废润滑油的糠醇抽提再生精制工艺研究
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摘要
润滑油是原油中价值最高的组分,但含量却很少,它在使用一段时间后因发生复杂的物理和化学变化变质成为废油。废润滑油中的重金属、多氯联苯、多环芳烃含量很高,如释放到环境中尤其是水体中时对人和环境的污染和危害极大。一旦水体受到废润滑油污染,很难采用常规方法去除污油。减少废润滑油对环境的影响响的最好办法是回收废油并再精炼成为再生基础油,减少废油的排放。
废润滑油再生方法较多,如白土工艺、溶剂抽提、蒸馏-白土过滤工艺、化学处理和白土吸附结合工艺、膜分离处理和加氢精制等。最近几年溶剂抽提精制废油受到广泛关注这种再生工艺成功取代易产生污染性酸渣的硫酸-白土处理工艺。溶剂抽提精制废油工艺简单,抽提剂和废油以适当比例混合,一定条件下就可以使废润滑油中的理想组分和非理想组分分离。溶剂通过蒸馏可以回收后循环使用。抽提精制的关键是抽提溶剂和抽提剂组分体系的选择和抽提参数(如抽提温度、剂油比等)评选。溶剂精制萃取回收废润滑油的有用组分是废油回收再生工艺中最经济、最有效的手段。
本文根据萃取缔合原理,经过理论分析和实验探究,选取含有一个呋喃基的糠醇作为抽提溶剂,通过单因素实验分析和正交实验手段,探索了废内燃机油和废真空泵油采用糠醇抽提方法再生精制的工艺方法和条件,结果表明影响废机油糠醇抽提再生精制的主要工艺条件是剂油比和精制温度。其中,对废机油的糠醇抽提再生而言,最佳工艺条件为：剂油比为1.5,精制温度为80℃。红外光谱1745cm-1 and 1160cm-1两处峰的消失表明了废油中非理想胶质和沥青质的脱除。最优工艺条件下,废机油回收后再生油的性质：运动粘度(40℃)为60.56mm2/s,折光率(25℃)为1.484,回收率93.9%,凝点为-17℃,密度为0.8781kg/m3。回收后的油品质量较好,经添加适当的添加剂调和后可循环使用。对废真空泵油的糠醇抽提再生而言,最佳工艺条件为：剂油比为1.5,精制温度为80℃。在此工艺条件下,回收油的性质：运动粘度(40℃)为57.25mm2/s,折光率(25℃)为1.479,回收率92.3%。
Lube oils are the most valuable but minor constituents in crude oil. because of complicated physics and chemistry changes lube oils become to used lube oils(ULO) after being used for a long time, It should be noted that heavy metals, polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) are main contaminants in ULO; these components are highly toxic when released to the environment, particularly to water courses as this causes the obstruction of sunlight and oxygen from the atmosphere to water, which consequently poses harmful effects to aquatic lives. Difficulties also arise during the treatment as ULO is not easily removed from the contaminated water by conventional treatment methods. Hence, the best solution for ULO is the recovery of waste lube oils and re-refining to base oil instead of discarding to the environment.
Different techniques have been practiced for recycling used lubricating oils. e.g. acid clay process, solvent extraction, distillation—clay filtration, chemical and clay treatment, membrane technology. Among the alternative processes proposed during recent years, solvent extraction process has received considerable attention. This process replaces successfully the classic acid/clay treatment whereby a useful organic sludge is produced instead of the toxic acidic sludge. Solvent extraction is a simple process; used oil and solvent are mixed in appropriate proportions to assure complete miscibility of the base oil in the solvent. The solvent is then recovered by distillation for recycle purpose.
