Preparation and Characterization of Modified Ethylene Tar Pitch

doi:10.12422/j.issn.1672-6952.2023.04.002

Journal of Liaoning Petrochemical University ›› 2023, Vol. 43 ›› Issue (4): 8-13.DOI: 10.12422/j.issn.1672-6952.2023.04.002

• Chemistry and Chemical Engineering • Previous Articles Next Articles

Preparation and Characterization of Modified Ethylene Tar Pitch

Shuo Zhang¹(), Huaijia Fu², Dongyun Han¹(), Haiyan Qiao¹, Weiwei Shi¹, Xiaodan Deng³

^1.School of Petrochemical Technology，Liaoning Petrochemical University，Fushun Liaoning 113001，China
^2.Zibo Qixiang Tengda Chemical Co. ，Ltd. ，Zibo Shandong 255438，China
^3.China Kunlun Contracting ＆ Engineering Corporation Shenyang Company，Shenyang Liaoning 110015，China

Received:2023-03-03 Revised:2023-03-23 Online:2023-08-25 Published:2023-09-04
Contact: Dongyun Han

改性乙烯焦油沥青的制备及表征分析

张硕¹(), 付怀佳², 韩冬云¹(), 乔海燕¹, 石薇薇¹, 邓小丹³

^1.辽宁石油化工大学石油化工学院，辽宁抚顺 113001
^2.淄博齐翔腾达化工股份有限公司，山东淄博 255438
^3.中国昆仑工程有限公司沈阳分公司，辽宁沈阳 110015

通讯作者: 韩冬云
作者简介:张硕（1998⁃），男，硕士研究生，从事清洁燃料生产方面的研究；E⁃mail：dashuo1002@163.com。
基金资助:
辽宁省教育厅科学研究项目(LJKZ0409)

Abstract

Abstract:

The effects of polymerization reaction temperature, polymerization reaction time, catalyst and crosslinker addition on the properties of modified ethylene tar pitch (METP) were investigated, and the optimal reaction conditions were obtained by combining elemental analysis, FT?IR, XRD, Raman and thermogravimetric analysis on ETP and METP: The polymerization reaction temperature was 370 ℃, and the polymerization reaction time was 6 h, besides the addition of catalyst and crosslinker was 1.50%. The softening point (SP) of METP obtained under these conditions was 182 ℃, the coking value (CV) was 57.66%, the β resin was 42.26%, and the quinoline insoluble matter (QI) was 0.87%, which met the requirements of high carbon material precursors； The yieid of METP was 73.26%.

Key words: ETP, Thermal polymerization, METP, β resin, Yield

摘要：

以乙烯焦油沥青（ETP）为原料，对其进行热聚合改性处理，探讨了聚合反应温度、聚合反应时间、催化剂及交联剂质量分数对改性乙烯焦油沥青（METP）的组成、性质及收率的影响，并结合元素分析、FT?IR、XRD、Raman、热重分析对ETP及METP进行研究，得到了最佳反应条件：聚合反应温度为370 ℃，聚合反应时间为6 h，催化剂和交联剂质量分数为1.50%。在此条件下得到的METP的软化点（SP）为182 ℃，结焦值（CV）为57.66%，β树脂质量分数为42.26%，喹啉不溶物（QI）质量分数为0.87%，符合高碳材料前驱体的要求；METP收率为73.26%。

关键词: 乙烯焦油沥青, 热聚合, 改性乙烯焦油沥青, β树脂, 收率

CLC Number:

TE65

Shuo Zhang, Huaijia Fu, Dongyun Han, Haiyan Qiao, Weiwei Shi, Xiaodan Deng. Preparation and Characterization of Modified Ethylene Tar Pitch[J]. Journal of Liaoning Petrochemical University, 2023, 43(4): 8-13.

张硕, 付怀佳, 韩冬云, 乔海燕, 石薇薇, 邓小丹. 改性乙烯焦油沥青的制备及表征分析[J]. 辽宁石油化工大学学报, 2023, 43(4): 8-13.

