.1%的KOH,20min后脂肪酸甲酯的转化率也达到了98.5%以上.     

超临界甲醇中制备生物柴油

研究了超临界甲醇法制备生物柴油中反应条件对甲酯生成率的影响。结果表明,醇油摩尔比越大,大豆油转化率越高;升温有助于提高反应速率,在临界温度239℃附近,温度的影响尤其明显;当压力高于13.5 MPa时,压力对反应的影响不明显;原料油中,不同脂肪酸酯甲酯化的速率不同,按亚油酸酯、油酸酯、棕榈酸酯、硬脂酸酯的顺序依次降低;大豆油中w(游离油酸)<50%时,不影响反应转化率;原料油中w(H2O)<20%时对反应影响不大。当醇油摩尔比为42∶1,反应温度280℃,反应1 h,油脂转化率可达78%。     

超临界连续化制备生物柴油单管扩大试验

在小试基础上,建立了一套百吨级超临界连续化制备生物柴油单管扩大试验装置,主要包括反应系统、产品精制系统和自动控制系统3个部分.以大豆油和甲醇为原料进行了扩大试验.考察了在连续反应条件下超临界甲醇法制备生物柴油中不同反应条件对脂肪酸甲酯收率的影响.试验结果表明,装置运行良好,适宜的工艺条件为:反应温度300℃,反应压力15 MPa,反应停留时间1 200 s,醇油摩尔比为40:1,在该条件下,生物柴油收率可达95%.反应物的混合状况对酯交换反应有重要影响.在相同工艺条件下,扩大试验装置中反应混合物流动的雷诺数是小试的2倍,传质系数增大,甲酯收率显著高于小试结果.     

微藻超临界甲醇直接酯交换法制备生物柴油

以规模化养殖的小球藻为原料,采用超临界甲醇酯交换法开展了制备生物柴油的实验研究。通过对原料藻粉的主要组成和实验产物的元素、化合物组成及基本理化特性进行分析,考察了不同工艺条件对产率的影响。结果表明,在甲醇与湿藻（50%含水量）配比为8∶1（mL∶g）、反应温度260℃、反应压力8 MPa和停留时间10 min的条件下,微藻生物柴油产率高达9%以上,具有与石化柴油接近的理化性质和成分组成。     

微藻超临界甲醇直接酯交换法制备生物柴油

以规模化养殖的小球藻为原料,采用超临界甲醇酯交换法开展了制备生物柴油的实验研究。通过对原料藻粉的主要组成和实验产物的元素、化合物组成及基本理化特性进行分析,考察了不同工艺条件对产率的影响。结果表明,在甲醇与湿藻(50% 含水量)配比为8∶1(mL∶g)、反应温度 260℃、反应压力 8 MPa 和停留时间 10 min 的条件下,微藻生物柴油产率高达 9% 以上,具有与石化柴油接近的理化性质和成分组成。     

微酸强化超临界甲醇法连续化合成生物柴油

超临界甲醇法合成生物柴油的苛刻反应条件制约其大规模工业化。加入微量酸可提高反应速率,降低苛刻的反应条件,且不会带来后续分离问题。实验在温度270—360℃,压力9—15 MPa,停留时间300—1 300 s,醇油摩尔比(20∶1)—(40∶1)的条件下,研究了加入油酸、硬脂酸和微量磷酸对过程的强化,并进行了比较。结果表明:磷酸是最佳的酸性催化剂,在磷酸催化的条件下,最佳反应条件为温度300℃、压力13 MPa、停留时间700 s、醇油摩尔比30∶1,磷酸加入量为使大豆油酸价为15 mg/g(以每g大豆油KOH质量计)的加入量。在此条件下,脂肪酸甲酯的收率达到95%以上。     

超临界甲醇制备生物柴油的研究

以菜籽油为原料,在超临界甲醇中制备了生物柴油,采用正交实验考察了反应温度、醇油摩尔比和反应时间对生物柴油收率的影响.结果表明,各因素对生物柴油收率影响的显著性顺序为:反应温度》醇油摩尔比》反应时间;最佳工艺条件为:反应温度300℃、醇油摩尔比42∶1、反应时间20 min,在此条件下生物柴油的收率达到97.95%.     

