超临界流体改质煤焦油研究进展

doi:10.16085/j.issn.1000-6613.2018-1485

摘要/Abstract

摘要：

中国是一个多煤少油的国家，煤制油技术在我国有着广泛的应用前景。由于超临界流体对有机物有较好的溶解性，因此越来越多地应用到煤焦油深加工过程中。本文总结了超临界流体改质煤焦油过程中，操作参数对煤焦油轻质化的影响和强化改质方法，重点分析了超临界水和超临界甲醇，超临界水改质煤焦油主要体现在物理上的溶解和分散作用，而超临界甲醇除此之外，有一定的供氢能力，可以为反应提供氢，但是供氢能力有限。因此，本文又讨论了添加催化剂、自由基引发剂、加氢等手段强化超临界流体改质煤焦油。在此基础上对超临界流体改质煤焦油进行了展望，将超临界流体的萃取和超临界改质耦合在一起，充分发挥超临界流体优越性；选择新的超临界流体、催化剂等促进煤焦油轻质化。

关键词: 超临界水, 超临界甲醇, 改质, 煤焦油, 强化

Abstract:

Given the backdrop of China’s coal-rich but oil and gas-short condition, the utilization rate of coal is not high. Developing the coal-to-liquid (CTL) technologies has a great potential for coal applications. Because supercritical fluids (SCF) have high solubility for a variety of organic compounds, they have been widely used to upgrade coal tar. This paper summarized the effect of operating parameters on the process of supercritical fluid upgrading coal tar, and the reaction mechanism, with a focuson the analysis of supercritical water (SCW) and supercritical methanol (SC-MeOH). Previous studies found that the SCW and SC-MeOH could modify coal tar mainly through the physical dissolution and dispersion. The SC-MeOH can also produce hydrogen but its capacity of supplying hydrogen is limited. Therefore, the addition of catalysts, free radical initiators, and hydrogenation were discussed to enhance supercritical coal tar upgrading process. Future research may focus on the combination of SCF extraction and reaction, developing and applying new types of SCF and catalysts.

Key words: super critical water, supercritical methanol, upgrading, coal tar, process intensification

中图分类号:

TQ 522

陈康, 闫挺, 姜召, 方涛. 超临界流体改质煤焦油研究进展[J]. 化工进展, 2019, 38(04): 1702-1713.

Kang CHEN, Ting YAN, Zhao JIANG, Tao FANG. Progress on application of supercritical fluids to upgrade coal tar[J]. Chemical Industry and Engineering Progress, 2019, 38(04): 1702-1713.

图/表 8

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流体	操作温度 /K	压力 /MPa	密度 /g·cm^-3	黏度 /μPa·s	扩散系数 /cm2·s^-1	介电常数	电离常数 /mol²·kg^-2	用途
超临界二氧化碳	304～373	5.8～30	0.240～0.940	20～30	10^-3	1.0～1.5	难电离	萃取分离、有机化学反应、印染
超临界甲醇	513～623	7.5～15.0	0.177～0.550	30～60	10^-3	2.0～7.0	难电离，在323K、25MPa，值为10^-16.6	生物柴油、重油的轻质化、有机化学反应
超临界水	623～873	15.0～35.0	0.065～0.475	28～56	10^-3	1.0～9.0	难电离，在713K、25MPa，值为10^-21.33	燃料加工、生物资源的处理、有害材料无毒化、有机化学反应
水	298	0.1	0.998	1000	10^-5	80	难电离，值为10^-14

流体	操作温度 /K	压力 /MPa	密度 /g·cm^-3	黏度 /μPa·s	扩散系数 /cm2·s^-1	介电常数	电离常数 /mol²·kg^-2	用途
超临界二氧化碳	304～373	5.8～30	0.240～0.940	20～30	10^-3	1.0～1.5	难电离	萃取分离、有机化学反应、印染
超临界甲醇	513～623	7.5～15.0	0.177～0.550	30～60	10^-3	2.0～7.0	难电离，在323K、25MPa，值为10^-16.6	生物柴油、重油的轻质化、有机化学反应
超临界水	623～873	15.0～35.0	0.065～0.475	28～56	10^-3	1.0～9.0	难电离，在713K、25MPa，值为10^-21.33	燃料加工、生物资源的处理、有害材料无毒化、有机化学反应
水	298	0.1	0.998	1000	10^-5	80	难电离，值为10^-14

