Transesterification Reaction of Waste Cooking Oil and Chicken Fat by Homogeneous Catalysis

In the last years, biodiesel production has been on a steady increase due to it is renewable and biodegradable fuel. The process to obtain biodiesel can be carried out using different raw materials. It is conlmonly performed by transesterification reaction of vegetable oils with methanol and using a homogeneous or heterogeneous catalyst. This work seeks to compare the results produced in transesterification of wasted cooking oil and chicken fat by homogeneous catalysis with NaOH. Due to in each case triglyceride comes from different raw materials, operation conditions differ slightly, which is more evident in the values used for the temperature. For chicken fat was used temperature variations between 35 ℃ and 55 ℃, varying catalyst in percentages between 0.3% and 0.7% with a molar ratio 6：1 in all cases and a reaction time of I h. Likewise, the conditions used in the tmnsesterification process of waste cooking oil were temperature between 50 ℃ and 60 ℃ with a molar ratio 6/1 and 9/1 for alcohol and oil, and catalyst percentage between 0.5% and 0.7% by weight. The yields obtained were between 78% and 94%, or 83% and 95%, for chicken fat and wasted cooking oil, respectively.     

Production Optimization of Biodiesel from Frying Oil Waste to Reduce the Environmental Impacts

The objective of this study was to reduce the environmental impacts of used frying oil waste through the production of biodiesel. A 22 factorial planning has been used to evaluate the influences of alcohol/oil and reaction time on the biodiesel production yield. The optimal condition to produce the biodiesel has been found by use of the response surface methodology and analysis of variance to obtain the fitting model. This study was conducted in Campinas city, Brazil, where were collected the waste oil. An analysis of ecological cost also has been developed. Cooking oils collected from Campinas homes were mixed with ethanol in planned proportions （1：9, 1：7 and 1：5） and were transesterified at 60 ℃ and planned reaction times （30, 60 or 90 min）, in order to obtain biodiesel, using 0.1% NaOH as a catalyst. The results of the physical-chemical analyses demonstrated that the biodiesels obtained possessed characteristics close to those required by Brazilian standards. This fuel could be used in fleets of buses, trucks and machines, or even sold to fuel distributors, which results in a solving between US$0.8 and US$4.5 millions. Thus, Campinas would gain environmental credits and become a sustainable city.     

正交实验法优化地沟油制生物柴油产物粗甘油的提纯

Purification of original crude glycerol obtained from biodiesel production was conducted in a laboratory scale equipment by means of a combined chemical and physical treatment method based upon repeated cycles of acidification of liquid phase to the desired pH value by using 5.85% H3PO4 solution for pH value adjustment, and the mixture was kept at 70℃ for 60min to make phase separation for obtaining a glycerol-rich middle phase. The yield of crude glycerol reached 81.2%. Subsequently, upon reaction of the obtained glycerol phase with 0.03% of sodium oxalate at 80℃ for 30min the impurity removal rate was equal to 19.8%. The fraction boiling between 164℃ and 200℃ was collected by vacuum distillation followed by decolorization with 2% of active carbon at 80℃ for two times to yield the product glycerol with an acceptable purity of 98.10%.     

均相催化废餐饮油制备生物柴油工艺研究

考察了用浓H2SO4及NaOH催化废餐饮油和甲醇反应制备生物柴油的反应条件.结果表明,用NaOH作催化剂的2步酯交换法制备生物柴油时,预处理过程的最佳条件为:醇油质量比为0.4,催化剂H2SO4用量占原料油的质量分数为2.0%,反应时间为0.5 h,反应温度为65℃.主反应的最佳条件为:醇油质量比为0.25,催化剂用量为0.8%,反应温度为65℃,反应时间为1 h.在上述工艺条件下,产品生物柴油的收率可达95%,其各项性能实测值均达到欧洲生物柴油的标准要求.     

