废弃油脂原料SRCA生物柴油技术的研发与工业应用示范

针对废弃油脂品质差,酸值高,难于采用传统的碱催化酯交换技术加工生产生物柴油,中国石化石油化工科学研究院开展了超/近临界甲醇介质中油脂溶解和反应的基础研究,相继解决了甲醇与油脂的互溶、降低反应条件,三脂肪酸甘油酯和游离脂肪酸的深度转化,以及产品质量等问题,成功开发了近临界醇解生物柴油技术(以下简称SRCA),于2009年建成了6万吨/年工业化示范装置,以酸化油和餐厨废油为原料,生产连续稳定,产品收率高且满足国家生物柴油质量标准(GB/T20828-2007).     

气相色谱法测定生物柴油中脂肪酸甲酯含量

生物柴油是利用动植物油脂等可再生资源通过酯交换技术制造的可以替代石化柴油的新型清洁安全燃料[1-3]它的主要成分是脂肪酸甲酯。由于不同油脂原料所生产的生物柴油的脂肪酸甲脂组成不同因而测定时所需的气相色谱条件与方法也不尽相同[4-6]。本文采用HP-innowax毛细管色谱柱,     

多频超声反应槽连续强化酸化油酯交换制备生物柴油研究

以平均酸值高达33.07 mgKOH/g不可食用的廉价酸化油为原料,利用自行设计的多频超声溢流槽连续强化酯交换反应生物柴油生产装置,先后经预酯化、酯交换两步反应,高效、低耗的制备生物柴油。主要考察了室温下物料流量(停留时间)、超声功率、超声频率及组合、KOH用量、醇油物质的量比对酯交换反应的影响及单位产品能耗。结果表明,多频组合超声辐射比单频更有利于生物柴油的制备;预酯化后的油料在流量为25 L/h(物料停留时间为54 min),催化剂(KOH)用量为1.2%(质量分数),醇油物质的量比为6∶1和各反应槽功率为200 W的条件下,甲酯产率达96.83%。50 L废弃酸化油能制得符合国标GB19147—2009的生物柴油48L,整个生物柴油制备过程总耗时和总耗电量仅为8.667 h、5.42 kWh。     

游离脂肪酶NS81006催化油脂醇解制备生物柴油的酶促反应动力学

探究了游离脂肪酶NS81006催化油脂甲(乙)醇解制备生物柴油的反应历程,并对该体系进行了酶促反应动力学研究.结果表明,催化过程中油脂同时存在酯交换及先水解再酯化两种反应历程.在以甲醇或乙醇作为酰基受体的反应过程中,酯交换反应速率明显大于水解反应速率.进一步研究表明,油脂甲醇解反应速率常数大于乙醇解,揭示了以甲醇或乙醇为不同酰基受体时反应速率存在差异的主要原因在于乙醇解反应的酯交换过程较慢.     

气相色谱法测定生物柴油中甲醇和乙醇的残留量

正生物柴油是由可再生的动植物油脂甲醇(或者乙醇)在催化剂的作用下,经酯交换反应而得到的长链脂肪酸酯,是一种可以替代普通石化柴油的可再生清洁燃料~([1-3])。随着世界范围内车辆的快速增加,柴油的需求量愈来愈大。而石油资源的日益枯竭和人们环保意识的提高,大大促进了世界各国加快柴油替代燃料的开发步伐,生物柴油以其优越的环保性能和可再生性受到各国的重视~([4-6])。醇是生产生物柴油的原料之一,只有在适当的     

钙基负载型固体碱催化酯交换反应活性评价

动植物油脂与醇通过酯交换反应制备生物柴油,目前,工业上一般采用NaOH、KOH、NaOCH,等均相催化剂。均相催化剂的缺点是产品后处理复杂,产生大量含碱含油工业废水。而非均相固体碱催化酯交换反应,产品与催化剂分离容易,产品不需要水洗,避免了大量废液的排放。采用非均相固体碱制备生物柴油的文献报道较多,但固体碱的碱中心数、碱中心强度对酯交换反应影响的报道较少。本研究制备了钙基负载型固体碱催化剂,重点研究钙基负载型固体碱的制备工艺条件对碱强度、碱量分布的影响,考察碱强度、碱量分布对催化菜籽油与甲醇的酯交换反应制备生物柴油转化率的影响。     

