两步法催化餐饮废油制备生物柴油及其可行性研究
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摘要
随着环境意识的增强和能源危机的影响,人们开始寻找一种能够替代石油燃料并对环境破坏小的新能源。最近石油价格的升高和石油的缺乏,使人们开始思考利用植物油去替代柴油。同时,餐饮废油不仅污染环境,而且还危害人们的健康,因此餐饮废油的有效利用成为一个值得研究的问题。
酯交换法制取生物柴油是当今最容易实现工业化的一种方式。在众多的清洁替代能源中,脂肪酸甲酯作为柴油的替代品有很多的优点。影响酯交换反应的主要因素有醇油比、催化剂、反应温度和压力、反应时间以及游离脂肪酸和油中水分含量。基于酸催化和碱催化的方法,本课题主要讨论了如何将废油转化为可以替代2#柴油并应用于柴油发动机中的技术路线,通过气相色谱(GC)分析其中的转化率,通过正交实验得到碱催化进行酯交换实验的最优条件。通过对合成的生物柴油作了石油标准检测,对其燃烧特性作了初步的研究。实验结果证实了用生物柴油替代2#号柴油的可行性。通过Grunberg-Nissan公式,研究了生物柴油粘度与转化率的关系,得出了靠粘度评价转化率的方法。
餐饮废油酸败程度较高,酸价达7.25,酸度达8.8%。考虑到原料油的这种特性,在第一步反应中采用酸催化法将游离脂肪酸甲酯化,避免直接采用碱催化法使游离脂肪酸皂化产率降低的不足。酸催化法的酯化工艺最佳操作条件为:催化剂为98%浓硫酸,催化剂用量为14.6%(占反应总底物的质量比);反应温度为60℃;醇油比为50﹕1(摩尔比);反应时间6h,转化率达到为65.9%。在第二步反应中,采用碱催化法将酸价降低的原料油中的主要成分甘油三酯转化为脂肪酸甲酯。碱催化法的酯交换工艺最佳操作条件为:醇油比为9﹕1,催化剂质量分数为1.3%,反应温度为50℃,反应90min,转化率达到为75.3%。在本试验中确定了从生物柴油的粘度分析甲酯转化率的方法。在所转化的废油各主要成分己知的情况下,由公式可以较为准确的测定甲酯的百分比,其中重要参数GMG = -2.41026mPa·s。
本文还对餐饮废油酯交换生产生物柴油的技术可行性进行了论证,并对其经济成本分析进行了研究。本可行性研究报告根据相关行业规范,并结合当前的生产和销售市场的动态,对该项目的建设规模、采用的技术方案、设备计算选型等各项指标进行了详细的可行性分析。并对该项目的投资估算、社会效益和经济效益进行了综合评估。该项目总投资3252万元人民币,年销售收入为4505万元人民币,年均利润为605万元人民币。本项目对餐饮废油的综合利用提供了广阔的应用前景,同时解决了餐饮废油的环境污染问题。
With the increase of environmental awareness and depletion of energy resources, a novel energy source that has little environmental damage must be found out to replace of petroleum. And vegetable oil has been used for diesel substitution. However, this conflicts with people’s demand for food, although there is great breakthrough in using vegetable oil for diesel substitution. Waste cooking oil is discarded oil, which can be used as raw materials for biodiesel production. And this can also protect our environment. So producing biodiesel with waste cooking oil as raw materials is an efficient way.
