乙丙共聚物热管氧化沉积物研究

doi:10.12422/j.issn.1006-396X.2025.06.004

摘要/Abstract

摘要：

随着节能环保标准持续攀升，优化润滑油高温清净性能、减少发动机活塞沉积物，已成为润滑油领域的当务之急。采用热管氧化实验法，针对乙丙共聚物（OCP型黏度指数改进剂），分别在温度为250、280、310 ℃的条件下开展氧化沉积物实验，并借助FT?IR、SEM/EDS、1H?NMR等表征手段，对氧化沉积物的形貌特征、元素组成及官能团结构进行了表征。结果表明，在温度为250 ℃的条件下，基础油与混合样品（质量分数为1%的OCP型黏度指数改进剂+质量分数为99%的基础油）的沉积物量较为接近；在温度为280 ℃的条件下，混合样品的沉积物量多于基础油，且沉积物中C、S元素的质量分数上升，O元素的质量分数下降；在温度为310 ℃的条件下，因OCP型黏度指数改进剂与基础油产生协同作用，混合样品沉积物中的烃类、含氧官能团占比变动幅度减小，同时硫化物以SO?的形式逸散，导致S元素的质量分数降低。

关键词: 基础油, 乙丙共聚物, 氧化沉积物, 热管氧化实验法, 黏度指数改进剂

Abstract:

With the continuous rise of energy conservation and environmental protection standards, optimizing the high temperature cleaning performance of lubricating oil and reducing engine piston deposits have become a top priority in the field of lubricating oil. In this study, the heat pipe oxidation test was adopted to conduct oxidation deposit tests on ethylene?propylene copolymer （OCP?type viscosity index improver）at 250, 280, and 310 ℃ respectively. Characterization of the wall deposits was performed using Fourier Transform Infrared Spectroscopy （FT?IR）, Scanning Electron Microscopy/Energy Dispersive Spectroscopy （SEM/EDS）, and 1H Nuclear Magnetic Resonance （¹H?NMR） to analyze their morphological features, elemental composition, and functional group structures. The results indicate that at a temperature of 250 ℃, the deposit contents of the base oil and the mixed sample (1% mass fraction of OCP?type viscosity index improver + 99% mass fraction of base oil) were relatively close. The deposit amount of the mixed sample was greater than that of the base oil at 280 ℃, and the contents of C and S elements increased in this deposit, while the content of O element decreased. Due to the synergistic effect between the OCP and the base oil, the changes in hydrocarbons and oxygen?containing functional groups in the deposits of the mixed sample were reduced at 310 ℃, and sulfides escaped in the form of SO?, leading to a decrease in S element content.

Key words: Base oil, Ethylene?propylene copolymer, Oxidation deposit, Heat pipe oxidation test mothod, Viscosity index improver

中图分类号:

TE626

鄂红军, 阿合波塔·巴合提null, 吴思, 金佳佳. 乙丙共聚物热管氧化沉积物研究[J]. 石油化工高等学校学报, 2025, 38(6): 33-39.

Hongjun E, AHEBOTA·Bahet, Si WU, Jiajia JIN. Study on the Heat Pipe Oxidation Deposits of Ethylene⁃Propylene Copolymer[J]. Journal of Petrochemical Universities, 2025, 38(6): 33-39.

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链接本文: https://journal.lnpu.edu.cn/syhg/CN/10.12422/j.issn.1006-396X.2025.06.004

https://journal.lnpu.edu.cn/syhg/CN/Y2025/V38/I6/33

图/表 7

表1 1号基础油、OCP型黏度指数改进剂和混合样品的理化分析结果

Table 1 Physical and chemical analysis results of base oil No.1, OCP?type viscosity index improver, and mixed samples