耦合闪蒸的连续超临界甲醇法制备生物柴油

在耦合闪蒸装置的管式反应器中,以菜籽酸化油为原料,采用超临界甲醇法连续制备生物柴油,同时绝热闪蒸回收甲醇,考察了醇油摩尔比、反应温度、反应压力、反应时间以及闪蒸压力对生物柴油收率、甲醇回收率及气相中甲醇含量的影响。结果显示,在醇油摩尔比35∶1,反应温度300℃,反应压力13 MPa,反应时间600 s的最优条件下,生物柴油收率可达83.1%(以菜籽酸化油质量计);在最优条件及闪蒸压力为常压条件下,闪蒸甲醇回收率可达90.5%,气相中甲醇含量达97.7%;对闪蒸回收的甲醇循环使用5次后,甲醇回收率为86.8%,回收甲醇中甲醇的质量分数为93.7%,该组成的回收甲醇对生物柴油收率无明显影响。     

超临界甲醇法制备生物柴油的动力学研究进展

超临界甲醇法制备生物柴油技术由于其独特的优势,从首次被提出以来,就受到国内外众多研究者的关注和研究。综述了超临界甲醇无催化制备生物柴油的相关动力学研究成果,讨论了反应机理、反应速率常数和活化能等,旨在阐明反应规律。另外也介绍了超临界流体二步法制备生物柴油技术及其动力学研究成果,并提出了这种技术的优势、存在问题及发展方向。     

超临界法制备生物柴油的研究进展

介绍了国内外对超临界法制备生物柴油的研究进展,着重阐述了反应温度、醇油比、水和游离脂肪酸、共溶剂及催化剂等因素对酯交换反应的影响,概述了超临界流体制备生物柴油的优势、问题及发展趋势。     

A review of laboratory-scale research on lipid conversion to biodiesel with supercritical methanol (2001-2009)

Biodiesel production from lipids (vegetable oils and animal fats) with non-catalytic supercritical methanol (SCM) has several advantages over that of homogeneous catalytic process, including a high production efficiency, environmentally friendliness and a wide range of possible feedstocks. This article reviews the effect of the operating parameters on the lipid conversion to biodiesel with SCM, such as the temperature, pressure, methanol to oil molar ratio, and reaction time, for both batch and continuous systems, including the effect of the mixing intensity and dispersion in tubular reactors. The operating temperature is the key parameter to control either extent of reaction or other parameters. Studies on evaluating the chemical kinetics, phase behavior, binary vapor-liquid equilibrium (VLE) of lipid conversion in SCM are summarized. The pseudo-first order model is suitable to simplify the system at high methanol to oil molar ratios, but it is inadequate at a low methanol concentration which instead requires the second order model. Transition temperatures of reaction mixture depend on the critical point of reaction mixture which is assigned by methanol to oil molar ratio and amount of co-solvents in the system. For binary VLE studies, no single thermodynamic model for the overall process is available, probably because of the differences in the polarity between the initial and the final state of the reaction system. Since traditional operating parameters of the lipid conversion in SCM involve elevated temperatures and pressures, techniques for allowing milder operating conditions that employ the addition of co-solvents or catalysts are discussed. The ongoing and more extensive research on co-solvents, heterogeneous catalysts, phase behavior and multicomponent VLE of lipid conversion to biodiesel with SCM should provide a better understanding and achieve the goal of green biodiesel production technology in the near future.     

Continuous production of biodiesel fuel from vegetable oil using supercritical methanol process

A system for continuous transesterification of vegetable oil using supercritical methanol was developed using a tube reactor. Increasing the proportion of methanol, reaction pressure and reaction temperature can enhance the production yield effectively. However, side reactions of unsaturated fatty acid methyl esters (FAME) occur when the reaction temperature is over 300 °C, which lead to much loss of material. There is also a critical value of residence time at high reaction temperature, and the production yield will decrease if the residence time surpasses this value. The optimal reaction condition under constant reaction temperature process is: 40:1 of the molar ratio of alcohol to oil, 25 min of residence time, 35 MPa and 310 °C. However, the maximum production yield can only be 77% in the optimal reaction condition of constant reaction temperature process because of the loss caused by the side reactions of unsaturated FAME at high reaction temperature. To solve this problem, we proposed a new technology: gradual heating that can effectively reduce the loss caused by the side reactions of unsaturated FAME at high reaction temperature. With the new reaction technology, the methyl esters yield can be more than 96%.     

Preparation of biodiesel from soybean oil using supercritical methanol and co-solvent

Transesterification of soybean oil in supercritical methanol has been carried out in the absence of catalyst. A co-solvent was added to the reaction mixture in order to decrease the operating temperature, pressure and molar ratio of alcohol to vegetable oil. With propane as co-solvent in the reaction system, there was a significant decrease in the severity of the conditions required for supercritical reaction, which makes the production of biodiesel using supercritical methanol viable as an industrial process. A high yield of methyl esters (biodiesel) was observed and the production process is environmentally friendly. Furthermore the co-solvent can be reused after suitable pretreatment.     

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.     

Kinetics of hydrolysis and methyl esterification for biodiesel production in two-step supercritical methanol process

For high-quality biodiesel fuel production from oils/fats, the catalyst-free two-step supercritical methanol process has been developed in a previous work, which consists of hydrolysis of triglycerides to fatty acids in subcritical water and subsequent methyl esterification of fatty acids to their methyl esters in supercritical methanol. In this paper, therefore, kinetics in hydrolysis and subsequent methyl esterification was studied to elucidate reaction mechanism. As a result, fatty acid was found to act as acid catalyst, and simple mathematical models were proposed in which regression curves can fit well with experimental results. Fatty acid was, thus, concluded to play an important role in the two-step supercritical methanol process.     