利用高酸值餐饮废油脂制备生物柴油

以高酸值餐饮废油脂为原料,在酯化反应后再经两步酯交换反应制备生物柴油。在酯化反应中添加吸水剂可降低油脂的酸值,经一次酯化反应即可将油脂的酸值降至2m g/g左右,满足酯交换反应的要求。考察了酯化反应中吸水剂的添加方式、种类及其用量对酯化反应的影响,以及酯交换催化剂的种类及用量对脂肪酸甲酯(FAME)收率和产物组成的影响。实验结果表明,以凹凸棒土为吸水剂(用量为餐饮废油脂中游离脂肪酸质量的3%),且在酯化反应30m in时加入,酯化效果较好;以质量比为1∶1的NaOH和KOH混合物为催化剂进行两步酯交换反应时,催化剂的最佳用量依次为1.00%和0.75%(质量分数,基于油脂的质量),FAME收率最高达到96.33%。     

废食用油用于沥青再生的应用前景分析

我国废食用油已成为环境污染物,并冲击食品安全,如近年来地沟油事件频发,严重危害着人们身心健康。废食用油中含有大量不饱和脂肪酸,类似于沥青中的油分,而沥青老化后其油分会减少。根据沥青再生理论与相关研究,废食用油可作为低粘度油分用于沥青再生,有望通过以废治废的方式,实现废食用油与废旧沥青路面材料的同时利用,有利于环境保护,具有广阔的应用前景。为了实现废食用油在沥青再生领域的应用,应该重点开展废食用油的分类与处理技术、废食用油对老化沥青的再生效果、再生机理以及应用技术等方面的研究。     

酶促合成生物柴油反应动力学

以Candidasp.99-125脂肪酶为催化剂,甘油三油酸酯和甲醇为底物,采用有序机制模型对酶促合成生物柴油的酯交换反应动力学进行了研究,并与经典乒乓机制模型进行了比较。研究结果表明,反应初速率的实验值与有序机制模型方程的计算值吻合很好。对于固定化Candidasp.99-125脂肪酶催化合成生物柴油的酯交换反应机理进行研究,采用有序机制模型比经典乒乓机制模型更为精确。反应过程中,醇抑制为竞争性抑制,在甘油三油酸酯浓度较小的范围内,醇抑制作用较为显著,醇浓度越低反应初速率越快。该有序机制模型可用来预测生物柴油的生产批次或连续反应器中酯交换反应的速率,确定最佳底物油脂和醇的浓度。     

超声波辅助下海滨锦葵油制备生物柴油工艺的优化

以海滨锦葵油为原料、KOH 为催化剂,在超声波辅助下制备了生物柴油。通过单因素实验及正交实验研究了超声波频率、超声波功率、催化剂用最、反应温度、醇了油摩尔比等因素对酯交换率的影响实验结果表明,各影响因素对酯交换率影响的大小顺序为:超声波功率>催化剂用量>反应温度>醇与油摩尔比。海滨锦葵油在超声波辅助下制备生物柴油的最佳工艺条件为:超声波频率45 Hz、超声波功率180 W、催化剂 KOH 用量为海滨锦葵油质量的0.6%、反应温度65℃、醇与油摩尔比7,在该条件下酯交换率达到99.85%。     

化学改性餐饮废油制备双酯衍生物作为矿物基润滑油基础油的替代品

In order to provide a new way for waste cooking oil(WCO) resource utilization, several diester derivatives were obtained from WCO through a three-step chemical modifications, viz.: transesterification, epoxidation and oxirane ring opening with carboxylic acids. The effects of the chain length of side chain groups on the viscosity, acid value, low temperature fluidity, thermo-oxidative stability, tribological properties and surface tension of diester derivatives were investigated. The results showed that increasing the chain length of side chain groups had a positive influence on the viscosity, viscosity index, acid value, pour point, friction coefficient and wear scar diameter along with a negative influence on the oxidation onset temperature, volatile loss, insoluble deposit, maximum non-seizure load and surface tension. These diester derivatives exhibited improved physicochemical and tribological properties that make themselves promising environmentally friendly biolubricant basestocks.     

