油页岩热解挥发分产物二次反应对油气收率与组成的影响

张玉明; 管俊涛; 乔沛; 李家州; 张炜

doi:10.1016/S1872-5813(21)60046-4

油页岩热解挥发分产物二次反应对油气收率与组成的影响

doi: 10.1016/S1872-5813(21)60046-4

中国石油大学（北京）重质油国家重点实验室，北京 102249

基金项目: 国家自然科学基金（U1862107），国家重点研发计划（2018YFE0183600）和中国石油大学（北京）科研基金（20200127）资助

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E-mail: ymzhcup@163.com

中图分类号: TE662
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出版历程
- 收稿日期: 2020-12-03
- 修回日期: 2021-01-31
- 网络出版日期: 2021-06-21
- 刊出日期: 2021-07-15

Effects of secondary reaction of primary volatiles on oil/gas yield and quality in oil shale pyrolysis

State Key Laboratory of Heavy Oil Processing, China University of Petroleum-Beijing, Beijing 102249, China

Funds: The project was supported by the National Natural Science Foundation (U1862107), National Key R&D Program of China (2018YFE0183600) and Science Foundation of China University of Petroleum, Beijing (20200127)

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Corresponding author: E-mail: ymzhcup@163.com

摘要

摘要: 采用两段反应器对油页岩热解释放的一次挥发分产物进行不同热态条件下的二次反应特性研究，考察第二段温度、气氛与停留时间对油气收率及品质的影响。研究结果表明，转化温度对油气产率的影响最明显，在优化第一段热解反应条件的基础上，当反应器第二段温度由600 ℃提高到650 ℃时，油页岩热解油产率下降15%（质量分数，下同），气体产率增加约20%。与氮气气氛相比，水蒸气作为第二段反应气氛能够提高液体油品收率约5%，并且热解油主要集中在馏程 < 350 ℃的汽柴油馏分。结合GC-MS分析表明，停留时间0−3 s二次反应主要为裂解过程，水蒸气能够提高油品中芳烃含量，同时抑制芳烃缩聚；3−5 s二次反应主要为缩聚过程，焦炭生成量增加，汽柴油馏分收率保持稳定，VGO馏分油收率下降约30%。
- 油页岩 /
- 热解挥发分 /
- 水蒸气重整 /
- 二次反应
Abstract: The reaction behaviors of primary volatiles from oil shale pyrolysis were investigated using a two-stage reactor under different in-situ thermal reaction conditions. The reaction parameters of secondary reactor, such as, reactor temperature, atmosphere and residence time, were studied for their effects on the pyrolysis oil/gas yield and quality. The results showed that the reaction temperature had profound influence on the oil and gas yield. The pyrolyzed shale oil and gas yield reduced by 15% and increased by 20% (mass) respectively, with the temperature of 2^nd stage reactor increasing from 600 to 650 °C under optimized reaction condition of 1^st stage. Comparing with nitrogen atmosphere, the liquid oil yield could be enhanced by 5% when steam was added as the reaction atmosphere in the second stage, and the corresponding oil was mainly concentrated in the gasoline and diesel distillations (that is, boiling point < 350 °C). The GC-MS analysis illustrated that the secondary reaction at the residence time of 0−3 s was mainly pyrolysis while the presence of steam could increase the content of aromatics in the oil and meanwhile suppress the condensation of aromatics. When the residence time was greater than 3−5 s, the secondary reaction was mainly condensation of poly-aromatics, which led to the increase of coke. Meanwhile, the gasoline and diesel oil yield remained stable, and the VGO fractions decreased by about 30%.
- oil shale /
- pyrolysis volatiles /
- steam reforming /
- secondary reaction

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FIG. 798. FIG. 798.

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图 1 实验装置流程示意图

Figure 1 Schematic diagram of experimental apparatus

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图 2 不同温度与停留时间下水蒸气添加对热解油气产量变化的影响

Figure 2 Pyrolysis oil and gas yields varying with volatile residence time, temperature and steam addition

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图 3 油页岩热解气体组成随停留时间的变化

Figure 3 Gas yields per kilogram oil shale varying with residence time

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图 4 不同停留时间下热解油减少量和气体增加量的相对变化

Figure 4 Relative change of pyrolysis oil decrease and gas increase under different volatile residence time

Gas yield increase; Oil yield loss

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图 5 油页岩热解油模拟蒸馏所得的馏程组分变化

Figure 5 Shale oil composition and shale oil yield at different residence time

N-600; S-600 Gasoline & diesel; N-600; S-600 VGO

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图 6 不同停留时间和二段反应气氛下油页岩热解烃类组分含量

Figure 6 Hydrocarbon contents of oil shale pyrolysis under different residence time and second-stage reaction atmosphere

(PAH: Poly-aromatic hydrocarbon; SAH: Single-aromatic hydrocarbon; CH: Cyclo-paraffin hydrocarbon; AH: Alkane hydrocarbon)

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图 7 添加水蒸气以及不同停留时间油页岩热解油脂肪烃产量的对比

Figure 7 Comparison of aliphatic hydrocarbon with different carbon numbers at residence time of 1, 3, and 5 s

(S-600 1 s—N-600 1 s: difference value between S-600 and N-600 at the residence time of 1 s)

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表 1 桦甸油页岩的工业分析、元素分析和铝甑分析

Table 1 Proximate, ultimate and Fischer assay analyses of Huadian oil shale

Proximate analysis w_d/%			Ultimate analysis w_ad/%					Fischer assay w_ad/%
A	V	FC	C	H	O*	N	S	oil	gas	water	coke
49.94	33.14	16.92	34.32	3.56	11.02	0.89	0.78	11.30	9.62	3.92	75.16
d: dry basis; ad: air-dried basis; *: calculated by difference

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