乙烯渣油沥青的氧化改性及其热转化行为

doi:10.16085/j.issn.1000-6613.2020-1012

摘要/Abstract

摘要：

乙烯渣油沥青具有较高的芳香度和良好的理化性质，有可能作为制备高品质人造炭材料的原料。充分了解和认识乙烯渣油沥青热转化行为是制备高品质乙烯渣油沥青基炭材料的关键。本文研究了乙烯渣油沥青（ETP）及常压空气氧化改性沥青（MP1和MP2）在恒温和变温条件下的热转化行为，用元素分析、FTIR、TGA、偏光显微镜、SEM、XRD、Raman光谱等方法，研究了三种沥青在热转化过程中的结构和性质变化规律。发现改性沥青的热稳定性、C $? ????$ O和C—O含量均明显高于乙烯渣油沥青。热转化过程中，沥青分子中的C $? ????$ O官能团作为反应活性位点诱导热转化反应的发生。恒温热转化有利于热转化产物中纤维状结构的形成，变温热转化使得沥青焦显微结构中片状组分含量相对较高。改性沥青焦的碳微晶排列规整程度均低于乙烯渣油沥青焦的碳微晶排列规整程度。

关键词: 乙烯渣油沥青, 热转化行为, 微观结构

Abstract:

Ethylene tar pitch with high aromaticity and good physical-chemical properties has been widely used as the raw materials for the production of artificial carbon materials. To fully understand the thermal conversion behaviors of ethylene tar pitch is important to the production of high-quality carbon materials from the ethylene tar pitch. In this paper, the thermal conversion of the ethylene tar pitch (ETP) and two atmospheric air oxidation modified pitches (MP1 and MP2) was examined and monitored by elemental analyzer, FTIR, TGA, polarized microscope, SEM, XRD and Raman spectroscopy. The results showed that the thermal-stability and content of C $? ????$ O and C—O groups of the modified pitches were significantly higher than those of the ethylene tar pitch. The C $? ????$ O groups functioned as the reactive site can initiate the thermal reactions. The constant temperature treatment conditions were beneficial to the formation of fibrous structure in the pitch coke, and the content of leaflet structure was relatively higher in the pitch coke under the variable temperature treatment conditions. The regularity of the carbon microcrystallites of the modified pitch coke was lower than that of the ethylene tar pitch coke.

Key words: ethylene tar pitch, thermal conversion behavior, microstructure

中图分类号:

TQ522.63

赵春雷, 朱亚明, 高丽娟, 程俊霞, 赖仕全, 赵雪飞. 乙烯渣油沥青的氧化改性及其热转化行为[J]. 化工进展, 2021, 40(4): 2130-2137.

ZHAO Chunlei, ZHU Yaming, GAO Lijuan, CHENG Junxia, LAI Shiquan, ZHAO Xuefei. Oxidization-modification and thermal conversion behavior of ethylene tar pitch[J]. Chemical Industry and Engineering Progress, 2021, 40(4): 2130-2137.

图/表 12

表1 沥青的工业分析结果

样品	SP/℃	CV/%	QI/%	TI/%
ETP	112	33.19	0.08	0.18
MP1	174	64.41	0.56	29.81
MP2	236	70.64	0.86	43.30

表2 乙烯渣油沥青和改性沥青的元素分析

样品	C/%	H/%	N/%	S/%	O/%
ETP	92.75	6.90	0.20	0.06	0.09
MP1	94.78	4.62	0.18	0.06	0.36
MP2	95.32	4.08	0.17	0.04	0.39

表3 红外光谱不同官能团的波数分布

波数/cm^-1	归属
1772	芳香脂
1703	羧基
1650	C $? ????$ O共轭
1610	芳香族C $? ????$ C
1586	芳香族C $? ????$ C
1500	芳香族C $? ????$ C
1458	非对称CH₃—,CH₂—
1437	芳香族C $? ????$ C
1410	非对称CH—(CH₃),—OH
1377	对称CH₃—Ar,R
1350	对称CH₂—C $? ????$ O
1274	芳香醚C—O
1222	C—O和—OH 苯氧基、醚
1168	脂肪酚、醚C—O
1094	仲醇C—O
1036	烷基醚

表3 红外光谱不同官能团的波数分布

波数/cm^-1	归属
1772	芳香脂
1703	羧基
1650	C $? ????$ O共轭
1610	芳香族C $? ????$ C
1586	芳香族C $? ????$ C
1500	芳香族C $? ????$ C
1458	非对称CH₃—,CH₂—
1437	芳香族C $? ????$ C
1410	非对称CH—(CH₃),—OH
1377	对称CH₃—Ar,R
1350	对称CH₂—C $? ????$ O
1274	芳香醚C—O
1222	C—O和—OH 苯氧基、醚
1168	脂肪酚、醚C—O
1094	仲醇C—O
1036	烷基醚

图1 沥青的红外光谱及ETP在1800～1000cm-1的拟合谱图

图2 样品的TG和DTG曲线

图3 沥青焦的典型偏光显微结构

图4 恒温与变温处理条件下沥青焦的显微组分含量（FL=Fc+Ff+Le）

图5 恒温与变温处理条件下沥青焦的SEM图

图6 恒温与变温条件下沥青焦的X射线衍射谱

表4 沥青焦的XRD相关参数

样品	2θ(002) /(°)	β₀₀₂	2θ(100) /(°)	β₁₀₀	d₀₀₂/?	L_c/?	L_a/?
ETP-C-C	25.563	0.09310	43.528	0.07168	3.4835	1.51006	4.25730
MP1-C-C	25.462	0.09337	43.428	0.07189	3.4971	1.50543	4.24346
MP2-C-C	25.462	0.09336	43.381	0.07201	3.4971	1.50550	4.23632
ETP-V-C	25.563	0.09136	43.530	0.06910	3.4835	1.53878	4.41638
MP1-V-C	25.521	0.09492	43.528	0.07293	3.4892	1.48105	4.18454
MP2-V-C	25.553	0.09388	43.530	0.07254	3.4848	1.49747	4.20701

图7 沥青焦的拉曼光谱及ETP-C-C在500~2500cm-1区间的拟合谱图

表5 沥青焦的拉曼光谱参数

样品	I_G/I_All	I_D1/I_G	I_D2/I_G	I_D3/I_G	I_D4/I_G
ETP-C-C	0.088	6.610	0.772	1.358	1.656
MP1-C-C	0.086	7.061	0.873	1.372	1.351
MP2-C-C	0.083	7.346	0.911	1.356	1.462
ETP-V-C	0.105	5.733	0.584	1.079	1.128
MP1-V-C	0.078	7.729	1.069	1.464	1.597
MP2-V-C	0.081	7.495	1.080	1.402	1.443

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