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材料研究学报  2016, Vol. 30 Issue (6): 448-456    DOI: 10.11901/1005.3093.2015.685
  研究论文 本期目录 | 过刊浏览 |
中温煤沥青喹啉不溶物的脱除及炭化制备针状焦*
唐闲逸1, 魏晓慧1, 许德平1(), 张海永1, 贺欣1, 熊楚安1,3, 唐瀚滢2
1. 中国矿业大学(北京)化学与环境工程学院 北京 100083
2. 中国科学院化学研究所 北京 100190
3. 黑龙江科技大学 哈尔滨 150022
Removal of QI from Medium-temperature Coal Tar Pitch and Preparation of Needle Coke through Carbonization
TANG Xianyi1, WEI Xiaohui1, XU Deping1,**(), ZHANG Haiyong1, HE Xin1, XIONG Chu'an1,3, TANG Hanying2
1. School of Chemistry& Environmental Engineering, China University of Mining & Technology (Beijing), Beijing 100083, China
2. Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
3. Heilongjiang Institute of Science and Technology, Harbin 150022, China
引用本文:

唐闲逸, 魏晓慧, 许德平, 张海永, 贺欣, 熊楚安, 唐瀚滢. 中温煤沥青喹啉不溶物的脱除及炭化制备针状焦*[J]. 材料研究学报, 2016, 30(6): 448-456.
Xianyi TANG, Xiaohui WEI, Deping XU, Haiyong ZHANG, Xin HE, Chu'an XIONG, Hanying TANG. Removal of QI from Medium-temperature Coal Tar Pitch and Preparation of Needle Coke through Carbonization[J]. Chinese Journal of Materials Research, 2016, 30(6): 448-456.

全文: PDF(1665 KB)   HTML
摘要: 

以中温煤沥青为原料, 研究其在弹管反应器中的炭化以及“反溶剂法”脱出喹啉不溶物(QI)后的精制沥青的炭化效果。结果表明: 含有较高QI的非精制沥青不能制备出较好的针状焦, 但在500℃, 0.2 MPa, 10h的炭化条件下, 能够得到相对较优热膨胀系数(CTE)的炭化结果; 以煤油和洗油为混合溶剂, 反溶剂法能够有效地脱除喹啉不溶物, 在芳脂比0.4, 沉降温度100℃, 搅拌时间0.5 h, 沉降时间4 h, 溶剂比1.8、2的条件下, QI含量分别降到0.0914%和0.0695%, 将其在500℃、0.2 MPa、10 h的条件下炭化, 可制备出热膨胀系数(CTE)较低的针状焦。
关键词 ： 材料合成与加工工艺,  中温煤沥青,  反溶剂法,  喹啉不溶物,  炭化,  针状焦    
Abstract：

The carbonization in a tube bomb of medium-temperature coal tar pitch and the purified coal tar pitch, of which quinoline insoluble (QI) had been removed by anti-solvent method, was comparatively studied. The results show that coal tar pitch with high QI contents could not be suitable for preparation of needle coke of high quality. However, the coke which was obtained through carbonization under 0.2 MPa at 500℃ for 10 h had a relatively lower coefficient of thermal expansion (CTE). The QI could be removed effectively by anti-solvent method when kerosene and wash oil were mixed as solvents. By a precipitation process at 100℃ and precipitation time for 4 h with the ratio of wash oil to kerosene was 0.4 and stirring for 0.5 h, the QI contents of the refined coal tar pitch could be reduced to 0.0914% and 0.0695% for the ratios of solvents to coal tar pitch as 1.8 and 2 respectively. The needle coke which were prepared by such refined coal tar pitch showed lower CTE after being carbonized at 500℃, by 0.2 MPa and for 10 h.
Key words： synthesizing and processing technics    medium-temperature coal tar pitch    anti-solvent method    QI    carbonization    needle coke
收稿日期: 2015-12-01     
ZTFLH:  TQ522.65  
基金资助:* 国家自然科学基金联合项目基金U1361124资助项目
作者简介: 本文联系人: 许德平
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唐闲逸
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贺欣
熊楚安
唐瀚滢

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https://www.cjmr.org/CN/10.11901/1005.3093.2015.685      或      https://www.cjmr.org/CN/Y2016/V30/I6/448

图1  喹啉不溶物增大示意图
图2  炭化反应装置示意图
Solvent d15.615.61 Initial boiling
point /℃		 TV/℃ Final boiling
point/℃		 BMCI2
Kerosene 0.794 103 191.2 281 24
Wash oil 1.001 212 259.6 330 109
表1  煤油与洗油性质
Sample CTP0 CTP1 CTP2 CTP3 CTP4 Sample CTP0 CTP1 CTP2 CTP3 CTP4
C,% 92.14 93.64 92.06 92.87 92.66 Har ,% 79.60 80.48 77.64 75.31 74.55
H,% 4.75 4.90 5.80 5.05 5.04 Hα ,% 17.16 18.76 20.05 21.12 21.88
O3,% 1.67 0 0.25 0.81 1.01 Hβ ,% 3.11 0.46 1.74 3.26 3.52
N,% 1.20 1.15 1.37 0.96 0.96 Hγ ,% 0.13 0.30 0.57 0.31 0.05
S,% 0.24 0.31 0.52 0.31 0.33 fa5 0.9477 0.9488 0.9256 0.9328 0.9307
C/H 1.62 1.59 1.32 1.53 1.53 σ5 0.08 0.089 0.097 0.105 0.109
Ash,% 0 0 0 0 0 HS,% 13.64 49.80 31.39 70.50 85.40
H2O,% 0.50 0.59 0.17 0.35 0.39 HI-TS,% 72.06 46.24 66.57 28.27 14.46
SP4 77.8℃ 23.8℃ 22.4℃ - - TI-QS,% 12.79 3.87 1.97 1.19 0.10
- - - - - QI,% 1.49 0.09 0.07 0.04 0.03
表2  煤沥青性质
图3  不同炭化条件生焦偏光显微照片
Sample CTE
(×10-6/℃)		 RD6
(g/cm3)		 Yield7(W%) Sample CTE
(×10-6/℃)		 Sample CTE
(×10-6/℃)		 Sample CTE
(×10-6/℃)
CTP1 0.56 1.95 52.1 A 2.60 E 2.59 I 2.92
CTP2 0.47 2.09 53.0 B 1.84 F 3.19 J 2.28
CTP3 - - 49.3 C 2.83 G 1.85 K 2.19
CTP4 - - 42.9 D 2.18 H 1.98 L 2.82
表3  针状焦性质
图4  QI含量与收率随芳脂比变化
图5  QI含量与收率随沉降温度变化
图6  QI含量与收率随沉降时间变化
图7  QI含量与收率随溶剂比变化
图8  精制沥青炭化生焦偏光显微照片
图9  CTP3与CTP4炭化生焦照片
图10  针状焦的XRD谱
图11  针状焦的XRD特征峰
Sample β002E-2/rad 2θ002/(°) β100E-2/rad 2θ100/(°) d002/nm D/nm
La(100) Lc(002)
CTP1 1.107 25.700 0.934 43.079 0.3463 0.177 0.127
CTP2 1.066 25.859 0.854 43.263 0.3442 0.194 0.132
G 1.074 25.480 0.423 43.383 0.3493 0.391 0.131
表4  针状焦XRD微观结构参数
图12  针状焦的SEM像
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