超声及表面活性剂对柴油微乳化的影响
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摘要
微乳柴油作为一种较佳的节能、环保燃料,在能源紧缺、环境问题日益严重的今天越来越受到科研工作者的重视。其节能、降污原理为:水的加入使微乳柴油燃烧时内部的微小水珠产生“微爆”效应,从而油滴雾化,增加油滴与空气接触的比表面积,减少了燃料的不完全燃烧,降低烟灰和氮氧化合物的排放,提高了燃烧效率。
超声波是一种较为新型的乳化设备,作为制备微乳化柴油的主要方法,目前报道尚少。超声乳化主要原理是超声的空化效应。超声波用于微乳化,不仅可以降低乳化剂的用量,而且可以降低微乳柴油中水滴粒径,改善微乳液的性质,提高其稳定性。
乳化剂是一种表面活性剂,对于微乳柴油的制备至关重要。本文利用普通乳化实验从十几种常见的乳化剂中筛选出对于柴油—水体系乳化能力较强的阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)为主要的乳化剂;通过对十种短链、中长链醇的筛选确定以正丁醇/正辛醇混合醇作为最佳助剂,可以辅助CTAB制备出外观和普通柴油相似的微乳化柴油。
本文测定并优化了以超声波为主要分散手段,制备上述体系微乳柴油的最佳超声参数:超声频率40kHz,超声声强0.266W·cm~(-2),超声作用时间20min。通过粒径分析仪测得在此最佳超声条件下制备的微乳柴油粒径达到45.3nm。
讨论了微乳柴油稳定性的表征方式,并以粘度指标法和高温分层时间法测定、比较了微乳柴油的相对稳定性。
为了进一步降低制备微乳化柴油的成本,进行了乳化剂复配实验,筛选出能与CTAB复配制备微乳化柴油的乳化剂。分别为非离子表面活性剂Span80、Span60,阴离子表面活性剂ABS;其中Span80的效果最佳。采用复配乳化剂制备微乳柴油,可以大大降低乳化剂和助剂醇的使用量,乳化剂用量仅占微乳柴油的2%左右。通过粗略成本核算,筛选出的三种复配方案,其成本均低于目前市售柴油的价格,即在4070元/吨以下;且稳定性良好,至今已放置6个月以上,外观诱明,无明显变化。
Emulsification of diesel oil by making micro-water-droplet dispersed in oil is considered as one of the promising techniques to save energy and reduce air pollution. It can be used as an alternative fuel for diesel engines. More and more researchers pay their attention to this technique, since the energy and environment concerning problems become very essential for development of the society and people's life. As the result of the micro-explosions of water droplets in emulsion, diesel oil can be atomized and the contact area of the oil droplets atmosphere increases. Therefore, the effect of the micro-explosions can reduce the imperfect combustion of diesel and its exhaust emission.Ultrasound s one of the new-style means of emulsion. Ultrasonic cavitation is an important effect to assist micro-emulsification. It can reduce emulsifier dosage and change the properties of micro-emulsion, such as reducing the water size of the micro-emulsion to improve the stability of the micro-emulsion.The key to the preparation of diesel-water micro-emulsion is the selection of the emulsifier. Through the experimental ultrasonic emulsification, Cetyltrimethyl Ammonium Bromide (CTAB) was selected as emulsifier and 1-octyl alcohol/1-butyl alcohol as the optimal co-emulsifier were used to prepare the micro-emulsion of water-in-diesel oil. The two techniques of stirrer and ultrasound were compared in this paper. Ultrasound technique is better than stirring, for the average diameter of the water particles in diesel produced by the former was only 30% of that of the latter. The ultrasound effect is studied and a series of ultrasonic parameters are optimized in the research. The optimum ultrasonic condition to get the micro-emulsion was obtained: the ultrasonic frequency 40kHz, the ultrasonic intensity 0.266 W/cm"2, and the treatment time 20min. Then the average diameter of the water particles was 45.3nm in this condition.The representations of the micro-emulsion's stability were studied. The viscosity index method and the high temperature sedimentary time method were used to
compare the stabilities of the micro-emulsion prepared.The built emulsifier prepared with CTAB was studied to reduce the cost of the emulsifier. By the large numbers of experimental test, the built emulsifier Span80/CTAB(3:2)> Span80/CTAB(7:3), Span60/CTAB(l:l)> ABS/CTAB(1:4) were selected to prepare the micro-emulsion of diesel-water. Using the built emulsifier made the dosage of the emulsifier reached 2% of the mass of micro-emulsion. The price of the micro-emulsion diesel oil was estimated to be under 4070 Y/t. The micro-emulsion is transparent and its stable time can keep at least 6 months. The combustion test of the micro-emulsion demonstrated that the micro-emulsion oil could reduce air pollution.
