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

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

Abstract

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

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

CLC Number:

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.

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.

Figures/Tables 13

References 14

15	DE SILVA Sousa Leanne, DE MOURA Carla Verônica Rodarte, DE MOURA Edmilson Miranda. Influence of binary, ternary and quaternary mixtures on oxidative stability and study of kinetics and thermodynamic parameters of the degradation process of soybean biodiesel[J]. Fuel, 2020, 259: 116235.
16	滕雯, 陈勇, 隋猛, 等. TEPA与[MI][C₆H₂(OH)₃COO]复配对小桐子生物柴油抗氧化性的影响[J]. 化工进展, 2020, 39(11): 4427-4434.
	TENG Wen, CHEN Yong, SUI Meng, et al. Effect of TEPA and[MI][C₆H₂(OH)₃COO]compound on antioxidant property of biodiesel[J]. Chemical Industry and Engineering Progress, 2020, 39(11): 4427-4434.
17	耿再新, 孟娟, 彭桢, 等. TBHQ、VC、邻苯二胺复配抗氧化剂对地沟油制生物柴油抗氧化性能及抗氧化机理研究[J]. 化学世界, 2013, 54(10): 577-579, 584.
	GENG Zaixin, MENG Juan, PENG Zhen, et al. Study on antioxidtive properties and mechanism of TBHQ, VC and o-diamine benzene compound antioxidants for waste oil-made biodiesel[J]. Chemical World, 2013, 54(10): 577-579, 584.
18	ALMEIDA Eduardo S, PORTELA Flaysner M, SOUSA Raquel M F, et al. Behaviour of the antioxidant tert-butylhydroquinone on the storage stability and corrosive character of biodiesel[J]. Fuel, 2011, 90(11): 3480-3484.
19	Ferdinand BÄR, HOPF Henning, KNORR Markus, et al. Rancimat and PetroOxy oxidation stability measurements of rapeseed oil methyl ester stabilized with hydrazides and antioxidants[J]. Fuel, 2018, 232: 108-113.
20	WANG Wenchao, LI Fashe, WANG Hua. The effect of tetrethylenepentamine (TEPA) on the oxidation stability and the lubrication performance of biodiesel[J]. Industrial Crops and Products, 2021, 171: 113910.
21	国家质量监督检验检疫总局, 国家标准化管理委员会. 石油产品铜片腐蚀试验法: [S]. 北京: 中国标准出版社, 2017.
	Standardization Administration of the People's Republic of China. Test method for corrosiveness to copper from petroleum products by copper strip test: [S]. Beijing: Standards Press of China, 2017.
22	SUI Meng, LI Fashe. Effect of TEPA on oxidation stability and metal ion content of biodiesel[J]. Renewable Energy, 2019, 143: 352-358.
23	隋猛, 王霜, 李法社, 等. 酚胺类抗氧化剂复配对生物柴油抗氧化性能影响研究[J]. 中国油脂, 2018, 43(4): 88-91.
1	NOMANBHAY Saifuddin, Mei Yin ONG, CHEW Kit Wayne, et al. Organic carbonate production utilizing crude glycerol derived as by-product of biodiesel production: A review[J]. Energies, 2020, 13(6): 1483.
2	MUNIR Mamoona, AHMAD Mushtaq, MUBASHIR Muhammad, et al. A practical approach for synthesis of biodiesel via non-edible seeds oils using trimetallic based montmorillonite nano-catalyst[J]. Bioresource Technology, 2021, 328: 124859.
3	IDERIS Fazril, SHAMSUDDIN Abd Halim, NOMANBHAY Saifuddin, et al. Optimization of ultrasound-assisted oil extraction from Canarium odontophyllum kernel as a novel biodiesel feedstock[J]. Journal of Cleaner Production, 2021, 288: 125563.
4	Homa HOSSEINZADEH-BANDBAFHA, KUMAR Dipesh, SINGH Bhaskar, et al. Biodiesel antioxidants and their impact on the behavior of diesel engines: A comprehensive review[J]. Fuel Processing Technology, 2022, 232: 107264.