B酸离子液体催化棉籽油酯交换制备生物柴油

制备了5种对水稳定性好、带—SO3H官能团的磺酸类B酸离子液体,并以它们作催化剂进行了棉籽油酯交换反应制备生物柴油的研究。实验结果表明,这些磺酸类B酸离子液体的催化活性高,它们的催化活性与含氮官能团的种类和碳链长度有关,其中,吡啶丁烷磺酸硫酸氢盐离子液体的催化活性最高。考察了吡啶丁烷磺酸硫酸氢盐离子液体的用量、醇与油摩尔比、反应温度对酯交换反应的影响及离子液体的稳定性,实验结果表明,在反应温度170℃、n(甲醇)∶n(棉籽油)∶n(离子液体)=12∶1∶0.057、反应时间5h的条件下,产物中脂肪酸甲酯的质量分数可达92.0%,且离子液体的稳定性好,可循环使用。     

Synthesis of Diesel Fuel From Waste Cooking Oil Through Catalytic Hydrotreating

Diesel fuel was synthesized from waste cooking oil using a commercial NiMo/Al₂O₃ catalyst in a batch reactor under different reaction conditions. The influence of reaction conditions, such as pressure, reaction time, and catalyst-to-oil ratio, were studied during hydrotreating through a response surface methodology and a polynomial model was obtained. The feedstock was characterized to quantify its acid number and density/viscosity. The diesel fuel obtained was characterized to obtain the pour point and density/viscosity. In addition, the yield of diesel fuel was obtained by simulated distillation. The maximum yield of diesel obtained was 91 wt% at the following reaction conditions: 72 bar, 3.6 h, and 3.5 wt%/wt% of catalyst-to-oil ratio.     

NaOH催化微波法制备生物柴油的工艺研究

采用NaOH为催化剂,在微波加热下进行均相酯化反应制备生物柴油,得到最佳工艺条件为：醇油摩尔比14,催化剂含量1．2％,微波输出功率360W,反应时间2min,大豆油的平均转化率达到98．2％,优于水浴加热方式。     

米糠油酯交换反应制备生物柴油的研究

以米糠油和甲醇为原料,在硫酸催化剂作用下进行预酯化,在碱催化剂(氢氧化钾)下进行酯交换反应制备生物柴油.考察酯交换反应过程中甲醇与米糠油物质的量比、反应温度、反应时间及催化剂用量(以米糠油质量计)对生物柴油产率的影响.结果表明,在甲醇与米糠油物质的量比为6:1、反应温度为65℃、反应时间为1.5 h及催化剂用量为1.5...     

KF/CaO催化剂催化大豆油酯交换反应制备生物柴油

采用等体积浸渍法制备了KF/CaO催化剂,并将其用于催化大豆油与甲醇酯交换反应制备生物柴油。考察了催化剂制备条件和反应条件对酯交换反应的影响。实验结果表明,通过等体积浸渍并在873K煅烧4h,可以制得理想的KF添加量(KF与CaO的质量比)为14.3%的KF/CaO催化剂,采用该催化剂,当醇与油摩尔比为12∶1、催化剂用量(催化剂与油的质量比)为3%、反应温度为60～65℃、反应时间为1h时,生物柴油的收率可以达到90%。与CaO催化的酯交换反应结果相比,KF/CaO催化剂的催化活性明显提高。XRD与TG-DTG分析结果表明,KF/CaO催化剂酯交换活性的增强与KF与CaO经过高温煅烧发生相互作用而形成新的晶相密切相关。     

采用废弃油脂生产生物柴油的SRCA技术工业应用及其生命周期分析

废弃油脂是食用油生产和使用过程中产生的非食用性油脂,全世界要产生30Mt/a以上,对其处置不当将危害环境。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针对废弃油脂的质量特性,开发了近临界甲醇醇解(SRCA)生物柴油技术。2009年首次建成了60kt/a工业化示范装置,以酸化油为原料,打通了全流程,实现了连续运行生产,产品质量满足国家标准(GB/T 20828)要求。在实验室和工业运行数据的基础上,对选择废弃油脂生产生物柴油的SRCA工艺进行了生命周期分析。与传统工艺相比,SRCA工艺没有增加环境负担。     

负载型固体碱催化棕榈油酯交换制备生物柴油

采用浸渍法制备了KF/CaO,K2CO3/CaO,KF/γ-Al2O3,K2CO3/γ-Al2O34种负载型固体碱催化剂。考察了催化剂种类对棕榈油与甲醇进行酯交换反应的影响,并研究了催化剂重复使用的可能性。实验结果表明,4种催化剂均具有较高的活性,在催化剂中活性组分负载量为20.0%(相对于载体的质量分数)、n(甲醇):n(棕榈油)=12、m(催化剂):m(棕榈油)=0.09、反应温度65℃、反应时间6h的条件下,生物柴油的收率依次为97.3%,93.4%,77.7%,96.2%。以CaO为载体的催化剂再生后活性较低,而以γ-Al2O3为载体的催化剂再生后活性较高。X射线衍射和热重-差热分析结果显示,催化剂活性的差异与煅烧过程中活性组分和载体相互作用形成的新晶相有关,再生后催化活性的降低是由于活性组分流失所致。     

