TEPA/TBHQ复配对生物柴油氧化安定-腐蚀性的影响

doi:10.16085/j.issn.1000-6613.2022-2240

化工进展 ›› 2023, Vol. 42 ›› Issue (11): 5661-5668.DOI: 10.16085/j.issn.1000-6613.2022-2240

TEPA/TBHQ复配对生物柴油氧化安定-腐蚀性的影响

何需要¹^,²^,³(), 陈仁义⁴, 刘明⁴, 李恒龙¹, 李法社¹^,²^,³(), 张慧聪¹^,²^,³

^1.昆明理工大学冶金与能源工程学院, 云南昆明 650093
^2.省部共建复杂有色金属资源清洁利用国家重点实验室, 云南昆明 650093
^3.冶金节能减排教育部工程研究中心, 云南昆明 650093
^4.瀚蓝绿电固废处理(佛山)有限公司, 广东佛山 528225

收稿日期:2022-12-02 修回日期:2023-01-30 出版日期:2023-11-20 发布日期:2023-12-15
通讯作者: 李法社
作者简介:何需要（1996—），男，硕士研究生，研究方向为生物质能利用与转换。E-mail：1031473560@qq.com。
基金资助:
国家自然科学基金(52166013);云南省基础研究计划(202101AS070115);国家自然科学基金联合基金(U1602272)

Effect of TEPA/TBHQ combination on oxidative stability-corrosion of biodiesel

HE Xuyao¹^,²^,³(), CHEN Renyi⁴, LIU Ming⁴, LI Henglong¹, LI Fashe¹^,²^,³(), ZHANG Huicong¹^,²^,³

^1.Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, Yunnan, China
^2.State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming 650093, Yunnan, China
^3.Engineering Research Center of Metallurgical Energy Conservation and Emission Reduction Ministry of Education, Kunming 650093, Yunnan, China
^4.Hanlan Green Electric Solid Waste Treatment (Foshan) Co. , Ltd. , Foshan 528225, Guangdong, China

Received:2022-12-02 Revised:2023-01-30 Online:2023-11-20 Published:2023-12-15
Contact: LI Fashe

摘要/Abstract

摘要：

生物柴油作为一种绿色低碳液体燃料，由于其氧化安定性差，易腐蚀金属，限制了其大规模应用。本文以小桐子生物柴油为研究对象，复配了四乙烯五胺（TEPA）/叔丁基对苯二酚（TBHQ）高效抗氧化-缓蚀剂；采用Rancimat法、扫描电子显微镜等技术探究复配抗氧化-缓蚀剂对生物柴油氧化安定性与腐蚀性能的影响规律及机制。结果表明，添加0.1‰（质量分数）比例为4∶1的复配抗氧化-缓蚀剂时可使生物柴油诱导期从4.24h提升到7.83h。同时其也有很好的缓蚀性能，使生物柴油的铜片腐蚀等级从3a降到1a；铜片表面碳元素质量分数从10.5%降为8.5%，氧元素质量分数由10%降为0。TEPA螯合铜离子，TBHQ中断生物柴油链式反应，TEPA能提供H自由基还原再生作用后的TBHQ，两者复配有良好的协同作用，可改善生物柴油氧化安定性与腐蚀性能。可为生物柴油大规模应用提供理论支撑。

关键词: 液体燃料, 四乙烯五胺, 叔丁基对苯二酚, 复配抗氧化-缓蚀剂, 抗氧化性, 缓蚀性

Abstract:

Biodiesel is a green low-carbon liquid fuel. Poor oxidation stability and tendency to corrode metals limit its large-scale application. In this study, tetraethylenepentamine (TEPA) and tert-butylhydroquinone (TBHQ) were compounded to an highly effective inhibitor of oxidation-corrosion taking Jatropha biodiesel as the object of study. The Rancimat method, scanning electron microscope and other characterization methods were used to investigate the effect and mechanism of the oxidation-corrosion inhibitor on the oxidation stability and corrosion performance of biodiesel. The results showed that the oxidation induction period was increased from 4.24h to 7.83h by adding 0.1‰ inhibitor with the ratio of 4∶1 oxidation-corrosion into Jatropha biodiesel. Meanwhile, it had better corrosion inhibition. The corrosion grade on a copper strip of biodiesel was decreased from 3a to 1a, the carbon element on the surface of the copper strip was reduced from 10.5% to 8.5%, and the oxygen element was decreased from 10% to 0. TEPA chelated Cu²⁺, and TBHQ provided H radicals to interrupt the biodiesel auto-oxidation chain reaction. TEPA could provide H radicals to restore and regenerate the used TBHQ. The combination of the two had a good synergistic effect, which could improve biodiesel oxidative stability and corrosion. This study provided theoretical support for the large-scale application of biodiesel.

Key words: liquid fuel, tetraethylenepentamine (TEPA), tert-butylhydroquinone (TBHQ), oxidation-corrosion inhibitor, antioxidation, corrosion inhibition

中图分类号:

何需要, 陈仁义, 刘明, 李恒龙, 李法社, 张慧聪. TEPA/TBHQ复配对生物柴油氧化安定-腐蚀性的影响[J]. 化工进展, 2023, 42(11): 5661-5668.

HE Xuyao, CHEN Renyi, LIU Ming, LI Henglong, LI Fashe, ZHANG Huicong. Effect of TEPA/TBHQ combination on oxidative stability-corrosion of biodiesel[J]. Chemical Industry and Engineering Progress, 2023, 42(11): 5661-5668.

图/表 13

表1 小桐子生物柴油脂肪酸甲酯组成

组成	分子式	相对分子质量	相对含量/%
肉豆蔻酸甲酯	C₁₅H₃₀O₂	242.40	0.13
棕榈酸甲酯	C₁₇H₃₄O₂	270.45	13.10
棕榈油酸甲酯	C₁₇H₃₂O₂	268.44	0.39
硬脂酸甲酯	C₁₉H₃₈O₂	298.50	7.78
油酸甲酯	C₁₉H₃₆O₂	296.49	38.18
亚油酸甲酯	C₁₉H₃₄O₂	294.47	39.52
亚麻酸甲酯	C₁₉H₃₂O₂	292.456	0.65
花生酸甲酯	C₂₁H₄₂O₂	326.56	0.25

图1 氧化稳定性试验装置流程

图2 测试样品氧化稳定性曲线图

图3 单一抗氧化剂与复配抗氧化-缓蚀剂对生物柴油氧化安定性影响

图4 TEPA对小桐子生物柴油抗氧化机理

图5 TBHQ对小桐子生物柴油抗氧化机理及被还原路径

图6 复配抗氧化-缓蚀剂不同浓度对小桐子生物柴油氧化稳定性的影响

图7 单一抗氧化剂与复配抗氧化-腐蚀剂对小桐子生物柴油缓蚀性能影响

图8 TBHQ在铜表面的吸附示意图

图9 铜片腐蚀等级对照A—添加0.5‰复配抗氧化-缓蚀剂；B—添加1‰复配抗氧化-缓蚀剂；C—添加1.5‰复配抗氧化-缓蚀剂；D—添加2‰复配抗氧化-缓蚀剂

图10 生物柴油铜片腐蚀形貌

图11 铜片腐蚀后的表面能谱图

表2 金属表面元素质量分数

元素	未添加复配抗氧化-缓蚀剂/%	添加复配抗氧化-缓蚀剂/%
Cu	76.2	91.3
C	10.5	8.5
O	10.0	0.0
N	2.8	0.2
Cl	0.4	0.0
Ca	0.1	0.1

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TEPA/TBHQ复配对生物柴油氧化安定-腐蚀性的影响

Effect of TEPA/TBHQ combination on oxidative stability-corrosion of biodiesel

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