Compared with other new renewable and clean engine fuel alternatives, methyl esters of vegetable oils have many outstanding advantages. The transesterification process is most likely to be an industrial process method in future. Producing biodiesel by transesterification of waste cooking oil and methanol was studied and a two-step acid-base catalyzed route for producing biodiesel was established in the paper. The main factors that affecting the yields of fatty acid methyl ester, such as the molar ratio of methanol to oil, catalyst concentration, reaction temperature, pressure, reaction time, and the contents of free fatty acids and water in oils, were also discussed. The task of this paper was how to change waste vegetable oils to biodiesel for a substitute of 2# diesel by using acid & base catalyst ,and analyzed the transform ratio of the waste oils by gas chromatography (GC),so determined the optimum experimental conditions of base-catalyzed transesterification through orthogonal experiments. Moreover, the properties of biodiesel products were analyzed according to the national diesel standard of China, and the performance of combustion was also tested. The result showed that biodiesel has a large possibility to replace the 2# diesel. According to the formula of Grunberg-Nissan, the relationship of the biodiesel viscosity and conversion rate was clarified and justifying the biodiesel yield based on viscosity change was established.
The acid value of waste cooking oils is as high as 7.25, that is 8.8% (wt%). Firstly it important to transform the free fatty acid in oils to methyl ester by acid catalyst add-in , and avoid free fatty acid have a reaction with base catalyst. The optimum experiment conditions of acid-catalyzed esterification is determined as follows : using oil of vitriol with concentration as 98% for acid catalyst ,the dosage of acid is 14.6%(wt/wt) in 60 centigrade for 6 hours , the molar ratio of methanol to oils is 50:1,so the transform ratio of biodiesel is 65.9%. Secondly the triglycerides transformed into fatty acid methyl ester with base catalyst add-in. The optimum experiment conditions of base-catalyzed esterification is determined as follows : the molar ratio of methanol to oils is 9:1,the dosage of base catalyst is 1.3%(wt/wt) in 50 centigrade for 90 minutes , so the transform ratio of biodiesel is 75.3%. the relationship of the biodiesel viscosity and conversion rate was clarified and was established. According to the formular of Grunberg-Nissan, it determined the value of GMG is -2.41026mPa?s by experiment.
The paper also studies the feasibility of technology and economy for producing biodiesel using waste cooking oils, which based on related industry standards and combined with market developments of biodiesel. And the feasibility study has analyzed the capacity and choice of project and equipments. It also evaluated comprehensively the social and economic profits of the project. The total investment of this project is 32,520,000 RMB. The total income of this project is 45,050,000 RMB per year. And the profit is 6,050,000 RMB per year. This project has made a widely applying foreground for waste cooking oil, and also solved the environmental pollution of waste cooking oil.
酯交换法制取生物柴油是当今最容易实现工业化的一种方式。在众多的清洁替代能源中,脂肪酸甲酯作为柴油的替代品有很多的优点。影响酯交换反应的主要因素有醇油比、催化剂、反应温度和压力、反应时间以及游离脂肪酸和油中水分含量。基于酸催化和碱催化的方法,本课题主要讨论了如何将废油转化为可以替代2#柴油并应用于柴油发动机中的技术路线,通过气相色谱(GC)分析其中的转化率,通过正交实验得到碱催化进行酯交换实验的最优条件。通过对合成的生物柴油作了石油标准检测,对其燃烧特性作了初步的研究。实验结果证实了用生物柴油替代2#号柴油的可行性。通过Grunberg-Nissan公式,研究了生物柴油粘度与转化率的关系,得出了靠粘度评价转化率的方法。
餐饮废油酸败程度较高,酸价达7.25,酸度达8.8%。考虑到原料油的这种特性,在第一步反应中采用酸催化法将游离脂肪酸甲酯化,避免直接采用碱催化法使游离脂肪酸皂化产率降低的不足。酸催化法的酯化工艺最佳操作条件为:催化剂为98%浓硫酸,催化剂用量为14.6%(占反应总底物的质量比);反应温度为60℃;醇油比为50﹕1(摩尔比);反应时间6h,转化率达到为65.9%。在第二步反应中,采用碱催化法将酸价降低的原料油中的主要成分甘油三酯转化为脂肪酸甲酯。碱催化法的酯交换工艺最佳操作条件为:醇油比为9﹕1,催化剂质量分数为1.3%,反应温度为50℃,反应90min,转化率达到为75.3%。在本试验中确定了从生物柴油的粘度分析甲酯转化率的方法。在所转化的废油各主要成分己知的情况下,由公式可以较为准确的测定甲酯的百分比,其中重要参数GMG = -2.41026mPa·s。