固定化脂肪酶催化棉籽油与碳酸二甲酯反应制备生物柴油

以叔丁醇为有机溶剂,采用固定化脂肪酶Novozym435催化棉籽油与碳酸二甲酯进行酯交换反应制备了生物柴油,考察了加水量、碳酸二甲酯与棉籽油的摩尔比、反应温度、反应时间、搅拌转速、Novozym435用量(基于棉籽油的质量分数)和叔丁醇与碳酸二甲酯的体积比对脂肪酸甲酯收率的影响,以及Novozym435的重复使用性能。实验结果表明,在碳酸二甲酯与棉籽油的摩尔比为4、叔丁醇与碳酸二甲酯体积比为1.5、Novozym435用量(基于棉籽油的质量分数)12.5%、反应温度50℃、反应时间24h、搅拌转速160r/min、不加水的优化反应条件下,脂肪酸甲酯收率可达96%以上;与石油醚溶剂相比,Novozym435在叔丁醇溶剂中的稳定性较好。     

KF/水滑石的合成及催化大豆油酯交换制备生物柴油

采用浸渍法制备了KF/水滑石固体碱催化剂,并将其用于催化大豆油与甲醇进行酯交换反应制备生物柴油;考察了催化剂制备条件和酯交换反应条件对生物柴油收率的影响,并对催化剂进行了XRD,TG-DTA,SEM表征。研究结果表明,KF/水滑石的最佳制备条件为:KF负载量(占水滑石的质量)80%、焙烧温度500℃、焙烧时间3 h。将此条件下制备的KF/水滑石催化剂用于大豆油与甲醇酯交换反应,最佳的反应条件为:催化剂用量(占大豆油的质量)2%,甲醇与大豆油的摩尔比12∶1,反应时间3 h,反应体系处于回流状态。在此条件下,生物柴油的收率高达90.4%。表征结果显示,KF/水滑石的催化活性与KF和水滑石在高温煅烧时相互作用形成新的晶相KMgF3和K3AlF6有关。     

模板法制备CaO/ZrO_2催化剂催化菜籽油合成生物柴油

以桦木为模板,通过模板法制备了不同CaO含量的CaO/ZrO2复合氧化物固体碱催化剂,用于催化菜籽油与甲醇进行酯交换反应合成生物柴油。利用BET,XRD,XPS,SEM等手段对所制备的催化剂进行表征。实验结果表明,采用该方法制备的CaO/ZrO2催化剂具有桦木的生物形态,且桦木模板的使用有助于改善其孔道结构并提高其比表面积、孔径和孔体积;具有生物形态的复合氧化物保持了较高的碱强度,催化活性较高;当CaO/ZrO2催化剂中n(Ca)∶n(Zr)=0.3、催化剂用量(基于菜籽油的质量)8%(w)、甲醇与菜籽油的摩尔比72、反应温度150℃、反应时间6 h时,生物柴油的收率最高可达到91.0%。     

无甘油副产生物柴油的组分分析及其燃烧性能

以氢氧化钾为催化剂催化棕榈油和新型甲酯化试剂MC进行酯交换反应制备生物柴油,采用气相色谱和气质联用的方法对反应产物进行了定性、定量分析。分析结果表明,由该工艺制得的生物柴油由主产物脂肪酸甲酯和副产物甘油碳酸酯组成。测定了生物柴油的主要物理性能指标,同时在柴油机未作任何调整的情况下进行了台架试验,考察了生物柴油与0#柴油混合燃料对柴油机燃烧过程、经济性和排放性的影响。实验结果表明,制得的生物柴油的密度、酸值和运动黏度均符合国家标准,将其与0#柴油混合(生物柴油体积分数20%)后可直接应用于柴油机,MC和甘油碳酸酯对缸内燃烧过程和经济性影响很小;燃用添加MC和甘油碳酸酯的混合燃料能有效降低柴油机碳烟、碳氢化合物和CO的排放量,NOx排放量稍有增加。