高黏度烷基苊基础油的合成及润滑性能研究

doi:10.11949/0438-1157.20220523

摘要/Abstract

摘要：

目前润滑基础油主要来源于石油资源，基于我国富煤贫油的现状，开发煤基原料合成润滑基础油的工艺路线具有重要意义。以煤化工过程产生的多环芳烃（苊）和烯烃为原料，以离子液体（[Et₃NH][Al₂Cl₇]）为催化剂通过烷基化反应探索了高黏度润滑基础油的合成。通过调控烯烃（己烯或辛烯）和苊的反应比例，合成了四种不同组成和结构的多烷基苊基础油，通过GC和GC-MS对其成分进行了分析。对不同油品的物化性能指标进行表征，揭示了产物组成结构和性质的关系，烷基苊基础油具有高的黏度（10.1~19.5 mm²·s^-1，100℃）、苯胺点（<63℃）和起始氧化温度（>190℃）；同时，烷基苊作为润滑基础油表现出优良的摩擦学性能，且随着苊环侧链烷基化程度的增加，其抗载荷能力会增强。

关键词: 离子液体, 润滑基础油, 苊, 烯烃, 烷基化

Abstract:

At present, lubricating base oil mainly comes from petroleum resources. Based on the current situation of rich coal and lean oil in China, it is of great significance to develop a process route for synthesizing lubricating base oil from coal-based raw materials. Acenaphthene and α-olefins are the products of coal coking and coal-to-oils, respectively. Herein, the ionic liquid ([Et₃NH][Al₂Cl₇]) was used as catalyst for the acenaphthene alkylation with α-olefins (C₆ and C₈) to produce high-viscosity lubricating base oil. Four alkylated acenaphthene products with various alkyl lengths were obtained by adjusting the feeding ratio, and their structures were analyzed by GC and GC-MS. Moreover, the physicochemical properties of synthetic oils were investigated to reveal their structure-properties relationship, the synthetic alkylated products showed high viscosity (10.1—19.5 mm²·s^-1, 100℃), the aniline points (<63℃), and the oxidative onset temperatures (>190℃). The alkylated acenaphthenes as base oils displayed excellent tribological performance, the increase of side-chains on acenaphthene was beneficial to enhance their load-carrying capacity and tribological property.

Key words: ionic liquid, lubricating base oil, acenaphthene, olefin, alkylation

中图分类号:

TQ 241.5

崔敬泽, 汤琼, 陈晨, 刘宇婕, 徐红, 刘雷, 董晋湘. 高黏度烷基苊基础油的合成及润滑性能研究[J]. 化工学报, 2022, 73(8): 3659-3668.

Jingze CUI, Qiong TANG, Chen CHEN, Yujie LIU, Hong XU, Lei LIU, Jinxiang DONG. Synthesis of high viscosity alkylated acenaphthene and investigation of their lubrication property[J]. CIESC Journal, 2022, 73(8): 3659-3668.

图/表 13

图1 离子液体催化苊与1-己烯/1-辛烯合成润滑基础油

Fig.1 Synthesis of lubricating base oils by acenaphthene alkylation with 1-hexene / 1-octene catalyzed by ionic liquid

图2 己基苊（a）和辛基苊（b）的气相谱图

Fig.2 Gas chromatogram of the hexylacenaphthene (a) and octylacenaphthene (b)

图3 不同烯苊比对产物分布的影响

Fig.3 Effect of different ratio of olefins to acenaphthene on product distribution

表1 己基苊和辛基苊的产物分布

Table 1 Product distribution of hexylacenaphthene and octylacenaphthene

样品名称	烯烃/苊（摩尔比）	产物分布/%
样品名称	烯烃/苊（摩尔比）	单烷基苊	二烷基苊	三烷基苊	四烷基苊
己基苊-2	2/1	22.60	54.50	22.39	0.51
己基苊-3	3/1	3.55	31.48	58.37	6.59
辛基苊-2	2/1	25.08	46.27	28.00	0.64
辛基苊-3	3/1	7.17	38.10	50.51	4.22

图4 反应前后离子液体的乙腈探针红外吸收谱图

Fig.4 FT-IR absorption spectra with acetonitrile probe of ionic liquid before and after reaction

表2 烷基苊产物的基本物化性质

Table 2 Physicochemical properties of alkylated acenaphthenes

产品名称	密度/ (g·cm^-3)	运动黏度/(mm²·s^-1)		黏度指数	苯胺点/℃	倾点/℃	闪点/℃	起始氧化温度/℃
产品名称	密度/ (g·cm^-3)	40℃	100℃	黏度指数	苯胺点/℃	倾点/℃	闪点/℃	起始氧化温度/℃
己基苊-2	0.9534	171.9	10.1	—	15.2	-18	201	192
己基苊-3	0.9343	349.6	15.4	—	34.5	-16	208	198
辛基苊-2	0.9372	190.5	12.5	24	38.5	-23	219	201
辛基苊-3	0.9186	331.6	19.5	52	62.4	-19	236	205