脂肪酸在超临界甲醇中的酯化反应研究

超临界甲醇中的酯化和酯交换反应是利用植物油、动物油或废油脂制备生物柴油的新工艺.它的最大特点是不需要添加催化剂,超临界甲醇既是反应媒介,又是反应物.     

酯交换法制备可生物降解脂肪族聚碳酸酯及其应用的研究进展

脂肪族聚碳酸酯（APC）作为一类重要的可生物降解高分子材料,具有良好的生物降解性、生物相容性和物理机械性能,受到人们的广泛关注。APC的制备方法主要有光气法、开环聚合法、二氧化碳／环氧化物共聚法和酯交换法。近年来,有关开环聚合法和二氧化碳／环氧化物共聚法制备APC的研究越来越多,而酯交换法制备APC的研究相对较少。本文...     

油菜籽与超临界甲醇原位萃取-酯交换反应制备生物柴油

生物柴油;超临界甲醇;萃取;酯交换法;油菜籽;原位     

固体碱催化剂K_2CO_3/Al_2O_3的制备及其催化餐饮废油制生物柴油的性能

采用浸渍法制备了K2CO3/Al2O3固体碱催化剂,考察了活性组分负载量、焙烧温度、焙烧时间等制备条件对催化剂在催化餐饮废油合成生物柴油的酯交换反应中催化活性的影响,并对其进行了FT-IR、XRD、TG-DTG、SEM和BET表征分析。实验结果表明,所制备的催化剂在催化餐饮废油合成生物柴油的酯交换反应中表现出良好的活性,在活性组分K2CO3负载量为50%、焙烧温度500℃、焙烧时间3 h的条件下制备的催化剂催化酯交换反应时,生物柴油产率可达86.70%。催化剂表征结果显示,K2CO3/Al2O3催化活性是因K2CO3与Al2O3经高温焙烧产生新的晶相有关。催化剂重复使用4次,生物柴油产率仍在75%以上。制得的生物柴油产品质量达到国家生物柴油B100标准。     

Transesterification of Waste Frying Oil and Soybean Oil by <Emphasis Type="Italic">Combi</Emphasis>-<Emphasis Type="Italic">lipases</Emphasis> Under Ultrasound-Assisted Reactions

This work describes the use of an ultrasound system for the enzymatic transesterification of oils using combi-lipases as biocatalyst. The reactions were carried out evaluating the individual use of waste oil and fresh soybean oil, and the immobilized lipases CALB, TLL, and RML were used as biocatalysts. It was performed in a mixture design of three factors to obtain the ideal mixture of lipases according to the composition of fatty acids present in each oil, and the main reaction variables were optimized. After 18 h of reaction, ultrasound provided a biodiesel yield of about 90% when using soybean oil and 70% using the waste oil. The results showed that ultrasound technology, in combination with the application of enzyme mixtures, known as combi-lipases, and the use of waste oil, could be a promising route to reduce the overall process costs of enzymatic production of biodiesel.     

Utilization of waste seashells and Camelina sativa oil for biodiesel synthesis

The seafood industry produces over 100 million pounds of seashell waste every year. With landfill space diminishing quickly, ways to recycle waste materials are becoming more sought for. Herein, we utilized waste mussel, clam and oyster shells as heterogeneous catalysts for the transesterification of Camelina sativa oil as a feedstock into biodiesel. Camelina sativa oil provides a reliable solution for biodiesel production because it has high tolerance of cold weather, drought, low-fertility soils and contains approximately 40% oil content. The catalysts from waste seashells were characterized by X-ray powder diffraction and Fourier transform infrared (FTIR) spectroscopy. High biodiesel yields were achieved at a 12:1 (alcohol:oil) molar ratio with 1?wt.% waste seashell catalysts in 2?h at 65°C. Biodiesel was analyzed by ¹H NMR and FTIR spectroscopy and the fuel properties of the biodiesel produced from Camelina sativa oil and waste seashells were compared with American Society for Testing and Materials standards.     