The most critical stage in designing this process is developing appropriate solvent extraction system that consists of type of solvent(s), extraction parameters (temperature, and solvent:oil ratio. etc.).Solvent extraction technique is one of the cheapest and most efficient processes experienced in recycling of used lubricating oils. In this paper, the performance of furfuryl alcohol in recycling used vacuum pump oil was evaluated experimentally. The effect of the most critical parameters (solvent to oil ratio, and extraction temperature) was investigated. The results show that viscosity index and refractive index of refined oil was related to the solvent to oil ratio. Viscosity index and the refractive index come to a feasible value at 80℃when solvent to oil ratio equal to 1.5. The difference of IR spectrum of the used vacuum pump oil and IR spectrum of refined vacuum pump oil show that absorption peaks at 1745cm-1 and 1160 cm 1 disappeared after solvent extraction. Under the optimal process conditions, the properties of the recovered oil were listed as follows:Viscosity (40℃) 60.56 mm2/s,25℃refractive index 1.484,recovery yield 93.9% solidifying point-1℃, density 0.8781kg/mJ.The recovery oil has a good quality,it can be reused for new base oils after adding appropriate additives. And the results of recovery of used vacuum pump oil with furfuryl alcohol are as follow; the solvent:oil ratio 1.5, refining temperature 80℃; Under the optimal Technology conditions, the properties of the recovered oil were listed as follows:Viscosity (40℃) 57.25 mm2/s,25℃refractive index 1.479,yield 92.3％.
废润滑油再生方法较多,如白土工艺、溶剂抽提、蒸馏-白土过滤工艺、化学处理和白土吸附结合工艺、膜分离处理和加氢精制等。最近几年溶剂抽提精制废油受到广泛关注这种再生工艺成功取代易产生污染性酸渣的硫酸-白土处理工艺。溶剂抽提精制废油工艺简单,抽提剂和废油以适当比例混合,一定条件下就可以使废润滑油中的理想组分和非理想组分分离。溶剂通过蒸馏可以回收后循环使用。抽提精制的关键是抽提溶剂和抽提剂组分体系的选择和抽提参数(如抽提温度、剂油比等)评选。溶剂精制萃取回收废润滑油的有用组分是废油回收再生工艺中最经济、最有效的手段。
本文根据萃取缔合原理,经过理论分析和实验探究,选取含有一个呋喃基的糠醇作为抽提溶剂,通过单因素实验分析和正交实验手段,探索了废内燃机油和废真空泵油采用糠醇抽提方法再生精制的工艺方法和条件,结果表明影响废机油糠醇抽提再生精制的主要工艺条件是剂油比和精制温度。其中,对废机油的糠醇抽提再生而言,最佳工艺条件为：剂油比为1.5,精制温度为80℃。红外光谱1745cm-1 and 1160cm-1两处峰的消失表明了废油中非理想胶质和沥青质的脱除。最优工艺条件下,废机油回收后再生油的性质：运动粘度(40℃)为60.56mm2/s,折光率(25℃)为1.484,回收率93.9%,凝点为-17℃,密度为0.8781kg/m3。回收后的油品质量较好,经添加适当的添加剂调和后可循环使用。对废真空泵油的糠醇抽提再生而言,最佳工艺条件为：剂油比为1.5,精制温度为80℃。在此工艺条件下,回收油的性质：运动粘度(40℃)为57.25mm2/s,折光率(25℃)为1.479,回收率92.3%。
Lube oils are the most valuable but minor constituents in crude oil. because of complicated physics and chemistry changes lube oils become to used lube oils(ULO) after being used for a long time, It should be noted that heavy metals, polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) are main contaminants in ULO; these components are highly toxic when released to the environment, particularly to water courses as this causes the obstruction of sunlight and oxygen from the atmosphere to water, which consequently poses harmful effects to aquatic lives. Difficulties also arise during the treatment as ULO is not easily removed from the contaminated water by conventional treatment methods. Hence, the best solution for ULO is the recovery of waste lube oils and re-refining to base oil instead of discarding to the environment.
