Separation and Characterization of Tahe Asphaltenes

doi:10.3969/j.issn.1006-396X.2022.01.003

Abstract

Abstract:

Tahe asphaltene (T_A) was separated into heavy component(T_A1) and light component (T_A2). The surface morphology, crystal structure and functional group structure of T_A, T_A1 and T_A2 were characterized by Scanning Electron Microscope (SEM), X?ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT?IR) and ¹H?Nuclear Magnetic Resonance Spectrum (¹H?NMR). The results show that TA has less long?chain structure, more branched chains in side chains, and is mainly composed of short branched alkyl structure such as methyl, ethyl and propyl. Sub?components T_A1 and T_A2 show obviously different microstructure after separated from T_A. TA1 has the highest degree of graphitization, the longest branched chain, more side?chains of aromatic ring, less branched chains of alkyl side?chains and relatively strong aromaticity, while T_A2 has lower degree of graphitization, more branched chains of alkyl side?chains, less side?chains of aromatic ring and relatively weak aromaticity.

Key words: Asphaltene, Separation, Composition, Structure

摘要：

采用甲苯?正庚烷法将塔河沥青质（T_A）分离成重组分（T_A1）和轻组分（T_A2），使用扫描电镜（SEM）、X射线衍射（XRD）、傅里叶变换红外光谱法（FT?IR）和核磁共振氢谱（¹H?NMR）等方法对T_A、T_A1和T_A2进行表征，分析其表面形态、晶体结构和官能团结构等组成和结构信息。结果表明，T_A具有较少的长链结构，侧链中支链化程度较高，并以甲基、乙基、丙基短支链烷基结构为主。T_A经分离后得到的亚组分T_A1、T_A2在微观结构上存在明显差异，T_A1石墨化程度最高，支链最长，芳环侧链较多，烷基侧链支化程度较差，芳香性相对较强；T_A2石墨化程度较差，烷基侧链支化程度较高，芳环侧链较少，芳香性相对较弱。

关键词: 沥青质, 分离, 组成, 结构

CLC Number:

TE65

Donghao Lin, Genxiang Luo, Mengshuang Zhu, Jin Huang, Mingyu Qi, Aimin Ning, Lingzi Xu. Separation and Characterization of Tahe Asphaltenes[J]. Journal of Petrochemical Universities, 2022, 35(1): 18-22.

林东浩, 罗根祥, 朱孟爽, 黄金, 齐名玉, 宁爱民, 许凌子. 塔河沥青质亚组分分离及表征[J]. 石油化工高等学校学报, 2022, 35(1): 18-22.

Figures/Tables 10

Table1 The fraction of Tahe asphaltene after separation

组分	m/g	w/%
T_A1	3.26	83.80
T_A2	0.63	16.20

Fig.1 Scanning electron microscopy of TA,TA1,TA2

Fig.2 XRD spectrum of TA,TA1,TA2

Table 2 The structural parameters of TA,TA1,TA2

样品	d_m/nm	d_γ/nm	L_a/nm	L_c/nm	M
T_A	3.484	4.629	10	27	8.750
T_A1	3.468	4.744	7	20	6.766
T_A2	3.551	4.519	8	23	7.477

Fig.3 Infrared absorption spectrogram of TA,TA1,TA2

Table 3 Functional group structure represented by different wave numbers

波数/cm^-1	官能团结构
1 700	C=O的拉伸
1 600	芳香环中C=C的拉伸
1 460	CH₂中C-H的对称弯曲，CH₃中C-H的不对称弯曲，芳香环中C=C的不对称拉伸
1 376	CH₃中C-H的对称弯曲
1 030	亚砜中S＝O的拉伸
864	芳香族化合物中C-H的平面外弯曲
814	芳香族化合物中C-H的平面外弯曲
743	芳香族化合物中C-H的平面外弯曲
724	芳香族化合物中C-H的平面外弯曲和CH₂中C-H的弯曲
2 953	CH₃中C-H的不对称拉伸和烷烃中C-H的不对称拉伸
2 923	CH₂中C-H的不对称拉伸
2 862	CH₃中C-H的对称拉伸和CH₂中C-H的不对称拉伸