本文还对餐饮废油酯交换生产生物柴油的技术可行性进行了论证,并对其经济成本分析进行了研究。本可行性研究报告根据相关行业规范,并结合当前的生产和销售市场的动态,对该项目的建设规模、采用的技术方案、设备计算选型等各项指标进行了详细的可行性分析。并对该项目的投资估算、社会效益和经济效益进行了综合评估。该项目总投资3252万元人民币,年销售收入为4505万元人民币,年均利润为605万元人民币。本项目对餐饮废油的综合利用提供了广阔的应用前景,同时解决了餐饮废油的环境污染问题。
With the increase of environmental awareness and depletion of energy resources, a novel energy source that has little environmental damage must be found out to replace of petroleum. And vegetable oil has been used for diesel substitution. However, this conflicts with people’s demand for food, although there is great breakthrough in using vegetable oil for diesel substitution. Waste cooking oil is discarded oil, which can be used as raw materials for biodiesel production. And this can also protect our environment. So producing biodiesel with waste cooking oil as raw materials is an efficient way.
Compared with other new renewable and clean engine fuel alternatives, methyl esters of vegetable oils have many outstanding advantages. The transesterification process is most likely to be an industrial process method in future. Producing biodiesel by transesterification of waste cooking oil and methanol was studied and a two-step acid-base catalyzed route for producing biodiesel was established in the paper. The main factors that affecting the yields of fatty acid methyl ester, such as the molar ratio of methanol to oil, catalyst concentration, reaction temperature, pressure, reaction time, and the contents of free fatty acids and water in oils, were also discussed. The task of this paper was how to change waste vegetable oils to biodiesel for a substitute of 2# diesel by using acid & base catalyst ,and analyzed the transform ratio of the waste oils by gas chromatography (GC),so determined the optimum experimental conditions of base-catalyzed transesterification through orthogonal experiments. Moreover, the properties of biodiesel products were analyzed according to the national diesel standard of China, and the performance of combustion was also tested. The result showed that biodiesel has a large possibility to replace the 2# diesel. According to the formula of Grunberg-Nissan, the relationship of the biodiesel viscosity and conversion rate was clarified and justifying the biodiesel yield based on viscosity change was established.
The acid value of waste cooking oils is as high as 7.25, that is 8.8% (wt%). Firstly it important to transform the free fatty acid in oils to methyl ester by acid catalyst add-in , and avoid free fatty acid have a reaction with base catalyst. The optimum experiment conditions of acid-catalyzed esterification is determined as follows : using oil of vitriol with concentration as 98% for acid catalyst ,the dosage of acid is 14.6%(wt/wt) in 60 centigrade for 6 hours , the molar ratio of methanol to oils is 50:1,so the transform ratio of biodiesel is 65.9%. Secondly the triglycerides transformed into fatty acid methyl ester with base catalyst add-in. The optimum experiment conditions of base-catalyzed esterification is determined as follows : the molar ratio of methanol to oils is 9:1,the dosage of base catalyst is 1.3%(wt/wt) in 50 centigrade for 90 minutes , so the transform ratio of biodiesel is 75.3%. the relationship of the biodiesel viscosity and conversion rate was clarified and was established. According to the formular of Grunberg-Nissan, it determined the value of GMG is -2.41026mPa?s by experiment.
The paper also studies the feasibility of technology and economy for producing biodiesel using waste cooking oils, which based on related industry standards and combined with market developments of biodiesel. And the feasibility study has analyzed the capacity and choice of project and equipments. It also evaluated comprehensively the social and economic profits of the project. The total investment of this project is 32,520,000 RMB. The total income of this project is 45,050,000 RMB per year. And the profit is 6,050,000 RMB per year. This project has made a widely applying foreground for waste cooking oil, and also solved the environmental pollution of waste cooking oil.
引文
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