图5 己基苊-2（a）、己基苊-3（b）、辛基苊-2（c）和辛基苊-3（d）在钢盘上的接触角

Fig.5 Contact angle of hexylacenaphthene-2 (a), hexylacenaphthene-3 (b), octylacenaphthene-2 (c) and octylacenaphthene-3 (d) on steel disc

图6 剪切黏度随剪切速率的变化

Fig.6 Shear viscosity versus shear rate

图7 在100 N（a）、200 N（b）和300 N（c）载荷下的摩擦曲线和平均摩擦系数（d）

Fig.7 Friction curves under the load of 100 N (a), 200 N (b) and 300 N (c) and average friction coefficient (d)

图8 钢盘的磨损体积

Fig.8 Wear volume of steel disc

图9 N4010润滑的钢盘的3D白光图和磨痕轮廓图(a) 100 N; (b) 200 N; (c) 300 N

Fig.9 3D images and profiles of wear scar of steel discs lubricated by N4010

图10 己基苊-2润滑的钢盘的3D白光图和磨痕轮廓图(a) 100 N; (b) 200 N; (c) 300 N

Fig.10 3D images and profiles of wear scar of steel discs lubricated by hexylacenaphthene-2

图11 己基苊-3润滑的钢盘的3D白光图和磨痕轮廓图(a) 100 N; (b) 200 N; (c) 300 N

Fig.11 3D images and profiles of wear scar of steel discs lubricated by hexylacenaphthene-3

