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）.
Key words
biodiesel /
desulfurization /
Ionic liquid /
H2O2 /
gutter oil
{{custom_sec.title}}
{{custom_sec.title}}
{{custom_sec.content}}
References
[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.
PDF(1569 KB)
