间歇式反应器中用于生物柴油生产的牛油超临界酯交换反应

Paola A. Buitrago, Victor Fernando Marulanda Cardona
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De la misma forma, se verifico la ocurrencia de reacciones de descomposicion de la glicerina por medio de la identificacion de eteres y del contenido de agua en el biodiesel. La maxima conversion de trigliceridos se verifico a 400°C, con una relacion molar de 15:1 y 40 minutos de tiempo de reaccion. A estas condiciones, el etil oleato (C18:1) se descompuso completamente para formar isomeros cis-trans asi como etil octadecanoato (C18:0). Los esteres etilicos de cadena corta y los productos de descomposicion del glicerol tienen el potencial de beneficiar ciertas propiedades del biocombustible. EnglishSupercritical transesterification experiments of beef tallow with ethanol were carried out in a batch reactor in order to assess the effect of temperature (350 - 400°C), reactant molar ratio (9:1 - 15:1) and reaction time (8 - 40 min). Composition of the produced biofuel was assessed in terms of the percentage of peak area of the long chain Fatty Acid Ethyl Esters (FAEEs) identified, including also the decomposition products generated as a result of thermal cracking or cis-trans isomerization reactions. Thermal decomposition of FAEEs produced from beef tallow included short chain ethyl esters (C8 - C13), ethyl pentadecanoate (C15:0), heptadecanoate (C17:0), not initially present or prevalent in triglycerides sources, as well as ethyl stearate (C18:0) and n-alkanes. Glycerol decomposition reactions were also verified by the presence of glycerol ethers and water content in the produced biodiesel. The highest conversion of triglycerides was verified at 400°C, 15:1 triglycerides to ethanol molar ratio and 40-minute reaction time. At these conditions, ethyl oleate (C18:1) decomposed completely to form cis-trans isomers as well as ethyl octadecanoate (C18:0), which was attributed to double bond hydrogenation reactions. Short chain ethyl esters and glycerol decomposition products have the potential to benefit certain properties of the fuel such as viscosity and cold flow. portuguesOs experimentos de transesterificacao supercritica de sebo de bovino com etanol foram realizados em um reator batch no intuito de avaliar o efeito da temperatura (350 - 400°C), relacao molar de reagentes (9:1-15:1) e tempo de reacao (8 - 40 min). A composicao do biocombustivel produzido foi avaliada em termos de porcentagem de area de picos dos esteres etilicos de acidos graxos ou FAEEs (Fatty Acid Ethyl Esters), bem como os produtos de decomposicao produzidos pelas reacoes de cracking ou isomerizacao. A decomposicao termica dos FAEEs produzidos incluiu esteres etilicos de caida curta (C8 - C13) etil pentadecanoato (C15:0), heptadecanoato (C17:0), nao procedentes de acidos graxos presentes no sebo, bem como etil estearato (C18:0) e n-alcanos. 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引用次数: 4

