Application of Petroleum Coke and Progress of Desulfurization Technology

doi:10.12422/j.issn.1006-396X.2023.05.002

Abstract

Abstract:

With the rise of electric revolution and the establishment of "carbon dioxide emission and carbon neutrality" strategy, petroleum coke has got great development in value?added applications such as lithium cathode materials and high?grade prebaked anode.However,high value?added applications of petroleum coke all have strict requirements for sulfur content of petroleum coke. The high sulfur content in petroleum coke will have a negative impact on the high value application of petroleum coke.The research status of main desulphurization technologies of petroleum coke,including solvent extraction desulfurization technology,high temperature calcination desulfurization technology,oxidation desulfurization technology, alkali metal compound desulfurization technology,hydrodesulfurization technology,microbial desulfurization technology and process intensification auxiliary desulfurization technology are summarized.It was found that the desulphurisation rate of process?enhanced assisted desulphurisation could reach 93.6%,which could reduce the sulphur mass fraction in petroleum coke from 7.57% to 0.48%. The desulfurization technology of petroleum coke should maintain the principle that the structure of petroleum coke after desulfurization is not destroyed to the greatest extent.Therefore,oxidative desulfurization coupled process enhancement assisted desulfurization should have bright prospect in industrial application of petroleum coke desulphurization.

Key words: Petroleum coke, Sulfide hazard, Desulphurization technology, Catalyst

摘要：

随着电动革命的兴起及“双碳”目标的确立，石油焦在锂电负极材料及高等级预焙阳极等高附加值应用领域获得长足发展，但是新兴石油焦高附加值的应用对石油焦中硫质量分数有严苛的要求。石油焦中硫质量分数过高，会对石油焦的高价值应用产生负面影响。对主要的石油焦脱硫技术，包括溶剂萃取脱硫法、高温煅烧脱硫法、氧化脱硫法、碱金属化合物脱硫法、加氢脱硫法、微生物脱硫法及过程强化辅助脱硫法等的研究现状进行了归纳与总结。研究发现，过程强化辅助脱硫法的脱硫率可以达到93.6%，可将石油焦中硫质量分数由7.57%降至0.48%。石油焦脱硫技术应遵循最大程度保持脱硫后石油焦本体结构不被破坏的原则，因此氧化脱硫法耦合过程强化辅助脱硫法是具有工业应用前景的石油焦脱硫技术。

关键词: 石油焦, 硫化物危害, 脱硫技术, 催化剂

CLC Number:

TQ072

Xujun HUANG, Yongyi SONG, Yang YU, Wei DING, Shudong ZHANG, Haile CAI, Rui MA. Application of Petroleum Coke and Progress of Desulfurization Technology[J]. Journal of Petrochemical Universities, 2023, 36(5): 15-23.

黄旭君, 宋永一, 于洋, 丁巍, 张舒冬, 蔡海乐, 马锐. 石油焦应用及脱硫技术进展[J]. 石油化工高等学校学报, 2023, 36(5): 15-23.

Figures/Tables 3

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年份	石油焦价格/（元·t^-1）
年份	1^#	2^#	3^#	4^#	5^#
2019	1 488	1 200	1 135	1 030	835
2020	2 300	1 710	1 665	1 121	905
2021	4 950	3 755	3 265	2 015	1 870
2022	7 250	6 475	5 655	2 455	2 275

年份	石油焦价格/（元·t^-1）
年份	1^#	2^#	3^#	4^#	5^#
2019	1 488	1 200	1 135	1 030	835
2020	2 300	1 710	1 665	1 121	905
2021	4 950	3 755	3 265	2 015	1 870
2022	7 250	6 475	5 655	2 455	2 275

方法	脱硫条件				脱硫率/%	文献
方法	试剂	温度/℃	剂焦质量比	反应时间/h	脱硫率/%	文献
溶剂萃取脱硫法	邻氯苯酚	160	10.0∶1.0	2.0	19.0	[33]
	四氯乙烯	常温	17.0∶1.0	2.0	35.0	[34]
	邻氯苯酚	常温	17.0∶1.0	4.0	28.5	[34]
高温煅烧脱硫法	-	1 200~1 400	-	4.0	76.4	[39]
氧化脱硫法	自制氧化性脱硫剂	60	30^*	12.0	75.0	[40]
碱金属化合物脱硫法	碱金属化合物	550	4.0∶1.0	2.0	99.5	[46]
	NaOH	500	2.0∶1.0	2.0	98.1	[47]
	NaOH	1 600	2.0∶1.0	2.0	98.5	[48]
	KOH	600	1.5∶1.0	2.0	84.3	[49]
加氢脱硫法	氢气	760	-	2.0	87.0	[29]
加氢脱硫法	氢气	950	-	0.2	83.0	[52]
微生物脱硫法	氧化亚铁酸性硫杆菌	19~22	-	24.0	38.3	[34]
过程强化辅助脱硫法	超声辅助	-	-	-	93.6	[55]
过程强化辅助脱硫法	微波辅助	-	-	0.5	73.9	[57]

方法	脱硫条件				脱硫率/%	文献
方法	试剂	温度/℃	剂焦质量比	反应时间/h	脱硫率/%	文献
溶剂萃取脱硫法	邻氯苯酚	160	10.0∶1.0	2.0	19.0	[33]
	四氯乙烯	常温	17.0∶1.0	2.0	35.0	[34]
	邻氯苯酚	常温	17.0∶1.0	4.0	28.5	[34]
高温煅烧脱硫法	-	1 200~1 400	-	4.0	76.4	[39]
氧化脱硫法	自制氧化性脱硫剂	60	30^*	12.0	75.0	[40]
碱金属化合物脱硫法	碱金属化合物	550	4.0∶1.0	2.0	99.5	[46]
	NaOH	500	2.0∶1.0	2.0	98.1	[47]
	NaOH	1 600	2.0∶1.0	2.0	98.5	[48]
	KOH	600	1.5∶1.0	2.0	84.3	[49]
加氢脱硫法	氢气	760	-	2.0	87.0	[29]
加氢脱硫法	氢气	950	-	0.2	83.0	[52]
微生物脱硫法	氧化亚铁酸性硫杆菌	19~22	-	24.0	38.3	[34]
过程强化辅助脱硫法	超声辅助	-	-	-	93.6	[55]
过程强化辅助脱硫法	微波辅助	-	-	0.5	73.9	[57]

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