棕榈油酯交换制备生物柴油的反应动力学

在甲醇与棕榈油的摩尔比为6∶1和催化剂KOH用量为棕榈油质量1.0%的条件下,研究不同温度下棕榈油制备生物柴油的酯交换反应动力学,采用Origin软件拟合曲线方程,建立棕榈油酯交换反应的宏观动力学模型。研究结果表明:棕榈油制备生物柴油的酯交换反应遵循1.40级动力学方程,反应速率随温度的升高而加快,二者符合Arrhenius方程,该反应的活化能为27.23 kJ/mol,频率因子为1.4×103。文中研究建立的反应动力学模型将对扩大试验研究提供理论依据和基础数据支持。     

Optimal integration for biodiesel production using bioethanol

The production of biodiesel from algae is optimized using bioethanol following four different transesterification paths: alkali, enzymatic, and heterogeneous catalysts and supercritical conditions. The reactors are modeled using response surface methodology based on experimental results from the literature. These reactor models are implemented together with short‐cut methods for the other equipment (distillation columns, gravity separators, etc.) in order to recover the ethanol, separate the polar and nonpolar phases, and purify the glycerol and biodiesel produced to formulate the problem as a superstructure of alternatives. The aim is to simultaneously optimize and heat integrate the production of biodiesel using ethanol in terms of the reaction technology and the operating conditions. The optimal conditions in the reactors differ from the ones traditionally used because these results take the separation stages into account. In terms of the optimal process, the alkali catalyzed process is the most profitable, while the enzymatic one is also promising due to the lower consumption of energy and water, although it requires significant enzyme cost. © 2012 American Institute of Chemical Engineers AIChE J, 59: 834–844, 2013     

Transesterification for biodiesel production catalyzed by combined lipases: Optimization and kinetics

Preparation of biodiesel from waste cooking oil catalyzed by combined lipases in tert‐butanol medium was investigated. Several crucial parameters affecting biodiesel yield were optimized by response surface methodology, such as dosage of combined lipases of Novozym 435 and Lipozyme TLIM, weight ratio of Novozym 435 to Lipozyme TLIM, amount of tert‐butanol, reaction temperature, and molar ratio of oil to methanol. Under the optimized conditions, the highest biodiesel yield was up to 83.5% The proposed model on biodiesel yield had a satisfactory coefficient of R² (= 94.02%), and was experimentally verified. The combined lipases exhibited high‐operational stability. After 30 cycles (300 h) successively, the activity of combined lipases maintained 85% of its original activity. A reaction kinetic model was proposed to describe the system and deduced to be a pseudo‐first‐order reaction, and the calculated activation energy was 51.71 kJ/mol. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Intensified production of biodiesel using a spinning disk reactor

This work achieves continuous transesterification of soybean oil and methanol in a spinning disk reactor. The effects of the methanol-to-oil molar ratio, catalyst type, catalyst concentration, reaction temperature, flow rate, and rotational speed were investigated. Optimal yield of 96.9% was obtained with a residence time of 2–3 s at a molar ratio of 6, potassium hydroxide concentration of 1.5 wt%, temperature of 60 °C, flow rate of 773 mL/min, and rotational speed of 2400 rpm. The production rate of 1.86 mol/min was high compared to that of other reactors for continuous transesterification process, indicating that a spinning disk reactor is a promising alternative method for continuous biodiesel production.     

Comparative kinetics of transesterification for biodiesel production from palm oil and mustard oil

The kinetics of palm oil and mustard oil transesterification are compared. Transesterification of palm oil and mustard oil using KOH as a catalyst was performed at various reaction temperatures ranging from 40 to 60°C. The reaction steps are reversible and transesterification is favoured at elevated temperatures. The reaction step of triglyceride to diglyceride is the rate determining step (RDS) that controls kinetics of overall transesterification with activation energies of 30.2 and 26.8 kJ/mol for palm oil and mustard oil transesterification, respectively. It is found that percentage of saturated compounds play a vital role on transesterification kinetics. © 2011 Canadian Society for Chemical Engineering     

Continuous biodiesel production using a fixed-bed Lewis-based catalytic system

It was developed a fixed bed tubular continuous reactor to produce biodiesel, using pellets of aluminum oxide doped with zinc oxide. The pellets were placed into a tubular reactor as a 30 cm long column (2.65 kg). The reactor was feed with soybean oil (168 g h⁻¹) and methanol or ethanol (89 g h⁻¹) with the temperature fixed at 100 °C. Under these conditions it was possible to convert soybean oil into biodiesel in up to 75% yield in the case of methanol and 35% for ethanol. Increasing the temperature to 180 °C, it was possible to ethanolise soybean oil with yields up to 78%. It is important to note that after a steady state is achieved the conversions remained approximately constant with time. It is also worth to mention that the fixed bed remained active for more than 120 h, showing no catalyst leaching or deactivation, and so far it was not possible to determine its overall productivity.     