Figures/Tables 11

References 20

1	王健涛.乙烯焦油综合利用研究［D］.抚顺：辽宁石油化工大学，2021.
2	孙鑫.重油混合相容性及结垢行为研究［D］.青岛：中国石油大学（华东），2013.
3	Yu Y Y，Wei Q，Wang F，et al.Carbonization characteristics of ethylene tar narrow fractions［J］.Journal of Fuel Chemistry and Technology，2022，50（3）：376⁃384.
4	杨志武.乙烯焦油沥青基通用级炭纤维的制备及研究［D］.天津：天津大学，2012.
5	Chai L N，Lou B，Yu R，et al.Study on structures and properties of isotropic pitches and carbon fibers from Co⁃carbonization of aromatic⁃rich distillate oil and polyethylene glycol［J］.Journal of Analytical and Applied Pyrolysis，2021，158：105260.
6	Yu Y Y，Wang F，Biney B W，et al.Co⁃carbonization of ethylene tar and fluid catalytic cracking decant oil：Development of high⁃quality needle coke feedstock［J］.Fuel，2022，322：124170.
7	Cheng X L，Zha Q F，Zhong J T， et al. Needle coke formation derived from Co⁃carbonization of ethylene tar pitch and polystyrene［J］.Fuel，2009，88（11）：2188⁃2192.
8	林起浪，李铁虎，谢钢，等.低温交联法制备炭材料用改性沥青［J］.炭素技术，2001（4）：1⁃4.
9	Lin X C，Sheng Z，He J，et al.Preparation of isotropic spinnable pitch with high⁃spinnability by Co⁃carbonization of coal tar pitch and bio⁃asphalt［J］.Fuel，2021，295：120627.
10	杜洋，孙然，刘进博，等.一种新型生物柴油降凝剂的制备与性能［J］.辽宁石油化工大学学报，2022，42（5）：38⁃42.
11	Li M，Liu D，Lou B，et al.Effects of inductive condensation on mesophase development during the aromatic⁃rich oil carbonization［J］.Energy & Fuels，2019，33（8）：7200⁃7205.
12	Li M，Liu D，Lv R Q，et al.Preparation of the mesophase pitch by hydrocracking tail oil from a naphthenic vacuum residue［J］.Energy & Fuels，2015，29（7）：4193⁃4200.
13	Andersen S I，Jensen J O，Speight J G.X⁃ray diffraction of subfractions of petroleum asphaltenes［J］.Energy & Fuels，2005，19（6）：2371⁃2377.
14	刘杰，史雪梅，崔楼伟，等.原料组成对针状焦结构的影响［J］.燃料化学学报，2021，49（4）：546⁃553.
15	Mochida I，Shimizu K，Korai Y，et al.Mesophase pitch catalytically prepared from anthracene with HF/BF3［J］.Carbon，1992，30（1）：55⁃61.
16	施逸帆，孙京.红薯生物质碳气凝胶的制备及其吸附性能［J］.辽宁石油化工大学学报，2022，42（2）：8⁃14.
17	Beyssac O，Goffe B，Petitet J P，et al.On the characterization of disordered and heterogeneous carbonaceous materials by Raman spectroscopy［J］.Spectrochimica Acta Part A： Molecular and Biomolecular Spectroscopy，2003，59（10）：2267⁃2276.
18	朱慧慧，顾诗豪，唐胤博，等.乙烯焦油沥青组分的分离及基础性质研究［J］.辽宁科技大学学报，2022，45（1）：52⁃58.
19	Gargiulo V，Apicella B，Alfè M，et al. Structural characterization of large polycyclic aromatic hydrocarbons.Part 1：The case of coal tar pitch and naphthalene⁃derived pitch［J］.Energy & Fuels，2015，29（9）：5714⁃5722.
20	Alhumaidan F S，Rana M S，Lababidi H，et al.Pyrolysis of asphaltenes derived from residual oils and their thermally treated pitch［J］.ACS Omega，2020，5（38）：24412⁃24421.