原料	溶剂	添加物	研究重点	参考文献
煤焦油沥青	超临界水	无	操作参数	[15]
高温煤焦油	超临界水	无	操作参数，模型化合物	[11]
3种煤焦油	超临界水	无	操作参数，反应机理，模型化合物	[12,32,33]
油砂沥青	超临界水	无	操作参数，超临界水的影响	[34]
沥青	超临界水	无	操作参数，反应机理	[14,35,36]
武钢煤焦油	超临界水	无	操作参数	[37]
埃索石油沥青	超临界水	O₂	操作参数，水煤气变换	[38]
减压渣油	超临界水	无	操作参数，反应机理	[39,40]
沥青	超临界水	无	反应机理，相变化	[19]
重油	超临界水	DTBP	反应机理	[41,42]
渣油	超临界水	无	反应机理，超临界水作用，相变化	[43]
沥青质	超临界水	NaOH	强化改质，三集总动力学	[44]
重油	超临界水	氧气，活性炭	水煤气变换，强化改质	[45]
沥青	超临界水	HCOOH	操作参数	[46]
重油	超临界水	十氢萘，软沥青	供氢强化改质，四集总动力学	[47]
沥青，重油	超临界水	过渡金属，催化剂	强化供氢，反应路径	[48,49,50,51]
渣油	超临界水	聚乙烯	相变化，反应机理	[52]
重油	超临界水	O₂	部分氧化，水煤气变换	[53]
减压渣油	超临界水	无	两相四集总动力学	[27]
沥青	超临界水	CO	水煤气变换	[54]
重油	超临界水	无	四集总动力学，五集总动力学	[24,25,26]
原油	超临界水	无	轻质化与脱硫	[17,18,55,56]
重油	超临界水	无	减粘裂化	[20]
低温煤焦油	超临界汽油	无	三集总动力学	[57]
高/低温煤焦油	超临界二甲苯，超临界汽油	无	操作参数	[16,58]
煤焦油	超临界汽油	催化剂，氢气	操作参数，催化剂特性	[59]
武钢煤焦油	超临界甲醇	无	操作参数	[23]
卡拉玛依重油	超临界甲醇	无	最优操作参数	[22]
减压渣油，沥青	超临界甲醇	无	操作参数，反应机理，杂原子脱除	[21,60,61,62,63]
重油	超临界甲醇	无	四集总动力学	[13]
减压渣油	超临界甲醇	二丁二酮肟合镍	催化剂性能，操作参数	[64]

原料	溶剂	添加物	研究重点	参考文献
煤焦油沥青	超临界水	无	操作参数	[15]
高温煤焦油	超临界水	无	操作参数，模型化合物	[11]
3种煤焦油	超临界水	无	操作参数，反应机理，模型化合物	[12,32,33]
油砂沥青	超临界水	无	操作参数，超临界水的影响	[34]
沥青	超临界水	无	操作参数，反应机理	[14,35,36]
武钢煤焦油	超临界水	无	操作参数	[37]
埃索石油沥青	超临界水	O₂	操作参数，水煤气变换	[38]
减压渣油	超临界水	无	操作参数，反应机理	[39,40]
沥青	超临界水	无	反应机理，相变化	[19]
重油	超临界水	DTBP	反应机理	[41,42]
渣油	超临界水	无	反应机理，超临界水作用，相变化	[43]
沥青质	超临界水	NaOH	强化改质，三集总动力学	[44]
重油	超临界水	氧气，活性炭	水煤气变换，强化改质	[45]
沥青	超临界水	HCOOH	操作参数	[46]
重油	超临界水	十氢萘，软沥青	供氢强化改质，四集总动力学	[47]
沥青，重油	超临界水	过渡金属，催化剂	强化供氢，反应路径	[48,49,50,51]
渣油	超临界水	聚乙烯	相变化，反应机理	[52]
重油	超临界水	O₂	部分氧化，水煤气变换	[53]
减压渣油	超临界水	无	两相四集总动力学	[27]
沥青	超临界水	CO	水煤气变换	[54]
重油	超临界水	无	四集总动力学，五集总动力学	[24,25,26]
原油	超临界水	无	轻质化与脱硫	[17,18,55,56]
重油	超临界水	无	减粘裂化	[20]
低温煤焦油	超临界汽油	无	三集总动力学	[57]
高/低温煤焦油	超临界二甲苯，超临界汽油	无	操作参数	[16,58]
煤焦油	超临界汽油	催化剂，氢气	操作参数，催化剂特性	[59]
武钢煤焦油	超临界甲醇	无	操作参数	[23]
卡拉玛依重油	超临界甲醇	无	最优操作参数	[22]
减压渣油，沥青	超临界甲醇	无	操作参数，反应机理，杂原子脱除	[21,60,61,62,63]
重油	超临界甲醇	无	四集总动力学	[13]
减压渣油	超临界甲醇	二丁二酮肟合镍	催化剂性能，操作参数	[64]

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