Transesterification of Soybean Oil Catalyzed by Calcium Hydroxide which Obtained from Hydrolysis Reaction of Calcium Carbide

Calcium carbide residue (CCR) was investigated in transesterification reaction of triglycerides to determine its viability as a solid catalyst for biodiesel synthesis. Literature survey showed that CCR has never been studied as a solid catalyst in the transesterification of triglyceride. The scope of the study includes the effects of CCR calcination temperature, calcination time, the alcohol/oil molar ratio, the catalyst amount (wt % of oil) and the reaction time. The relationship between chemical composition and catalytic activity of waste cement was also investigated. These CCR catalysts, thermally activated at 600 °C, can give rise to fatty acid methyl esters (FAME) purity higher than 99.5%, after 3 h of reaction, when oil/methanol molar ratio of 1/12 and 1 wt % of the catalyst were employed. Application of CCR as catalyst for biodiesel production in this study may not only provide a cost‐effective and environment friendly way of recycling CCR waste but also reduce hopefully the cost of biodiesel production.     

亚临界条件下地沟油制备生物柴油副产物中有机氯化物的定性检测及来源分析

该文介绍了一种生物柴油副产物粗甘油和拔出轻组分中有机氯化物的气相色谱-质谱（GC-MS）定性检测方法。样品来自于亚临界条件下地沟油与甲醇的酯交换反应，总氯含量较高。在GC-MS分析之前采用正己烷萃取脱除样品中的脂肪酸甲酯和游离脂肪酸等脂溶性干扰组分，对参考标准样品3-氯代甘油和2-氯代甘油以及样品的脱脂水相部分进行苯硼酸衍生化、正己烷萃取、浓缩等处理，经正己烷复溶后进行GC-MS分析。结果表明，生物柴油副产物中的有机氯化物主要为3-氯代甘油和2-氯代甘油。参考已有文献的研究结果和生物柴油制备工艺对有机氯化物的来源进行了讨论，推断原料地沟油中存在的大量无机氯盐是导致产生3-氯代甘油和2-氯代甘油的主要原因。     

Sodium and potassium silicate-based catalysts prepared using sand silica concerning biodiesel production from waste oil

Heterogeneous catalysts, named SPS (sodium potassium silicates), were synthesized with an alternative silica (MPI silica) obtained from beach sand. In this work, the MPI was modified with NaOH and KOH producing silicate-based catalyst for biodiesel synthesis from waste cooking oil (WCO). The obtained catalyst was characterized by XRD, CO₂-TPD, the Hammett basicity test, XRF, FESEM, EDX, FTIR and TG/DTG. The results confirmed the presence of K₂O/Na₂O oxides and their silicates, the main active sites responsible for the catalytic action. CO₂-TPD and the Hammett basicity data suggested the presence of weak, medium and strong basic sites. Biodiesel yield was about 92% and the SPS catalyst was reused for five cycles. The biodiesel conversion by NMR ¹H was about 93.89%. The DTG deconvolution revealed the decomposition of four typical biodiesel compounds (R² = 0.9987). The method applied for the WCO biodiesel production using SPS catalyst represents an environmentally friendly process, based on low-cost material and reuse of waste biomass.     