摘要

为了评价温度(350 ~ 400℃)、反应物摩尔比(9:1-15:1)和反应时间(8 ~ 40 min)的影响,在批处理反应器中进行了牛脂与乙醇的超临界酯交换实验。所生产的生物燃料的组成是根据脂肪酸乙酸酯(FAEEs)的峰值面积百分比以及裂解或异构化反应产生的分解产物来评估的。产生的油脂的热分解包括短链乙酸酯(C8 - C13)、戊十二酸乙酯(C15:0)、十七酸乙酯(C17:0),它们不是来自油脂中的脂肪酸,以及硬脂酸乙酯(C18:0)和正烷烃。同样,通过鉴定生物柴油中的醚和含水量来验证甘油分解反应的发生。甘油三酯的最大转化发生在400°C,摩尔比为15:1,反应时间为40分钟。在这些条件下,油酸乙酯(C18:1)完全分解形成顺反式异构体和十八烷乙酯(C18:0)。短链乙基酯和甘油分解产物有可能有利于生物燃料的某些特性。为了评估温度(350 - 400℃)、反应摩尔比(9:1 - 15:1)和反应时间(8 - 40分钟)的影响,在批式反应器中进行了英国牛粪与乙醇的超临界酯交换反应实验。所生产的生物燃料的组成是根据所确定的长链脂肪酸乙基酯的峰值面积百分比进行评估的,还包括热裂解或顺式反式异构化反应产生的分解产物。牛粪的热分解包括短链乙基酯(C8 - C13),戊二酸乙基酯(C15:0),七癸酸乙基酯(C17:0),最初不存在或普遍存在于甘油三酯来源,以及硬脂酸乙基酯(C18:0)和正烷基。通过生产生物柴油中甘油醚和含水率的存在,也验证了甘油分解反应。在400°C、15:1甘油三酯与乙醇摩尔比和40分钟反应时间下验证了甘油三酯的最高转化。在这些条件下,油酸乙酯(C18:1)完全分解形成顺反异构体和十八烷基乙酯(C18:0),这归因于双键氢化反应。短链乙基酯和甘油酯的产物有可能从燃料的某些特性中获得一些优势,如热流动和冷流动。在批处理反应器中进行了牛脂与乙醇的超临界酯交换实验,以评价温度(350 - 400℃)、反应物摩尔比(9:1-15:1)和反应时间(8 - 40 min)的影响。以脂肪酸乙酸酯(FAEEs)的峰面积百分比以及裂解或异构化反应产生的分解产物来评价生物燃料的组成。所产生的油脂的热分解包括短落乙酸酯(C8 - C13)、五癸酸乙酯(C15:0)、十七癸酸乙酯(C17:0)、硬脂酸乙酯(C18:0)和正烷烃。同样,通过鉴定生物柴油中的醚和含水量,验证了甘油分解反应的发生。在400℃下,摩尔比为15:1,反应时间为40分钟,观察到甘油三酯的最大转化。在这些条件下,油酸乙酯(C18:1)完全分解形成顺式反式异构体和十八烷乙酯(C18:0)。短链乙酯和甘油分解产物有可能有利于生物燃料的某些特性。
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Supercritical transesterification of beef tallow for biodiesel production in a batch reactor
espanolLos experimentos de transesterificacion supercritica de sebo vacuno con etanol se llevaron a cabo en un reactor batch con el fin de evaluar el efecto de la temperatura (350 - 400°C), relacion molar de reactantes (9:1-15:1) y tiempo de reaccion (8 - 40 min). La composicion del biocombustible producido se evaluo en terminos del porcentaje de area de picos de los esteres etilicos de acidos grasos o FAEEs (Fatty Acid Ethyl Esters) asi como los productos de descomposicion generados de reacciones de cracking o isomerizacion. La descomposicion termica de los FAEEs producidos incluyo esteres etilicos de cadena corta (C8 - C13), etil pentadecanoato (C15:0), heptadecanoato (C17:0), los cuales no proceden de acidos grasos presentes en el sebo, asi como etil estearato (C18:0) y n-alcanos. De la misma forma, se verifico la ocurrencia de reacciones de descomposicion de la glicerina por medio de la identificacion de eteres y del contenido de agua en el biodiesel. La maxima conversion de trigliceridos se verifico a 400°C, con una relacion molar de 15:1 y 40 minutos de tiempo de reaccion. A estas condiciones, el etil oleato (C18:1) se descompuso completamente para formar isomeros cis-trans asi como etil octadecanoato (C18:0). Los esteres etilicos de cadena corta y los productos de descomposicion del glicerol tienen el potencial de beneficiar ciertas propiedades del biocombustible. EnglishSupercritical transesterification experiments of beef tallow with ethanol were carried out in a batch reactor in order to assess the effect of temperature (350 - 400°C), reactant molar ratio (9:1 - 15:1) and reaction time (8 - 40 min). Composition of the produced biofuel was assessed in terms of the percentage of peak area of the long chain Fatty Acid Ethyl Esters (FAEEs) identified, including also the decomposition products generated as a result of thermal cracking or cis-trans isomerization reactions. Thermal decomposition of FAEEs produced from beef tallow included short chain ethyl esters (C8 - C13), ethyl pentadecanoate (C15:0), heptadecanoate (C17:0), not initially present or prevalent in triglycerides sources, as well as ethyl stearate (C18:0) and n-alkanes. Glycerol decomposition reactions were also verified by the presence of glycerol ethers and water content in the produced biodiesel. The highest conversion of triglycerides was verified at 400°C, 15:1 triglycerides to ethanol molar ratio and 40-minute reaction time. At these conditions, ethyl oleate (C18:1) decomposed completely to form cis-trans isomers as well as ethyl octadecanoate (C18:0), which was attributed to double bond hydrogenation reactions. Short chain ethyl esters and glycerol decomposition products have the potential to benefit certain properties of the fuel such as viscosity and cold flow. portuguesOs experimentos de transesterificacao supercritica de sebo de bovino com etanol foram realizados em um reator batch no intuito de avaliar o efeito da temperatura (350 - 400°C), relacao molar de reagentes (9:1-15:1) e tempo de reacao (8 - 40 min). A composicao do biocombustivel produzido foi avaliada em termos de porcentagem de area de picos dos esteres etilicos de acidos graxos ou FAEEs (Fatty Acid Ethyl Esters), bem como os produtos de decomposicao produzidos pelas reacoes de cracking ou isomerizacao. A decomposicao termica dos FAEEs produzidos incluiu esteres etilicos de caida curta (C8 - C13) etil pentadecanoato (C15:0), heptadecanoato (C17:0), nao procedentes de acidos graxos presentes no sebo, bem como etil estearato (C18:0) e n-alcanos. De igual modo, verificou-se a ocorrencia de reacoes de decomposicao da glicerina atraves da identificacao de eteres e do conteudo de agua no biodiesel. A maxima conversao de triglicerides foi verificada a 400°C, com uma relacao molar de 15:1 e 40 minutos de tempo de reacao. Sob essas condicoes, o etil oleato (C18:1) decompos-se completamente para formar isomeros cis-trans, bem como etil octadecanoato (C18:0). Os esteres etilicos de cadeia curta e os produtos da decomposicao do glicerol tem o potencial de beneficiar certas propriedades do biocombustivel.
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