Oxidation stability of biodiesel fuel as prepared by supercritical methanol

A non-catalytic supercritical methanol method is an attractive process to convert various oils/fats efficiently into biodiesel. To evaluate oxidation stability of biodiesel, biodiesel produced by alkali-catalyzed method was exposed to supercritical methanol at several temperatures for 30 min. As a result, it was found that the tocopherol in biodiesel is not stable at a temperature higher than 300 °C. After the supercritical methanol treatment, hydroperoxides were greatly reduced for biodiesel with initially high in peroxide value, while the tocopherol slightly decreased in its content. As a result, the biodiesel prepared by the supercritical methanol method was enhanced for oxidation stability when compared with that prepared by alkali-catalyzed method from waste oil. Therefore, supercritical methanol method is useful especially for oils/fats having higher peroxide values.     

Biodiesel production from highly unsaturated feedstock via simultaneous transesterification and partial hydrogenation in supercritical methanol

In this study, a supercritical one-pot process combining transesterification and partial hydrogenation was proposed to test its technical feasibility. Simultaneous transesterification of soybean oil and partial hydrogenation of polyunsaturated compounds over Cu catalyst in supercritical methanol was performed at 320 °C and 20 MPa. Hydrogenation proceeded simultaneously during the transesterification of soybean oil in supercritical methanol, and hydrogenation occurred during the reaction despite the absence of hydrogen gas. The polyunsaturated methyl esters obtained in the biodiesel were mainly converted to monounsaturated methyl esters by partial hydrogenation. Key properties of the partially hydrogenated methyl esters were improved and complied with standard specifications for biodiesel.     

Conversion of waste cooking oil to biodiesel using ferric sulfate and supercritical methanol processes

In this comparative study, conversion of waste cooking oil to methyl esters was carried out using the ferric sulfate and the supercritical methanol processes. A two-step transesterification process was used to remove the high free fatty acid contents in the waste cooking oil (WCO). This process resulted in a feedstock to biodiesel conversion yield of about 85-96% using a ferric sulfate catalyst. In the supercritical methanol transesterification method, the yield of biodiesel was about 50-65% in only 15 min of reaction time. The test results revealed that supercritical process method is probably a promising alternative method to the traditional two-step transesterification process using a ferric sulfate catalyst for waste cooking oil conversion. The important variables affecting the methyl ester yield during the transesterification reaction are the molar ratio of alcohol to oil, the catalyst amount and the reaction temperature. The analysis of oil properties, fuel properties and process parameter optimization for the waste cooking oil conversion are also presented.     

Continuous production of biodiesel with supercritical methanol: Optimization of a scale-up plug flow reactor by response surface methodology

A scale-up plug flow reactor was evaluated for the continuous production of biodiesel from refined palm kernel oil (PKO) with supercritical methanol and optimized by response surface methodology. The effects of the operating temperature (270–350 °C), pressure (15.0–20.0 MPa) and methanol:PKO molar ratio (20:1–42:1) were evaluated at a constant residence time of 20 ± 2 min by using a central composite design. Analysis of variance demonstrated that a modified quadratic regression model gave the best coefficient of determination (R² = 0.9615) and adjusted coefficient of determination (Adj. R² = 0.9273). The interaction terms in the regression model illustrated small synergistic effects of both temperature–pressure and temperature–methanol:PKO molar ratio. The optimal conditions were 325 ± 5 °C, 18.0 ± 0.5 MPa and a methanol:PKO molar ratio of 42 ± 2:1, attaining a maximum production rate of 18.0 ± 1.5 g biodiesel/min with a fatty acid methyl ester content of 93.7 ± 2.1%. The product obtained from the optimal conditions had high cetane number, and could be considered as a fuel additive for cetane number enhancement.     

Improvement of the oxidation stability of biodiesel as prepared by supercritical methanol method with lignin

An antioxidation effect of lignin‐derived products in biodiesel prepared using supercritical methanol (300°C/20 MPa) with molar ratio between rapeseed oil and methanol of 1:42 was studied. It was found that lignin could be decomposed to low molecular compounds that have a free radical‐trapping effect after supercritical methanol treatment. However, longer treatment time decreased the antioxidation effect of the lignin‐derived compounds. Rapeseed biodiesel prepared by supercritical methanol method at 300°C/20 MPa for 20 min with a small amount of added lignin showed an induction period longer than 6 h at 110°C in a Rancimat test. In addition, it was found that lignin had a catalytic effect in biodiesel production using the supercritical methanol method without significantly affecting other fuel properties of the prepared biodiesel. Thus, the study proved that lignin addition provides an inexpensive and technically acceptable way to improve the oxidation stability of biodiesel prepared by the supercritical methanol method with satisfactory fuel properties.