样品	SP/℃	质量分数/%				碳氢原子比	w(CV)/%	w(灰分)×10/%
样品	SP/℃	C	H	O	其他	碳氢原子比	w(CV)/%	w(灰分)×10/%
ET	-	91.34	7.63	0.18	0.85	0.997	14.60	0.05
ETP	110	92.81	5.94	1.17	0.08	1.302	38.70	0.05

样品	SP/℃	质量分数/%				碳氢原子比	w(CV)/%	w(灰分)×10/%
样品	SP/℃	C	H	O	其他	碳氢原子比	w(CV)/%	w(灰分)×10/%
ET	-	91.34	7.63	0.18	0.85	0.997	14.60	0.05
ETP	110	92.81	5.94	1.17	0.08	1.302	38.70	0.05

样品	w(C)/%	w(H)/%	w(O)/%	w(其他)/%	碳氢原子比
ETP	92.81	5.94	1.17	0.08	1.30
METP	94.06	5.32	0.59	0.03	1.47

样品	w(C)/%	w(H)/%	w(O)/%	w(其他)/%	碳氢原子比
ETP	92.81	5.94	1.17	0.08	1.30
METP	94.06	5.32	0.59	0.03	1.47

样品	I_g/%	L_C/nm	d₀₀₂/nm	N	n	（I_G/I_all）/%	（I_D2/I_G）/%
ETP	62.12	0.212	0.393	1.54	0.76	0.25	0.29
METP	69.48	0.232	0.383	1.61	0.83	0.29	0.21

Preparation and Characterization of Modified Ethylene Tar Pitch

改性乙烯焦油沥青的制备及表征分析

HTML

PDF

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 11

References 20

Related Articles 9

Recommended Articles

Metrics

[1]	Shuo Zhang, Zewu Jiang, Fuzhi Jia, Jiarui Du, Weiwei Shi, Yuqi Zhang, Dongyun Han. Refining and Polymerization of Coking Coal Oil Fraction to Produce High Viscosity Base Oil [J]. Journal of Liaoning Petrochemical University, 2023, 43(3): 21-27.
[2]	Zhao Mengjiao， Jia Guanlan， Meng Jiayu， Chen Jicheng. Pretreatment of Sunflower Stalk with CO₂ Compressed by High Temperature Liquid Water [J]. Journal of Liaoning Petrochemical University, 2020, 40(5): 39-43.
[3]	Lu Yanbin, Ma Biao, Zhang Weichen. Preparation of HZSM-5/Monolithic Catalyst and its Application in Conversion of Methanol to Gasoline [J]. Journal of Liaoning Petrochemical University, 2015, 35(1): 12-15.
[4]	Song Guanlong, Zhang Guowei, Gong Jianyuan, Zhao Dezhi. Intensifying Distillation of Crude Oil by LWS201 Additive and Its Industrial Application [J]. Journal of Liaoning Petrochemical University, 2014, 34(5): 4-6.
[5]	Feng Chenchen， Cao Zubin， Han Dongyun，Li Dandong， Shi Yan， Liang Feixue. Comprehensive Evaluation and Retorting Technology  Selection of Tacheng Oil Shales in Xinjiang [J]. Journal of Liaoning Petrochemical University, 2014, 34(2): 12-16.
[6]	XU Yao-hui， MA Guo-dong， LI Yun， CAO Zu-bin， LI Dan-dong. The Solvent Extraction Investigation on Kazakhstan Oil Sand [J]. Journal of Liaoning Petrochemical University, 2012, 32(3): 6-8.
[7]	Sun Feng. Technology Reform on Oil Shale Retorting With a Fushun Retort (Ⅰ) [WT4”]——Reason Analysis & Solving Schemes on Low Oil Yield Rate [J]. Journal of Liaoning Petrochemical University, 2012, 32(2): 24-26.
[8]	ZHANG Zhe-ming，ZHAO De-zhi，ZHANG Han-ming，ZHU Yun-yan, ZHENG Xiao-ming， ZHAO Bo. Removal of Basic Nitrogen Compounds From Shale Oil [J]. Journal of Liaoning Petrochemical University, 2011, 31(3): 24-27.
[9]	GUO Zi-geng, LI Li-hua, ZHANG Jin-sheng. Extracting of Cucumber-Seed Oils by Soxhlet Method [J]. Journal of Liaoning Petrochemical University, 2009, 29(4): 27-29.