Different techniques have been practiced for recycling used lubricating oils. e.g. acid clay process, solvent extraction, distillation—clay filtration, chemical and clay treatment, membrane technology. Among the alternative processes proposed during recent years, solvent extraction process has received considerable attention. This process replaces successfully the classic acid/clay treatment whereby a useful organic sludge is produced instead of the toxic acidic sludge. Solvent extraction is a simple process; used oil and solvent are mixed in appropriate proportions to assure complete miscibility of the base oil in the solvent. The solvent is then recovered by distillation for recycle purpose.
The most critical stage in designing this process is developing appropriate solvent extraction system that consists of type of solvent(s), extraction parameters (temperature, and solvent:oil ratio. etc.).Solvent extraction technique is one of the cheapest and most efficient processes experienced in recycling of used lubricating oils. In this paper, the performance of furfuryl alcohol in recycling used vacuum pump oil was evaluated experimentally. The effect of the most critical parameters (solvent to oil ratio, and extraction temperature) was investigated. The results show that viscosity index and refractive index of refined oil was related to the solvent to oil ratio. Viscosity index and the refractive index come to a feasible value at 80℃when solvent to oil ratio equal to 1.5. The difference of IR spectrum of the used vacuum pump oil and IR spectrum of refined vacuum pump oil show that absorption peaks at 1745cm-1 and 1160 cm 1 disappeared after solvent extraction. Under the optimal process conditions, the properties of the recovered oil were listed as follows:Viscosity (40℃) 60.56 mm2/s,25℃refractive index 1.484,recovery yield 93.9% solidifying point-1℃, density 0.8781kg/mJ.The recovery oil has a good quality,it can be reused for new base oils after adding appropriate additives. And the results of recovery of used vacuum pump oil with furfuryl alcohol are as follow; the solvent:oil ratio 1.5, refining temperature 80℃; Under the optimal Technology conditions, the properties of the recovered oil were listed as follows:Viscosity (40℃) 57.25 mm2/s,25℃refractive index 1.479,yield 92.3％.
引文
[1]Shing Tet Leong. An Environmental Approach for Used Oil Management in Asian Cities[J].Journal of Environmental Sciences,2003,115(6):734-743
[2]Muller Associates. Waste oil:reclaiming technology, utilization and disposal (Pollution Technology Review), No.1666. Westwood, New Jersey, USA:Noyes Data Corporation; 1989.
[3]Wilson B. Used oil reclamation process. Environmentally adapted lubricants. Ind Lube Tribol 1997;49(4):178-80.
[4]Gourgouillon D, Schrive L, Sarrade S, Rios GM. An environmental friendly process for the regeneration of used oils. Environ Sci Technol 2000; 34(16):3469-3473.
[5]Hamad A, Al-Zubaidy E, Fayed ME. Used lubricating oil recycling using hydrocarbon solvents. J Environ Manage 2005;74(2):153-159.
[6]Mshammad Farhat Ali, Faizur Rahman', Abdullah J. Hamdan. Techno-economic evaluation of waste lube oil re-refining[J]. Int. J. Production Economics 42 (1995) 263-273
[7]张春光；赵渊杰；邓永生,等.废润滑油再生技术现状及行业发展思路[J].润滑油,2008,23(2)：9-12
[8]Mshammad Farhat Ali, Faizur Rahman', Abdullah J. Hamdan. Techno-economic evaluation of waste lube oil re-refining[J]. Int. J. Production Economics 42 (1995) 263-273
[9]Hatgraove J D. New dewaxing process proven in operation[J].Oil and gas Journal,1997, 77(3),103-105.
[10]韩德奇,洪国忠,李萍,等.废白土无公害处理[J].石化技术,1999,6(2)：84-85.
[11]Mynin V N, Smirnovae B, Katserevaov, et al Treatment and regeneration of used lube oils with inorganic membranes[J]. Chemical and Technology of Fuels and Oils,2004,40(5): 345-361
[12]丁福臣.萃取-絮凝法再生废润滑油的研究[J].北京石油化工学院学报,1995,3(2)：44-48.
[13]裘峰.提高润滑油基础油质量的工艺研究[J].高桥石化,2008,23(1)：20-23.