Lipase-catalyzed production of biodiesel

Lipases were screened for their ability to transesterify triglycerides with short-chain alcohols to alkyl esters. The lipase fromMucor miehei was most efficient for converting triglycerides to their alkyl esters with primary alcohols, whereas the lipase fromCandida antarctica was most efficient for transesterifying triglycerides with secondary alcohols to give branched alkyl esters. Conditions were established for converting tallow to short-chain alkyl esters at more than 90% conversion. These same conditions also proved effective for transesterfying vegetable oils and high fatty acid-containing feedstocks to their respective alkyl ester derivatives. Presented in part at the 86th Annual Meeting of American Oil Chemists’ Society, San Antonio, Texas, May 1995.     

酰化吗啉生产技术及其应用进展

分析了国内甲酰吗啉(NFM)、乙酰吗啉(NAM)和丙烯酰吗啉(ACMO)的生产和应用情况;介绍了羧酸法、羧酸酯法、酸酐法和酰氯法制备酰化吗啉工业生产的技术特点和发展趋势。酰化吗啉具有优良的理化性质,对芳烃(或烯烃)有良好的选择性,对酸性气体能选择性脱除等特征,以及含有亲水性官能团吗啉,在芳烃抽提,碳四(C_4)分离、天然气净化、农药合成和高分子材料等领域受到重视。提出开发NFM和NAM混合溶剂为油田轻烃、FCC汽油、伴生气和天然气凝析油等众多富烷烃资源的开发应用提供新工艺或者新技术,开发适合国情的ACMO生产技术,推动其在高分子材料领域的大规模应用。     

废食用油生产生物柴油技术研究进展

综述了利用废食用油生产生物柴油的方法、以及所使用的催化剂研究状况.以废食用油为原料生产生物柴油主要有3种方法:两步催化法,一步催化法和超临界法.环境友好的廉价的固体酸碱催化废食用油连续生产生物柴油是今后的发展趋势.     

Simulation and cost estimate for biodiesel production using castor oil

Brazilian government has established a regulation that imposes the commercialization of diesel blended with 3% of biodiesel by volume. Castor oil has being considered an option to guarantee the supply of biodiesel needed. For this reason, in this work, a continuous biodiesel plant was designed and simulated in HYSYS simulator using castor oil as feedstock. The developed process was capable of producing biodiesel at high purity using an alkali catalyst. Material and energy flows, as well as sized unit operations were used to conduct an economic assessment of the process. Total capital investment, total manufacturing cost and after annual equivalent cost were also calculated. A study of production costs was performed considering the fluctuations of the raw material prices and the glycerin purification step.     

酰化吗啉生产技术及其应用进展

分析了国内甲酰吗啉(NFM)、乙酰吗啉(NAM)和丙烯酰吗啉(ACMO)的生产和应用情况;介绍了羧酸法、羧酸酯法、酸酐法和酰氯法制备酰化吗啉工业生产的技术特点和发展趋势。酰化吗啉具有优良的理化性质,对芳烃(或烯烃)有良好的选择性,对酸性气体能选择性脱除等特征,以及含有亲水性官能团吗啉,在芳烃抽提,碳四(C_4)分离、天然气净化、农药合成和高分子材料等领域受到重视。提出开发NFM和NAM混合溶剂为油田轻烃、FCC汽油、伴生气和天然气凝析油等众多富烷烃资源的开发应用提供新工艺或者新技术,开发适合国情的ACMO生产技术,推动其在高分子材料领域的大规模应用。     

Treatment of industrial glycerol from biodiesel production by adsorption operation: kinetics and thermodynamics analyses

Abstract

Equilibrium, thermodynamic, and kinetic analyses of the pigments adsorption of the industrial glycerol onto activated charcoal were performed. As the pigments concentration was not known, then, a relative adsorption capacity was defined using absorbance values measured in a spectrophotometer at a wavelength of 265?nm. Kinetic study showed that about 60?s were needed to reach equilibrium conditions. Relative adsorption capacity reached 8?g^?1 for 1% of adsorbent amount (w/w). Adsorption enthalpy was of –17.63?kJ mol^?1, while for isosteric heat values were obtained between –7.39 and –18.46?kJ mol^?1. The mathematical methodology used for the parameters determinations proved to be robust and able to express the relationships of kinetics, equilibrium and thermodynamics. Enthalpy values obtained by Van't Hoff method was confirmed by isosteric heat calculation, evidencing that this methodology can be used for systems whose compositions are unknown, but detectable by indirect form.     