Table 4 Formulas for calculating each index

结构指数	计算公式
芳香性指数	$I A r = A 1 600 ∑ A$
脂肪族指数	$I A l = A 1 460 + A 1 376 ∑ A$
支链指数	$I B = A 1 376 A 1 460 + A 1 376$
长链指数	$I L c = A 724 A 1 460 + A 1 376$
亚砜指数	$I S = O = A 1 030 ∑ A$
甲基和亚甲基氢碳比	$M M H C = A 1 380 5 + A 2 920 7 A 1 380 15 + A 2 920 14$

Table 4 Formulas for calculating each index

结构指数	计算公式
芳香性指数	$I A r = A 1 600 ∑ A$
脂肪族指数	$I A l = A 1 460 + A 1 376 ∑ A$
支链指数	$I B = A 1 376 A 1 460 + A 1 376$
长链指数	$I L c = A 724 A 1 460 + A 1 376$
亚砜指数	$I S = O = A 1 030 ∑ A$
甲基和亚甲基氢碳比	$M M H C = A 1 380 5 + A 2 920 7 A 1 380 15 + A 2 920 14$

Table 5 The structural indices of TA,TA1,TA2

样品	I_Ar	I_Al	I_B	I_Lc	I_S=O	MMHC
T_A	0.314 4	0.299 5	0.135 4	0.013 3	0.020 7	2.255 7
T_A1	0.330 1	0.244 6	0.121 3	0.071 9	0.033 3	2.202 2
T_A2	0.208 3	0.326 8	0.160 5	0.011 5	0.026 8	2.265 2

Table 6 1H?NMR hydrogen spectrum of TA,TA1,TA2

样品	H_γ	H_β	H_α	n	H_A
T_A	16.430	51.800	20.670	4.301	11.100
T_A1	16.530	51.560	21.170	4.216	10.740
T_A2	16.820	52.180	19.460	4.546	11.540

Table 7 The structure parameters of TA,TA1,TA2

样品	f_A	σ	H_AU/C_A
T_A	0.579	0.482	0.365
T_A1	0.633	0.496	0.319
T_A2	0.375	0.457	0.646