超声波是一种较为新型的乳化设备,作为制备微乳化柴油的主要方法,目前报道尚少。超声乳化主要原理是超声的空化效应。超声波用于微乳化,不仅可以降低乳化剂的用量,而且可以降低微乳柴油中水滴粒径,改善微乳液的性质,提高其稳定性。
乳化剂是一种表面活性剂,对于微乳柴油的制备至关重要。本文利用普通乳化实验从十几种常见的乳化剂中筛选出对于柴油—水体系乳化能力较强的阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)为主要的乳化剂;通过对十种短链、中长链醇的筛选确定以正丁醇/正辛醇混合醇作为最佳助剂,可以辅助CTAB制备出外观和普通柴油相似的微乳化柴油。
本文测定并优化了以超声波为主要分散手段,制备上述体系微乳柴油的最佳超声参数:超声频率40kHz,超声声强0.266W·cm~(-2),超声作用时间20min。通过粒径分析仪测得在此最佳超声条件下制备的微乳柴油粒径达到45.3nm。
讨论了微乳柴油稳定性的表征方式,并以粘度指标法和高温分层时间法测定、比较了微乳柴油的相对稳定性。
为了进一步降低制备微乳化柴油的成本,进行了乳化剂复配实验,筛选出能与CTAB复配制备微乳化柴油的乳化剂。分别为非离子表面活性剂Span80、Span60,阴离子表面活性剂ABS;其中Span80的效果最佳。采用复配乳化剂制备微乳柴油,可以大大降低乳化剂和助剂醇的使用量,乳化剂用量仅占微乳柴油的2%左右。通过粗略成本核算,筛选出的三种复配方案,其成本均低于目前市售柴油的价格,即在4070元/吨以下;且稳定性良好,至今已放置6个月以上,外观诱明,无明显变化。
Emulsification of diesel oil by making micro-water-droplet dispersed in oil is considered as one of the promising techniques to save energy and reduce air pollution. It can be used as an alternative fuel for diesel engines. More and more researchers pay their attention to this technique, since the energy and environment concerning problems become very essential for development of the society and people's life. As the result of the micro-explosions of water droplets in emulsion, diesel oil can be atomized and the contact area of the oil droplets atmosphere increases. Therefore, the effect of the micro-explosions can reduce the imperfect combustion of diesel and its exhaust emission.Ultrasound s one of the new-style means of emulsion. Ultrasonic cavitation is an important effect to assist micro-emulsification. It can reduce emulsifier dosage and change the properties of micro-emulsion, such as reducing the water size of the micro-emulsion to improve the stability of the micro-emulsion.The key to the preparation of diesel-water micro-emulsion is the selection of the emulsifier. Through the experimental ultrasonic emulsification, Cetyltrimethyl Ammonium Bromide (CTAB) was selected as emulsifier and 1-octyl alcohol/1-butyl alcohol as the optimal co-emulsifier were used to prepare the micro-emulsion of water-in-diesel oil. The two techniques of stirrer and ultrasound were compared in this paper. Ultrasound technique is better than stirring, for the average diameter of the water particles in diesel produced by the former was only 30% of that of the latter. The ultrasound effect is studied and a series of ultrasonic parameters are optimized in the research. The optimum ultrasonic condition to get the micro-emulsion was obtained: the ultrasonic frequency 40kHz, the ultrasonic intensity 0.266 W/cm"2, and the treatment time 20min. Then the average diameter of the water particles was 45.3nm in this condition.The representations of the micro-emulsion's stability were studied. The viscosity index method and the high temperature sedimentary time method were used to
compare the stabilities of the micro-emulsion prepared.The built emulsifier prepared with CTAB was studied to reduce the cost of the emulsifier. By the large numbers of experimental test, the built emulsifier Span80/CTAB(3:2)> Span80/CTAB(7:3), Span60/CTAB(l:l)> ABS/CTAB(1:4) were selected to prepare the micro-emulsion of diesel-water. Using the built emulsifier made the dosage of the emulsifier reached 2% of the mass of micro-emulsion. The price of the micro-emulsion diesel oil was estimated to be under 4070 Y/t. The micro-emulsion is transparent and its stable time can keep at least 6 months. The combustion test of the micro-emulsion demonstrated that the micro-emulsion oil could reduce air pollution.
引文
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[3] 韩德奇,李伟,张晓霞,等.环保型柴油替代燃料的开发和应用[J].石油与天然气化工,2003,32(1):33～37.
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[5] 刘蔚,乳化柴油及其实验研究[D].大连:大连理工大学,2003.
[6] 朱建良,张冠杰.国内外生物柴油研究生产现状及发展趋势[J].化工时刊,2004,(1):23～28.
[7] 陈登龙,丁以钿,林建生.乳化柴油的研究[J].化工科技,2002,10(1):15～18.
[8] Valentine J. Reduction of Nitrogen Oxides Emissions from Diesel Engines[P]. US5535708, 1996, 7.
[9] Cemenska, Richard A, Coleman, et al. Fuel Emulsion Blending System[P]. US 5873916, 1999, 2.
[10] Mezherisky A D, Halimi E. Water/Fuel Mixing System for a Diesel Engine[P]. US5904121, 1999, 5.
[11] 黄文,毛汉颖.燃油乳化研究和应用的现状[J].仪器仪表与分析监测,2002,(2):5～6.
[12] 顾全生,胡晶.柴油乳化剂和乳化柴油[P].CN1377941,2002-04-08.
[13] 陈良.柴油乳化剂及制得的乳化柴油和制造乳化柴油的工艺[P].CN1229121,1999,9.
[14] 陆翼德,木合塔尔·买提尼亚孜.用于乳化柴油的添加剂及其制备方法[P].CN1542099,2004,11.
[15] 李大楠.掺水微乳化汽油(或燃料油)的制备方法[P].CN87104283,1988,2.
[16] 梁治齐,李金华.功能性乳化剂与乳化液[M].北京:中国轻工业出版社, 2000,4.
[17] 陈振江,穆文俊,赵德智,等.柴油乳化液的制备及其稳定性能研究[J].节能技术,1998(1):14～16.
[18] 朱灵峰,吴翠莲,吴生林,等.CZF-A型乳化柴油的试验研究[J].河南师范大学学报,1997(3):48～52.
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