[14]徐先盛.我国废润滑油再生工艺及发展策略探讨[J]润滑油,1993,8(3)：22-23.
[15]任秋君.提高糠醛精制技术水平的有效途径[J]石油炼制与化工,1997(8)15-16；
[16]陈晓东,李晓欧.润滑油糠醛精制过程加助剂研究(Ⅱ)[J].石油化工高等学校学报,2000,13(2)：25-28.
[17]谭均权,张秀英,李俊岭,等.胜利原油350-510℃馏分糠醛精制的研究[J].炼油设计,2002,32(4)：28-30.
[18]王昌东,郭奇,王利君,等.润滑油原料溶剂精制技术的发展[J].当代化工,2004(4)35-37；
[19]杨道胜.世外润滑基础油的进展[J].润滑油,2003,18(3)：6-8.
[20]白雪松,于殿名.国内外润滑油基础油市场供求情况及需求预测[J].化工技术经济,2007,25(01)：28-34.
[21]唐光阳,施跃坚,刘满红等.废润滑油的的回收工艺初探[J].云南师范大学学报,2001,21(4)：23-25.
[22]徐先盛.我国废润滑油再生工艺及发展策略探讨[J]润滑油,1993,8(3)：22-23.
[23]顾彩香,顾卓明,范少卿.新型环保润滑油配方的研制[J].机械设计,2007,24(1)：51-54.
[24]李璐,郭大光,莫娅南.废润滑油再生工艺的研究[J]辽宁石油化工大学学报,2008(12)23-26.
[25]杨宏伟,费逸伟,胡建强.国内外废润滑油的再生[J].润滑油,2006(6)17-19；
[26]张贤明,焦昭杰,贾玉梅,等.工业污染废润滑油再生技术[J].环境科学与技术,2008,11(5)：3-8
[27]任天辉,王大璞.废润滑油再生加工技术[J].中国资源综合利用,2000(3)：8-12.
[28]刘建锟,张忠清,杨涛,等.废润滑油的再生工艺研究[J]当代化工,2010(5)55-58；
[29]刘发起.废润滑油再生工艺技术与研究[J].贵州化工,2004,29(2)：8-10.
[30]J.H. Hildebrand, J.M. Prausnitz, R.L. Scott, Regular and Related Solutions:The Solubility of Gases, Liquids and Solid, Van Nostrand Reinhold, NY,1970.
[31]莫娅南,郭大光,张廷雪.溶剂精制法回收废润滑油[J].石油与天然气化工2007,36(2)：124-134
[32]Vorapot Kanokkantapong,Worapon Kiatkittipong, Bunyarit Panyapinyopol,et.al. Used lubricating oil management options based on life cycle thinking[J] Resources, Conservation and Recycling,2009 (53) 294-299
[33]Santos J CO, LimaL N, Santos Ieda M G, et al. Spectroscopic and Rheological Study of Mineral Base Lubricating Oils[J].Journal of Thermal Analysis and Calorimetry,2007, 87(3):639-643.
[2]Muller Associates. Waste oil:reclaiming technology, utilization and disposal (Pollution Technology Review), No.1666. Westwood, New Jersey, USA:Noyes Data Corporation; 1989.
[3]Wilson B. Used oil reclamation process. Environmentally adapted lubricants. Ind Lube Tribol 1997;49(4):178-80.
[4]Gourgouillon D, Schrive L, Sarrade S, Rios GM. An environmental friendly process for the regeneration of used oils. Environ Sci Technol 2000; 34(16):3469-3473.
[5]Hamad A, Al-Zubaidy E, Fayed ME. Used lubricating oil recycling using hydrocarbon solvents. J Environ Manage 2005;74(2):153-159.