参考文献 35

1	Holmberg K, Erdemir A. The impact of tribology on energy use and CO₂ emission globally and in combustion engine and electric cars[J]. Tribology International, 2019, 135: 389-396.
2	Holmberg K, Erdemir A. Influence of tribology on global energy consumption, costs and emissions[J]. Friction, 2017, 5(3): 263-284.
3	Fan M J, Ai J, Hu C H, et al. Naphthoate based lubricating oil with high oxidation stability and lubricity[J]. Tribology International, 2019, 138: 204-210.
4	Liu S B, Bhattacharjee R, Li S, et al. Thiol-promoted catalytic synthesis of high-performance furan-containing lubricant base oils from biomass derived 2-alkylfurans and ketones[J]. Green Chemistry, 2020, 22(22): 7896-7906.
5	Fox I E. Numerical evaluation of the potential for fuel economy improvement due to boundary friction reduction within heavy-duty diesel engines[J]. Tribology International, 2005, 38(3): 265-275.
6	Hu S J, Zhu J H, Wu B C, et al. Green synthesis of ester base oil with high viscosity(Ⅰ): Catalyst preparation, characterization, evaluation, and mechanism analysis[J]. Fuel, 2020, 274: 117802.
7	Jiang H B, Xu X L, Hong X Z, et al. Preparation of high viscosity PAO from mixed alpha-olefins over metallocene catalyst[J]. China Petroleum Processing & Petrochemical Technology, 2018, 20(2): 90-96.
8	Hu S J, Zhu J H, Wu B C, et al. Green synthesis of ester base oil with high viscosity(Ⅱ): Reaction kinetics study[J]. Chemical Engineering Research and Design, 2021, 165: 51-60.
9	Li L, Zhao X R, Chen C, et al. Highly selective synthesis of polyalkylated naphthalenes catalyzed by ionic liquids and their tribological properties as lubricant base oil[J]. ChemistrySelect, 2019, 4(18): 5284-5290.
10	Chen C, Tang Q, Xu H, et al. Alkylation of naphthalene with n-butene catalyzed by liquid coordination complexes and its lubricating properties[J]. Chinese Journal of Chemical Engineering, 2021, 39: 306-313.
11	Nagendramma P, Kaul S. Development of ecofriendly/biodegradable lubricants: an overview[J]. Renewable and Sustainable Energy Reviews, 2012, 16(1): 764-774.
12	Yang T, Wang F J, Huang J P, et al. Efficient continuous-flow synthesis of long-chain alkylated naphthalene catalyzed by ionic liquids in a microreaction system[J]. Reaction Chemistry & Engineering, 2021, 6(10): 1950-1960.
13	Granda M, Blanco C, Alvarez P, et al. Chemicals from coal coking[J]. Chemical Reviews, 2014, 114(3): 1608-1636.
14	谷小会. 煤焦油分离方法及组分性质研究现状与展望[J]. 洁净煤技术, 2018, 24(4): 1-6, 12.
	Gu X H. Status and prospect of separation methods and composition characteristics of coal tar[J]. Clean Coal Technology, 2018, 24(4): 1-6, 12.
15	Ma Z H, Wei X Y, Liu G H, et al. Value-added utilization of high-temperature coal tar: a review[J]. Fuel, 2021, 292: 119954.
16	汪廷贵, 张乐涛, 蔡国星, 等. 一种烷基萘基础油的合成及润滑性能研究[J]. 石油炼制与化工, 2013, 44(11): 96-99.
	Wang T G, Zhang L T, Cai G X, et al. Study on synthesis of alkyl naphthalene base oils and their lubricating properties[J]. Petroleum Processing and Petrochemicals, 2013, 44(11): 96-99.
17	刘雷, 陈晨, 李磊, 等. 一种利用离子液体催化制备多烷基萘的方法及其应用: 109824467A[P]. 2019-05-31.
	Liu L, Chen C, Li L, et al. Method for preparing polyalkylnaphthalene through catalysis of ionic liquid and application of method: 109824467A[P]. 2019-05-31.
18	Peters A T. Acenaphthene series(Ⅰ): Mono- and di-tert.-butyl-acenaphthene, -acenaphthenequinone, and -naphthalic anhydride, and their derivatives[J]. Journal of the Chemical Society (Resumed), 1942: 562-565.
19	Nürsten H E, Peters A T. Acenaphthene series(Ⅲ): Orientation of tert.-butyl- and di-tert.-butyl-acenaphthene, and preparation of new derivatives[J]. Journal of the Chemical Society(Resumed), 1950: 729-736.
20	Illingworth E, Peters A T. Acenaphthene series(Ⅶ): The three isomeric tert.-butylacenaphthenes. Migration of tert.-butyl groups and disproportionation. Preparation and orientation of 1,3,6-tri-tert.-butylacenaphthene[J]. Journal of the Chemical Society (Resumed), 1952: 2730-2735.
21	Peters A T. Mechanisms of reactions in the acenaphthene series. Migration of t-butyl, and disproportionate[J]. Nature, 1965, 205(4967): 170-171.
22	Mock W L, Tsao L I. Isopropylation of acenaphthene[J]. Synthetic Communications, 1991, 21(3): 371-378.
23	Chen S, Wu T T, Zhao C. Conversion of lipid into high-viscosity branched bio-lubricant base oil[J]. Green Chemistry, 2020, 22(21): 7348-7354.
24	Covitch M J, Trickett K J. How polymers behave as viscosity index improvers in lubricating oils[J]. Advances in Chemical Engineering and Science, 2015, 5(2): 134-151.
25	Martini A, Ramasamy U S, Len M. Review of viscosity modifier lubricant additives[J]. Tribology Letters, 2018, 66(2): 1-14.
26	Fan M J, Zhang C Y, Wen P, et al. High-performance lubricant base stocks from biorenewable Gallic acid: systematic study on their physicochemical and tribological properties[J]. Industrial & Engineering Chemistry Research, 2017, 56(34): 9513-9523.
27	Zhmud B. Beyond the aniline point: critical solution point for the oil/aniline system as a measure of oil solubility[J]. Fuel, 2007, 86(16): 2545-2550.
28	Elhamarnah Y A, Nasser M, Qiblawey H, et al. A comprehensive review on the rheological behavior of imidazolium based ionic liquids and natural deep eutectic solvents[J]. Journal of Molecular Liquids, 2019, 277: 932-958.
29	Zhou S Q, Ni R, Funfschilling D. Effects of shear rate and temperature on viscosity of alumina polyalphaolefins nanofluids[J]. Journal of Applied Physics, 2010, 107(5): 054317.
30	Kerni L, Raina A, Haq M I U. Friction and wear performance of olive oil containing nanoparticles in boundary and mixed lubrication regimes[J]. Wear, 2019, 426/427: 819-827.
31	Liu X X, Li Q, Gao X X, et al. The palm oil-based microemulsion: fabrication, characterization and rheological properties[J]. Journal of Molecular Liquids, 2020, 302: 112527.
32	Jiang D, Hu L T, Feng D P. Crown-type ionic liquids as lubricants for steel-on-steel system[J]. Tribology Letters, 2011, 41(2): 417-424.
33	Mendonça A C F, Malfreyt P, Pádua A A H. Interactions and ordering of ionic liquids at a metal surface[J]. Journal of Chemical Theory and Computation, 2012, 8(9): 3348-3355.
34	Yu Q L, Zhang C Y, Dong R, et al. Physicochemical and tribological properties of gemini-type halogen-free dicationic ionic liquids[J]. Friction, 2021, 9(2): 344-355.
35	Guo Y X, Qiao D, Han Y Y, et al. Application of alkylphosphate ionic liquids as lubricants for ceramic material[J]. Industrial & Engineering Chemistry Research, 2015, 54(51): 12813-12825.

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