Biodiesel Production from Integration Between Reaction and Separation System: Reactive Distillation Process

Biodiesel is a clean burning fuel derived from a renewable feedstock such as vegetable oil or animal fat. It is biodegradable, non-inflammable, non-toxic, and produces lesser carbon monoxide, sulfur dioxide, and unburned hydrocarbons than petroleum-based fuel. The purpose of the present work is to present an efficient process using reactive distillation columns applied to biodiesel production. Reactive distillation is the simultaneous implementation of reaction and separation within a single unit of column. Nowadays, it is appropriately called “Intensified Process”. This combined operation is especially suited for the chemical reaction limited by equilibrium constraints, since one or more of the products of the reaction are continuously separated from the reactants. This work presents the biodiesel production from soybean oil and bioethanol by reactive distillation. Different variables affect the conventional biodiesel production process such as: catalyst concentration, reaction temperature, level of agitation, ethanol/soybean oil molar ratio, reaction time, and raw material type. In this study, the experimental design was used to optimize the following process variables: the catalyst concentration (from 0.5 wt.% to 1.5 wt.%), the ethanol/soybean oil molar ratio (from 3:1 to 9:1). The reactive column reflux rate was 83 ml/min, and the reaction time was 6 min.     

Utilisation of Non-Edible Source (Pongamia pinnata Seeds Shells) for Producing Methyl Esters as Cleaner Fuel in the Presence of a Novel Heterogeneous Catalyst Synthesized from Waste Eggshells

Waste eggshells were considered for synthesising a precursor (CaO) for a heterogeneous catalyst, further impregnated by alkali caesium oxide (Cs₂O). The following techniques were used to characterise the synthesised catalysts: X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Energy-dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and Temperature Programmed Desorption (CO₂-TPD). The synthesised catalyst revealed its suitability for transesterification to produce biodiesel. The biodiesel production process was optimised, and it showed that the optimal biodiesel yield is 93.59%. The optimal set of process parameters is process temperature 80 °C, process time 90 min, methanol-to-oil molar ratio 8 and catalyst loading 3 wt.%. It has been found that the high basicity of the catalyst tends to give a high biodiesel yield at low methanol-to-oil ratio 8 when the reaction time is also less (90 min). The fuel properties of biodiesel also satisfied the standard limits defined by ASTM and the EN standards. Thus, the synthesised catalyst from waste eggshells is highly active, improved the biodiesel production conditions and PPSS oil is a potential nonedible source.     

Effect of Biodiesel-derived Raw Glycerol on 1,3-Propanediol Production by Different Microorganisms

The microbial production of 1,3-propanediol (1,3-PD) from raw glycerol, a byproduct of biodiesel production, is economically and environmentally advantageous. Although direct use of raw glycerol without any pretreatment is desirable, previous studies have reported that this could cause inhibition of microbial growth. In this study, we investigated the effects of raw glycerol type, different microorganisms, and pretreatment of raw glycerol on the production of 1,3-PD. Raw glycerol from waste vegetable-oil-based biodiesel production generally caused more inhibition of 1,3-PD production and microbial growth compared to raw glycerol from soybean-oil-based biodiesel production. In addition, two raw glycerol types produced from two biodiesel manufacturers using waste vegetable oil exhibited different 1,3-PD production behavior, partially due to different amounts of methanol included in the raw glycerol from the two biodiesel manufacturers. Klebsiella strains were generally resistant to all types of raw glycerol while the growth of Clostridium strains was variably inhibited depending on the type of raw glycerol. The 1,3-PD production of the Clostridium strains using acid-pretreated raw glycerol was significantly enhanced compared to that with raw glycerol, demonstrating the feasibility of using raw glycerol for 1,3-PD production by various microorganisms.     

Nanocatalysts for biodiesel production

Biofuels are a class of clean fuels and promising for energy demand. Biodiesel is relatively costly, which limits the commercialization of the product. The waste edible oil and animal fats are raw materials for biodiesel production. This paper focuses on the catalytic production of biofuels and reviews the application of different catalysts to produce biodiesel from waste oils by using esterification and transesterification reactions. The reaction in the presence of nanocatalysts is carried out under mild operating conditions. Nowadays, magnetic nanocatalysts are preferred to bulk catalysts due to the absence of mass transfer resistance and fast deactivation as well as high recovery rate during the separation. Functionalized magnetic nanocatalysts are more attractive for biodiesel production. Further studies should do to develop highly active and selective nanocatalysts for industrial scale.