5	李法社, 李明, 包桂蓉, 等. 10种抗氧化剂对小桐子生物柴油氧化稳定性的影响[J]. 中国油脂, 2014, 39(1): 50-54.
	LI Fashe, LI Ming, BAO Guirong, et al. Effects of ten antioxidants on oxidation stability of Jatropha curcas L. biodiesel[J]. China Oils and Fats, 2014, 39(1): 50-54.
6	HAZRAT M A, RASUL M G, KHAN M M K, et al. Techniques to improve the stability of biodiesel: A review[J].Environmental Chemistry Letters, 2021, 19(3): 2209-2236.
7	SUNDUS F, FAZAL M A, MASJUKI H H. Tribology with biodiesel: A study on enhancing biodiesel stability and its fuel properties[J]. Renewable and Sustainable Energy Reviews, 2017, 70: 399-412.
8	张腾, 孙志春, 王珉, 等. 生物柴油腐蚀性试验研究[J]. 广州化工, 2012, 40(12): 109-110, 141.
	ZHANG Teng, SUN Zhichun, WANG Min, et al. Experimental studies of biodiesel corrosion[J]. Guangzhou Chemical Industry, 2012, 40(12): 109-110, 141.
9	AGARWAL Shilpi, SINGHAL Shailey, SINGH Manjeet, et al. Role of antioxidants in enhancing oxidation stability of biodiesels[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(8): 11036-11049.
10	FAZAL M A, HASEEB A S M A, MASJUKI H H. Comparative corrosive characteristics of petroleum diesel and palm biodiesel for automotive materials[J]. Fuel Processing Technology, 2010, 91(10): 1308-1315.
11	RODRIGUES Jailson Silva, VALLE Camila Peixoto DO, UCHOA Antonia Flávia Justino, et al. Comparative study of synthetic and natural antioxidants on the oxidative stability of biodiesel from Tilapia oil[J]. Renewable Energy, 2020, 156: 1100-1106.
23	SUI Meng, WANG Shuang, LI Fashe, et al. Effect of phenolic antioxidant compound amine antioxidant on antioxidant property of biodiesel[J]. China Oils and Fats, 2018, 43(4): 88-91.
24	项念念. 四乙烯五胺改性膨润土的制备及对铜、镍、镉的吸附研究[D]. 成都: 成都理工大学, 2014.
	XIANG Niannian. Preparation of bentonite modified tetraethylenepentamine and its adsorption of copper, nickel, cadmium[D]. Chengdu: Chengdu University of Technology, 2014.
12	隋猛, 李法社, 吴学华, 等. 阴离子功能化生物柴油离子液体抗氧化剂[X][C₆H₅COO]的制备[J]. 燃料化学学报, 2019, 47(1): 66-73.
	SUI Meng, LI Fashe, WU Xuehua, et al. Preparation of anionic functionalized ionic liquid antioxidant[X][C₆H₅COO]for biodiesel[J]. Journal of Fuel Chemistry and Technology, 2019, 47(1): 66-73.
13	YANG Jie, HE Quan Sophia, CORSCADDEN Kenneth, et al. Improvement on oxidation and storage stability of biodiesel derived from an emerging feedstock camelina[J]. Fuel Processing Technology, 2017, 157: 90-98.
14	吴永会, 李法社, 王霜, 等. 没食子酸酯类抗氧化剂对不同植物油氧化稳定性能影响的研究[J]. 中国粮油学报, 2019, 34(5): 56-61.
	WU Yonghui, LI Fashe, WANG Shuang, et al. Effects of Gallic acid antioxidants on oxidative stability of different vegetable oils[J]. Journal of the Chinese Cereals and Oils Association, 2019, 34(5): 56-61.

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

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

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

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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[13]	YUAN Haoran，CHEN Xinde，CHEN Yong. Advance in liquid fuel synthesis from organic wastes [J]. Chemical Industry and Engineering Progree, 2009, 28(7): 1151-.
[14]	HE Yongzhi，ZHANG Bingru，LI Fengting，WANG Sen. Research on performance of polyepoxysuccinic acid used in washing water of blast furnace gas [J]. Chemical Industry and Engineering Progree, 2007, 26(4): 590-.