References 23

1	Pfeiffer J，Saal R N J.Asphaltic bitumen as colloid system［J］.The Journal of Physical Chemistry，1940，44（2）：139⁃149.
2	Sheu E Y，Mullins O C.Asphaltenes fundamentals and applications［M］.New York：Plenum Press，1995．
3	张梦轲，吴玉国，常显扬，等.HLB对原油乳化降黏的影响及分析［J］.辽宁石油化工大学学报，2019，39（2）：27⁃33.
	Zhang M K，W Y G，Chang X Y，et al.The influence and analysis of HLB on emulsification and viscosity of crude oil［J］.Journal of Liaoning Shihua University，2019，39（2）：27⁃33.
4	Kharrat A M，Indo K，Mostowfi F，et al.Asphaltene content measurement using an optical spectroscopy technique［J］.Energy & Fuels，2013，27（5）：2452⁃2457.
5	Pereira J C，Lopez I，Salas R，et al.Resins：The molecules responsible for the stability/instability phenomena of asphaltenes［J］.Energy & Fuels，2007，21（3）：1317⁃1321.
6	贾雪娅，马凤云，洪琨，等.塔河常压渣油中不同沥青质的组成与结构研究［J］.石油炼制与化工，2018，49（12）：43⁃47.
	Jia X Y，Ma F Y，Hong K，et al.Compositions and and structures of different asphaltenes in Tahe atmospheric residue［J］.Petroleum Processing and Petrochemical，2018，49（12）：43⁃47.
7	Gutierrez L B，Ranaudo M A，Mendez B.Fractionation of asphaltene by complex formation with p⁃Nitrophenol：A method for structural studies and stability of asphaltene colloids［J］.Energy & Fuels，2001，15（3）：624⁃628.
8	Gould K A，Long R B.A new technique for the acid/base separation of petroleum and coal⁃derived fractions［J］.Fuel，1986，65（4）：572⁃576.
9	Nalwaya V，Tantayakom V，Piumsomboon P，et al.Studies on asphaltenes through analysis of polar fractions［J］.Industrial & Engineering Chemistry Research，1999，43（23）：964⁃972.
10	张艳芳，梁文杰，刘晨光.对孤岛及单家寺沥青中沥青质的X⁃射线衍射研究［J］.石油学报（石油加工），1989，5（3）：7⁃14.
	Zhang Y F，Liang W J，Liu C G.Investigation of asphaltenes in Gudao and Shanjiasi asphalts by XRD［J］.Acta Petrolei Sinica（Petroleum Processing Section），1989，5（3）：7⁃14.
11	樊亮，魏建明，胡家波.青川天然沥青的组成及其沥青质结构参数研究［J］.公路交通技术，2015（2）：40⁃44.
	Fan L，Wei J M，Hu J B.Research on composition of Qingchuan natural asphalt and structural parameters of asphaltene［J］.Technology of and Transport，2015（2）：40⁃44.
12	洪琨，马凤云，钟梅，等.渣油重组分沥青质结构分析及其对临氢热反应过程生焦的影响［J］.燃料化学学报，2016，44（3）：357⁃365.
	Hong K，Ma F Y，Zhong M，et al.Analysis of asphaltene structure and its effects on the coking behavior in the process of hydrothermal cracking［J］.Journal of Fuel Chemistry and Technology，2016，44（3）：357⁃365.
13	Siddiqui M N，Ali M F，Shirokoff J.Use of X⁃ray diffraction in assessing the aging pattern of asphalt fractions［J］.Fuel，2002，81（1）：51⁃58.
14	洪琨，马凤云，刘景梅，等.塔河常压渣油及其亚组分的非等温热转化反应性能研究［J］.石油炼制与化工，2015，46（12）：53⁃58.
	Hong K，Ma F Y，Liu J M，et al.Study on non⁃isothermal thermal conversion of Tahe atmospheric residual oil and its sub⁃fractions［J］.Petroleum Processing and Petrochemicals，2015，46（12）：53⁃58.
15	Asemani M，Rabbani A R.Oil⁃oil correlation by FTIR spectroscopy of asphaltene samples［J］.Geosciences Journal，2016，20（2）：273⁃283.
16	Ezeonyeka N L，Abdolhossein H S，Husein M M.Asphaltenes adsorption onto metal oxide nanoparticles：A critical evaluation of measurement techniques［J］.Energy & Fuels，2018，32（2）：2213⁃2223.
17	李萍，念腾飞，魏定邦，等.FTIR定量分析方法与老化沥青流变参数新探［J］.华中科技大学学报（自然科学版），2018，46（2）：34⁃39.
	Li P，Nian T F，Wei D B，et al.Quantitative analysis method for FTIR and exploration on rheological parameters of aging asphalt binders［J］.Journal of Huazhong University of Science and Technology（Natural Science Edition），2018，46（2）：34⁃39.
18	董雨明.硬质沥青及其混合料流变特性与低温性能研究［D］.哈尔滨：哈尔滨工业大学，2015.
19	Larbi A，Daaou M，Faraoun A.Investigation of structural parameters and self⁃aggregation of algerian asphaltenes in organic solvents［J］.Petroleum Science，2015，12（3）：509⁃517.
20	梅远飞，赵新，孙万赋，等.伊犁煤焦油成分的谱学分析［J］.石河子大学学报（自然科学版），2011，29（3）：384⁃389.
	Mei Y F，Zhao X，Sun W F，et al.Spectra analysis of Yili coal tar［J］.Journal of Shihezi University（Natural Science Edition），2011，29（3）：384⁃389.
21	Lim S H，Go K S，Nho N S，et al.Effect of aromatic additives on the coke reduction and the asphaltene conversion in a slurry⁃phase hydrocracking［J］.Korean Chemical Engineering Research，2019，57（2）：244⁃252.
22	梁文杰.重质油化学［M］.东营：石油大学出版社，2000.
23	Tojima M，Suhara S，Imamura M，et al.Effect of heavy asphaltene on stability of residual oil［J］.Catalysis Today，1998，43（3⁃4）：347⁃351.