[6]Mshammad Farhat Ali, Faizur Rahman', Abdullah J. Hamdan. Techno-economic evaluation of waste lube oil re-refining[J]. Int. J. Production Economics 42 (1995) 263-273
[7]张春光；赵渊杰；邓永生,等.废润滑油再生技术现状及行业发展思路[J].润滑油,2008,23(2)：9-12
[8]Mshammad Farhat Ali, Faizur Rahman', Abdullah J. Hamdan. Techno-economic evaluation of waste lube oil re-refining[J]. Int. J. Production Economics 42 (1995) 263-273
[9]Hatgraove J D. New dewaxing process proven in operation[J].Oil and gas Journal,1997, 77(3),103-105.
[10]韩德奇,洪国忠,李萍,等.废白土无公害处理[J].石化技术,1999,6(2)：84-85.
[11]Mynin V N, Smirnovae B, Katserevaov, et al Treatment and regeneration of used lube oils with inorganic membranes[J]. Chemical and Technology of Fuels and Oils,2004,40(5): 345-361
[12]丁福臣.萃取-絮凝法再生废润滑油的研究[J].北京石油化工学院学报,1995,3(2)：44-48.
[13]裘峰.提高润滑油基础油质量的工艺研究[J].高桥石化,2008,23(1)：20-23.
[14]徐先盛.我国废润滑油再生工艺及发展策略探讨[J]润滑油,1993,8(3)：22-23.
[15]任秋君.提高糠醛精制技术水平的有效途径[J]石油炼制与化工,1997(8)15-16；
[16]陈晓东,李晓欧.润滑油糠醛精制过程加助剂研究(Ⅱ)[J].石油化工高等学校学报,2000,13(2)：25-28.
[17]谭均权,张秀英,李俊岭,等.胜利原油350-510℃馏分糠醛精制的研究[J].炼油设计,2002,32(4)：28-30.
[18]王昌东,郭奇,王利君,等.润滑油原料溶剂精制技术的发展[J].当代化工,2004(4)35-37；
[19]杨道胜.世外润滑基础油的进展[J].润滑油,2003,18(3)：6-8.
[20]白雪松,于殿名.国内外润滑油基础油市场供求情况及需求预测[J].化工技术经济,2007,25(01)：28-34.
[21]唐光阳,施跃坚,刘满红等.废润滑油的的回收工艺初探[J].云南师范大学学报,2001,21(4)：23-25.
[22]徐先盛.我国废润滑油再生工艺及发展策略探讨[J]润滑油,1993,8(3)：22-23.
[23]顾彩香,顾卓明,范少卿.新型环保润滑油配方的研制[J].机械设计,2007,24(1)：51-54.
[24]李璐,郭大光,莫娅南.废润滑油再生工艺的研究[J]辽宁石油化工大学学报,2008(12)23-26.
[25]杨宏伟,费逸伟,胡建强.国内外废润滑油的再生[J].润滑油,2006(6)17-19；
[26]张贤明,焦昭杰,贾玉梅,等.工业污染废润滑油再生技术[J].环境科学与技术,2008,11(5)：3-8
[27]任天辉,王大璞.废润滑油再生加工技术[J].中国资源综合利用,2000(3)：8-12.
[28]刘建锟,张忠清,杨涛,等.废润滑油的再生工艺研究[J]当代化工,2010(5)55-58；
[29]刘发起.废润滑油再生工艺技术与研究[J].贵州化工,2004,29(2)：8-10.
[30]J.H. Hildebrand, J.M. Prausnitz, R.L. Scott, Regular and Related Solutions:The Solubility of Gases, Liquids and Solid, Van Nostrand Reinhold, NY,1970.
[31]莫娅南,郭大光,张廷雪.溶剂精制法回收废润滑油[J].石油与天然气化工2007,36(2)：124-134
[32]Vorapot Kanokkantapong,Worapon Kiatkittipong, Bunyarit Panyapinyopol,et.al. Used lubricating oil management options based on life cycle thinking[J] Resources, Conservation and Recycling,2009 (53) 294-299
[33]Santos J CO, LimaL N, Santos Ieda M G, et al. Spectroscopic and Rheological Study of Mineral Base Lubricating Oils[J].Journal of Thermal Analysis and Calorimetry,2007, 87(3):639-643.