Process optimization design for jatropha-based biodiesel production using response surface methodology

Biodiesel of non food vegetal oil origin is gaining attention as a replacement for current fossil fuels as its non-food chain interfering manufacturing processes shall prevent food source competition which is expected to happen with current biodiesel production processes. As a result, non edible Jatropha curcas plant oil is claimed to be a highly potential feedstock for non-food origin biodiesel. CaO–MgO mixed oxide catalyst was employed in transesterification of non-edible J. curcas plant oil in biodiesel production. Response surface methodology (RSM) in conjunction with the central composite design (CCD) was employed to statistically evaluate and optimize the biodiesel production process. It was found that the production of biodiesel achieved an optimum level of 93.55% biodiesel yield at the following reaction conditions: 1) Methanol/oil molar ratio: 38.67, 2) Reaction time: 3.44 h, 3) Catalyst amount: 3.70 wt.%, and 4) Reaction temperature: 115.87 °C. In economic point of view, transesterification of J. curcas plant oil using CaO–MgO mixed oxide catalyst requires less energy which contributed to high production cost in biodiesel production. The incredibly high biodiesel yield of 93.55% was proved to be the synergetic effect of basicity between the active components of CaO–MgO shown in the physicochemical analysis.     

炭基固体酸催化废油脂合成生物柴油动力学研究(英文)

The kinetics of simultaneous transesterification and esterification with a carbon-based solid acid catalyst was studied.Two solid acid catalysts were prepared by the sulfonation of carbonized vegetable oil asphalt and petroleum asphalt.These catalysts were characterized on the basis of elemental analysis,acidity site concentration,the Brunauer-Emmett-Teller(BET)surface area and pore size.The kinetic parameters with the two catalysts were determined,and the reaction system can be described as a pseudo homogeneous catalyzed reaction.All the forward and reverse reactions follow second order kinetics.The calculated concentration values from the kinetic equations are in good agreement with experimental values.     

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%.     

A new process for catalyst-free production of biodiesel using supercritical methyl acetate

Production of glycerol is unavoidable in the conventional processes for biodiesel fuel (BDF) production. In this research, therefore, we investigated conversion of rapeseed oil to fatty acid methyl esters (FAME) and triacetin (TA) by processing of supercritical methyl acetate. As a result, it was discovered that the trans-esterification reaction of triglycerides with methyl acetate can proceed without catalyst under supercritical conditions, generating FAME and triacetin. In order to study the effect of the triacetin addition to FAME, its effect was investigated on various fuel characteristics. It was, consequently, discovered that there were no adverse effects on the main fuel characteristics when the molar ratio of methyl oleate to triacetin was 3:1, corresponding to the theoretically derived mole ratio from the trans-esterification reaction of rapeseed oil with methyl acetate. Moreover, the addition of triacetin to methyl oleate improved the pour point and triacetin has high oxidation stability. Therefore, by defining BDF as a mixture of methyl oleate with triacetin, we can obtain an improved yield of 105% of BDF by the supercritical methyl acetate, in excess of the yield of the conventional process.     

Enzymatic transesterification for production of biodiesel using yeast lipases: An overview

Biodiesel has provided an eco-friendly solution to fuel crisis, as it is renewable, biodegradable and a non-toxic fuel that can be easily produced through enzymatic transesterification of vegetable oils and animal fats. Enzymatic production of biodiesel has many advantages over the conventional methods as high yields can be obtained at low reaction temperatures with easy recovery of glycerol. Microbial lipases are powerful biocatalysts for industrial applications including biodiesel production at lower costs due to its potential in hydrolyzing waste industrial materials. Among them, lipases from yeasts, Candida antarctica, Candida rugosa, Cryptococcus sp., Trichosporon asahii and Yarrowia lipolytica are known to catalyze such reactions. Moreover, stepwise addition of methanol in a three step, two step and single step reactions have been developed using yeast lipases to minimize the inhibitory effects of methanol. The latest trend in biodiesel production is the use of whole-cell as biocatalysts, since the process requires no downstream processing of the enzyme. Synthesis of value added products from the byproduct glycerol further reduces the production cost of biodiesel. This review aims at compiling the information on various yeast lipase catalyzed transesterification reactions for greener production of biodiesel.     

Life cycle analysis of biodiesel production

Biodiesel has attracted considerable attention as a renewable, biodegradable, and nontoxic fuel and can contribute to solving the energy problems, significantly reducing the emission of gases which cause global warming.The first stage of this work was to simulate different alternative processes for producing biodiesel. The method used for the production of biodiesel is the transesterification of vegetable oils with an alcohol in the presence of a catalyst. The raw materials used were palm oils and waste cooking oil.The second stage was a life cycle analysis for all alternatives under study, followed by an economic analysis for the alternatives that present minor impacts and which are more promising from an economic point of view. Finally, we proceeded to compare the different alternatives from both the point of view of life cycle and economic analysis.The feasibility of all processes was proven and the biodiesel obtained had good specifications.From the standpoint of life cycle analysis, the best alternative was the process of alkaline catalysis with acid pre-treatment for waste cooking oil.The economic analysis was done to the previous mentioned process and to the process that uses raw virgin oils, methanol, and sodium hydroxide. This process has lower investment costs but the process of alkaline catalysis with acid pre-treatment, whose main raw material is waste oil, is much more profitable and has less environmental impacts.