[1]	Xinjuan DU, Dalong DIAO, Longli ZHANG. Research Progress of Asphaltene Dispersants [J]. Journal of Petrochemical Universities, 2024, 37(4): 12-17.
[2]	Lele LI, Lisha SHEN, Zhiming TU, Zhuoxin LU, Hongyi TAN, Yi YANG, Changfeng YAN. Preparation of Cu⁃Doped WN Nanoarrays and Study on Their Hydrogen Evolution Performance [J]. Journal of Petrochemical Universities, 2024, 37(4): 57-65.
[3]	Ruijuan LIU, Lan YANG, Shiyu MIAO, Yanhong LI, Xiaoqiang AN, Huachun LAN. Performance Study of Carbon Adsorption of Spent Membranes for the Removal of Typical Pollutants in Wastewater [J]. Journal of Petrochemical Universities, 2024, 37(2): 1-8.
[4]	Yaqi ZHANG, Xuechuan LÜ, Xiaofan ZHANG, Yue KE, Xue HUANG, Xiaohan GAO. Structure and Properties of [LaCu₆（OH）₃（ClO₄）₃（Gly）₆（Im）₆]（ClO₄）₂· 3（MeOH） [J]. Journal of Petrochemical Universities, 2023, 36(5): 60-66.
[5]	Lei Guan, Xian Chen, Bowen Fan, Yaxu Chen, Pengpeng Yin, Ying Wang. Hydrothermal Synthesis, Crystal Structure and Fluorescence Property of a Tb Coordination Complex [J]. Journal of Petrochemical Universities, 2023, 36(3): 60-65.
[6]	Yuanyuan He, Huiying Zhong, Songlin Guo, Tingbao Yang. Influencing Factors of Microscopic Oil Displacement Efficiency by Polymer Flooding in Class II Reservoirs [J]. Journal of Petrochemical Universities, 2023, 36(2): 34-41.
[7]	Ya Zhou, Runna Shi, Xiaoshi Lang, Chuangang Yao, Kedi Cai. Research Progress of V₂O₅ Cathode Material for Sodium⁃Ion Batteries [J]. Journal of Petrochemical Universities, 2022, 35(6): 38-47.
[8]	Siwei Zhao, Gang Fu, Wenqing Zhen, Li Yang. First⁃Principle Studies on the Photocatalytic Properties of Nb₂C and Ni⁃Functionalized Materials [J]. Journal of Petrochemical Universities, 2022, 35(5): 46-53.
[9]	Zhichao Yu, Zhenguo Tang, Nan Zhang, Zeyue Cui, Linhe Hu, Gang Li. TiO₂ Nanotubes Modified by CdS Quantum Dots and Performance of Photocatalytic Water Splitting for Hydrogen [J]. Journal of Petrochemical Universities, 2022, 35(4): 38-45.
[10]	Ruonan Zhang, Shijie He, Xiaorong Wang, Fangfang Wang, Changdong Chen. Study on Soft Chemistry Preparation and Performance of BaTiO₃⁃TiO₂ Composites [J]. Journal of Petrochemical Universities, 2022, 35(4): 46-51.
[11]	Mengshuang Zhu, Genxiang Luo, Lingzi Xu, Donghao Lin, Jin Huang, Mingyu Qi. Study on the Adsorption of Asphaltenes and Their Sub⁃Components by Mg⁃Al⁃LDH in Tahe [J]. Journal of Petrochemical Universities, 2022, 35(3): 10-15.
[12]	Zugeng Wu, Yinyan Li, Xiaoling Li, Yuguo Wu. Effect of Surfactant/Organic Alkali on Liaohe Heavy Oil Emulsion [J]. Journal of Petrochemical Universities, 2021, 34(5): 74-79.
[13]	Jinyan Zhang, Huan Wang, Yucai Qin, Lijuan Song. Progress in Characterization Strategies Mass Transfer Mechanism of Hierarchical Zeolite [J]. Journal of Petrochemical Universities, 2021, 34(4): 1-8.
[14]	Daiyin Yin, Xudong Zhang. Study on Micro Pore Structure Characteristics of Yangdachengzi Oil Layer in Chaoyanggou Oilfield [J]. Journal of Petrochemical Universities, 2021, 34(4): 39-45.
[15]	Peng Jia, Jiaqing Chen, Xiaolei Cai, Lingzhen Kong, Chunsheng Wang, Chao Shang, Ming Zhang, Yi Shi. Study on Oil⁃Water Separation Characteristics of Hydrocyclone Based on CFD⁃PBM Numerical Simulation [J]. Journal of Petrochemical Universities, 2021, 34(4): 58-65.