分析指标	数值			测试标准
分析指标	1号基础油	OCP型黏度指数改进剂	混合样品	测试标准
运动黏度（100 ℃）/（mm²·s^-1）	4.98	-	9.87	GB/T 265-1988
黏度指数	95	-	133	GB/T 1995-1998
w（硫）/%	0.023 1	-	-	GB/T 17040-2019
蒸发损失率（诺亚克法，250 ℃，1 h）/%	9.7	-	-	NB/SH/T 0059-2010
w（饱和烃）/%	68.45	-	-	SH/T 0753-2005
运动黏度（柴油喷嘴剪切后，100 ℃）/（mm²·s^-1）	-	-	8.68	SH/T 0103-2007
高温高剪切黏度（150 ℃）/（mPa·s）	-	-	3.02	NB/SH/T 0703-2020
数均相对分子质量	-	8.5×10⁵	-	GB/T 21864-2008
分布系数	-	1.92	-	GB/T 21864-2008
n（乙烯）/n（丙烯）	-	45∶55	-	SH/T 1793-2015
支化度	-	12.3	-	ASTM D6474-2020

图1 1号基础油及混合样品在不同温度下的氧化沉积物分析结果

Fig.1 Analysis results of oxidation deposit of No.1 base oil and mixed samples at different temperatures

图2 混合样品的氧化沉积物在不同温度下的SEM分析结果

Fig.2 SEM analysis results of oxidation deposit from mixed samples at different temperatures

图3 混合样品的氧化沉积物在不同温度下的EDS分析结果

Fig.3 EDS analysis results of oxidation deposit from mixed samples at different temperatures

图4 混合样品的氧化沉积物在不同温度下的FT?IR分析结果

Fig.4 FT?IR analysis results of oxidation deposit from mixed samples at different temperatures

图5 混合样品的氧化沉积物在不同温度下的1H?NMR分析结果

Fig.5 1H?NMR analysis results of oxidation deposit from mixed samples at different temperatures

表2 氧化沉积物1H?NMR的化学位移、吸收峰归属以及峰面积

Table 2 1H?NMR chemical shift, absorption peak assignment, and peak area of oxidation deposit

编号	化学位移	吸收峰对应基团	峰面积
编号	化学位移	吸收峰对应基团	250 ℃	280 ℃	310 ℃
1	0.82~0.85	-CH₃	81.21	545.50	801.82
2	1.22~1.25	-CH₂	126.70	1 744.65	2 590.31
3	1.42~1.57	-CH₂	243.48	261.13	334.34
4	1.60~1.70	-CH-	3.52	44.37	15.10
5	2.10~2.20	-CH₂C=O	0.97	1.43	8.18

