采用地沟油等餐饮废弃油脂转化制备生物柴油中会含有一定量的硫化物,针对上述问题,考察传统的酸碱两步法制备生物柴油过程中硫化物的迁移,并以离子液体（[Hnmp]H2PO4）为萃取剂和催化剂,H2O2为氧化剂,对粗生物柴油进行萃取氧化脱硫,并利用正交实验法对萃取氧化脱硫反应工艺进行优化。结果表明：反应过程使用的试剂和操作条件几乎不会增大生物柴油制备过程中的硫含量以及改变硫化物在反应体系中的存在形态,硫化物含量及存在形式与原料油自身所含硫化物形态有关。S元素在地沟油原料及生物柴油粗成品中的存在形式主要以噻吩、硫醇、硫醚、硫胺素、硫代葡萄糖苷等物质为主,其中噻吩类硫化物约占地沟油原料或生物柴油中总含硫质量分数的93%以上。在粗生物柴油与离子液体体积比为10∶3,粗生物柴油与H2O2体积比为10∶1.2,反应温度75 ℃,反应时间70 min条件下,生物柴油脱硫率达94%以上,脱硫后的生物柴油满足最新国Ⅵ柴油排放标准（GB 17930—2016）硫含量≤10 mg/kg要求。
Abstract
The biodiesel produced from the waster cooking oil, such as gutter oil, usually contains a certain amount of sulfide, which would cause the environment pollutions during the combustion. In order to solve the above problems, this study investigated the migration of sulfides during the traditional acid-base two-step process to prepare biodiesel. Then, using ionic liquid （[Hnmp]H2PO4） as extractant and catalyst, H2O2 as oxidant, the extraction oxidative desulfurization of gutter oil biodiesel was studied, and the desulfurization reaction process was optimized by orthogonal experiment. The results show that the reagents, materials and operating conditions used in the preparation of biodiesel did not increase the sulfur content and change the form of sulfide in biodiesel products. The existing forms and contents of sulfides are related to the sulfides in the raw oil itself. The sulfides in biodiesel mainly exist in the form of alkylbenzothiophenes and alkyl dibenzothiophenes. Under the conditions of reaction temperature 75 ℃, volume ratio of biodiesel to ionic liquid 10∶3, volume ratio of biodiesel to H2O2 10∶1.2, and oxidation time of 70 min, the desulfurization rate of biodiesel can reach 94%, which meets the requirement of sulfur content ≤ 10 mg/kg in the latest national VI diesel emission standard（GB 17930—2016）.
关键词
生物柴油 /
脱硫 /
离子液体 /
H2O2 /
地沟油
Key words
biodiesel /
desulfurization /
Ionic liquid /
H2O2 /
gutter oil
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参考文献
[1] MIAO C L, LI H W, ZHUANG X S, et al.Synthesis and properties of porous CLEAs lipase by the calcium carbonate template method and its application in biodiesel production[J]. RSC advances, 2019, 9: 29665-29675.
[2] MIAO C L, YANG L, WANG Z, et al.Lipase immobilization on amino-silane modified superparamagnetic Fe3O4 nanoparticles as biocatalyst for biodiesel production[J]. Fuel, 2018, 224: 774-782.
[3] FAN P, XING S Y, WANG J Y, et al.Sulfonated imidazolium ionic liquid catalyzed transesterification for biodiesel synthesis[J]. Fuel, 2017, 188: 483-488.
[4] FAN P, WANG J Y, XING S Y, et al.Synthesis of glycerol-free biodiesel with dimethyl carbonate over sulfonated imidazolium ionic liquid[J]. Energy fuels, 2017, 31(4): 4090-4095.
[5] XIE Q L, CAI L, XIA F, et al.High vacuum distillation for low-sulfur biodiesel production: from laboratory to large scale[J]. Journal of cleaner production, 2019, 223(20): 379-385.
[6] 李惠文, 李志兵, 苗长林, 等. 废油脂生物柴油的脱硫处理研究[J]. 中国油脂, 2019, 44(11): 52-55, 96.
LI H W, LI Z B, MIAO C L, et al.Desulfurizatio of biodiesel prepared from waste oil[J]. China oils and fats, 2019, 44(11): 52-55, 96.
[7] 张成如. 一种生物柴油脱硫新方法: CN201810259032.1[P].2019-08-23.
ZHANG C R. A new desulphurization method for biodiesel: CN201810259032.1[P].2019-08-23.
[8] MELLO V S E, FARIAS A C M D, SOUZA E R D V, et al. Effect of desulfurization of diesel and its blends with biodiesel on metallic contact[J]. Materials research, 2014, 17(1): 82-88.
[9] BETHA R, BALASUBRAMANIAN R.Particulate emissions from a stationary engine fueled with ultra-low-sulfur diesel and waste-cooking-oil-derived biodiesel[J]. Journal of the air waste management association, 2011, 61(10): 1063-1069.
[10] MA H, ADDY M M, ANDERSON E, et al.A novel process for low-sulfur biodiesel production from scum waste[J]. Bioresource technology, 2016, 214: 826-835.
[11] MGUNI L L, YAO Y, NKOMZWAYO T, et al.Desulphurization of diesel fuels using intermediate Lewis acids loaded on activated charcoal and alumina[J]. Chemical engineering communications, 2019, 206(5): 572-580.
[12] 赵敏仲, 王子腾, 赵汇行, 等. 一种生物柴油粗品的连续汽提脱硫蒸馏系统: CN201920648967.9[P].2020-01-17.
ZHAO M Z, WANG Z T, ZHAO H X, et al. Continuous stripping desulfurization distillation system for biodiesel crude: CN201920648967.9[P].2020-01-17.
[13] 杨建斌, 张学旺. 生物柴油精馏脱硫系统: CN201721506443.3[P].2018-08-03.
YANG J B, ZHANG X W. Biodiesel distillation desulfurization system: CN201721506443.3[P].2018-08-03.
[14] 肖志红, 张爱华, 李昌珠, 等. 一种萃取脱硫剂、其制备方法与生物柴油脱硫精制方法: CN201810564042.6[P].2018-11-16.
XIAO Z H, ZHANG A H, LI C Z, et al. An extraction desulfurizer, preparation method and biodiesel desulfurization and refining method: CN201810564042.6 [P].2018-11-16.
[15] 聂勇, 计建炳, 蔡莉, 等. 一种生物柴油脱硫新方法: CN201610766466.1[P].2017-01-18.
NIE Y, JI J B CAI L, et al. A new method for desulphurization of biodiesel: CN201610766466.1[P].2017-01-18.
基金
国家重点研发计划（2019YFB1504003; 2017YFD0601003）; 广东省科技计划（201804010125）
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