针对采用废油脂为原料转化制备的生物柴油会含有一定量的硫化物的问题,采用真空精馏法脱除生物柴油中的硫化物,并对硫化物附存形态进行分析。结果表明：生物柴油中硫化物主要包括低沸点的硫化氢、硫醇、硫醚、硫胺素等,以及高沸点的苯并噻吩、二苯并噻吩等。采用控制精馏脱硫塔塔顶温度150 ℃、操作绝对压力300~500 Pa、回流比1的条件下,先对生物柴油中低沸点硫化物进行脱除,再将塔顶温度升至210 ℃,将中间馏分（生物柴油）从塔顶精馏出来,高沸点重馏分（生物重油、高沸点硫化物）留在塔釜底部,两步精馏切割法能将达标的生物柴油与其他馏分分离开来,可有效降低生物柴油的硫含量,脱硫率达97%,满足最新国Ⅵ柴油排放标准（GB 17930—2016）的硫含量≤10 mg/kg要求,且硫含量达标的生物柴油得率达到85%以上。
Abstract
There will be a certain amount of sulfides in the biodiesel produced by the conversion of waste oil. In view of the above problems, the vacuum distillation method was used to remove the sulfides from the crude biodiesel, and the existing forms of sulfides were analyzed. The results showed that the sulfides in biodiesel mainly include those with low boiling point, such as hydrogen sulfide, mercaptan, thioether, thiamine, etc., and those with high boiling point, such as thiophene, benzothiophene, dibenzothiophene, etc. Under the conditions of controlling the top temperature of distillation desulfurization tower at 150 ℃, operating absolute pressure of 300-500 Pa, reflux ratio of 1, the low boiling point sulfide in crude biodiesel was firstly removed. And then the tower top temperature was increased to 210 ℃, so that the middle distillate （biodiesel） was distilled out, and the high boiling point heavy fraction （bio heavy oil, high boiling point sulfide） remained at the bottom of the tower bottom. Using this two-step cutting distillation method, biodiesel meeting the requirements of the latest national Ⅵ diesel emission standard （GB17930—2016, sulfur content≤10 mg/kg） can be obtained. This method can effectively reduce the sulfur content of biodiesel, and the desulfurization rate reaches 97%, and the yield of biodiesel up to the standard reaches more than 85%.
关键词
生物柴油 /
脱硫 /
精馏 /
地沟油
Key words
biodiesel /
desulfurization /
rectification /
waste oil
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基金
国家重点研发计划（2019YFB1504003; 2017YFD0601003）; 广东省科技计划（201804010125）
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