参考文献 23

[1]	KRYSHTANOVYCH M， TANASHCHUK K， KUPCHAK V， et al. Increasing the effectiveness of state policy in ensuring energy security and environmental protection［J］. International Journal of Energy Production and Management， 2024， 9（1）： 9⁃17.
[2]	DAVID L O， NWULU N I， AIGBAVBOA C O， et al. Integrating fourth industrial revolution （4IR） technologies into the water， energy & food nexus for sustainable security： A bibliometric analysis［J］. Journal of Cleaner Production， 2022， 363： 132522.
[3]	杨昊治，苏鹏，吴江，等. 发动机颗粒物产生机理及排放特性的研究现状［J］. 当代化工， 2023， 52（6）： 1430⁃1435.
	YANG H Z， SU P， WU J， et al. Research status of engine particulate matter generation mechanism and emission characteristics［J］. Contemporary Chemical Industry， 2023， 52（6）： 1430⁃1435.
[4]	YASUNORI S， YUKITOSHI F， MORITSUGU K. The performance of diesel engine oil using ashless anti⁃wear additive and detergent［J］. SAE International Journal of Advances and Current Practices in Mobility， 2024， 6（3）： 1393⁃1398.
[5]	DIABY M， SABLIER M， LE NEGRATE A， et al. Understanding carbonaceous deposit formation resulting from engine oil degradation［J］. Carbon， 2009， 47（2）： 355⁃366.
[6]	AHMED N S， NASSAR A M， ABDEL⁃HAMEED H S， et al. Preparation， characterization， and evaluation of some ashless detergent/dispersant additives for lubricating engine oil［J］. Applied Petrochemical Research， 2016， 6（1）： 49⁃58.
[7]	谢欣. 添加剂对SP/GF⁃6发动机油活塞清净性和节能性能的影响［J］. 石油炼制与化工， 2025， 56（3）： 113⁃120.
	XIE X. Effect of additives on piston cleanliness and energy reduction performance of SP/GF⁃6 engine oil［J］. Petroleum Processing and Petrochemicals， 2025， 56（3）： 113⁃120.
[8]	KASAI M， KOSHIMA H， TAKASHIMA Y. Piston detergency and anti⁃wear performance of non⁃phosphorus and non⁃ash engine oil： 2019⁃01⁃0021［R］. Warrendale： SAE International， 2019.
[9]	KAUL B， KASS M， NAFZIGER E， et al. Lubricant impacts on piston deposit formation in the enterprise marine diesel research engine［R］. Oak Ridge： Oak Ridge National Laboratory（ORNL）， 2023.
[10]	KASAI M， KOSHIMA H， TAKASHIMA Y. Piston detergency and anti⁃wear performance of non⁃phosphorus and non⁃ash engine oil： 2019⁃01⁃0021［R］. Warrendale： SAE International， 2019.
[11]	CHENG S S. The effects of engine oils on intake valve deposits and combustion chamber deposits： 932810［R］. Warrendale， PA： SAE International， 1993.
[12]	UEDA M， HANYUDA K， KUBO K. Effect of thermal stability of additives on diesel engine piston underside deposit： 2015⁃01⁃2036［R］. Warrendale： SAE International， 2015.
[13]	TAN K W， EISENBERG B， HUTCHINSON P A， et al. Impact of viscosity index improvers （Ⅶ） on the formation of piston deposits in fuel economy engine oils： 2019⁃01⁃2202［R］. Warrendale： SAE International， 2019.
[14]	MENDIRATTA R L， SINGH D. Effect of base oil and additives on combustion chamber and intake valve deposits formation in IC engine： 2004⁃28⁃0089［R］. Pune： The Automotive Research Association of India， 2004.
[15]	TAYLOR R I. Fuel⁃lubricant interactions： Critical review of recent work［J］. Lubricants， 2021， 9（9）： 92.
[16]	ANSOMBOON J， WUTTIMONGKOLCHAI A， PANNOI S， et al. Characterization of deposits and effects of detergent additive， olefin content and engine oil on intake valve deposit formation： 2000⁃01⁃2856［R］. Warrendale： SAE International， 2000.
[17]	YOSHIDA S， NAITOH Y. Analysis of deposit formation mechanism on TEOST 33C by engine oil containing MoDTC［J］. SAE International Journal of Fuels and Lubricants， 2008， 1（1）： 1534⁃1539.
[18]	HANTHORN J， SCHMIESING J. Identifying the limitations of the hot tube test as a predictor of lubricant performance in small engine applications： 2019⁃32⁃0510［R］. Tokyo： SAE Technical Paper， 2020.
[19]	OHKAWA S， SETO K， NAKASHIMA T， et al. "Hot tube test"⁃analysis of lubricant effect on diesel engine scuffing： 840262［R］. Warrendale： SAE International， 1984.
[20]	杨睿，杜斌，张志凌，等. 润滑油结焦行为的实验室评价［J］. 石油学报（石油加工）， 2013， 29（5）： 813⁃817.
	YANG R， DU B， ZHANG Z L， et al. Experimental evaluation of coking behavior of lubricating oils［J］. Acta Petrolei Sinica （Petroleum Processing Section）， 2013， 29（5）： 813⁃817.
[21]	UY D， PRANIS G， MORELLI A， et al. Correlating laboratory oil aerosol coking rig tests to diesel engine tests to understand the mechanisms responsible for turbocharger compressor coking： 2017⁃01⁃0887［R］. Warrendale： SAE International， 2017.
[22]	HAMIDULLAYEVNA A Z， PARPIYEVNA N G， KABULOVNA S D. Causes of contamination of lubricants used in diesel engines［J］. Texas Journal of Engineering and Technology， 2022， 13： 44⁃46.
[23]	GATTO V， MOEHLE W， SCHNELLER E， et al. A review of engine oil oxidation bench tests and their application in the screening of new antioxidant systems for low Phosphorus engine oils［J］. Journal of ASTM International， 2007， 4（7）： 1⁃13.