大港油浆流化焦化行为及其富芳烃油制备基础研究

doi:10.11949/0438-1157.20201786

化工学报 ›› 2021, Vol. 72 ›› Issue (8): 4325-4335.DOI: 10.11949/0438-1157.20201786

大港油浆流化焦化行为及其富芳烃油制备基础研究

张玉明¹(),万利锋^1,²,管俊涛¹,宋海朋³,杨行³,高士秋²

^1.中国石油大学（北京）重质油国家重点实验室，北京 102249
^2.中国科学院过程工程研究所多相复杂系统国家重点实验室，北京 100190
^3.中国石油天然气股份有限公司石油化工研究院，北京 102206

收稿日期:2020-12-09 修回日期:2021-01-27 出版日期:2021-08-05 发布日期:2021-08-05
通讯作者: 张玉明
作者简介:张玉明（1985—），男，博士，副教授，ymzhcup@163.com
基金资助:
国家自然科学基金项目(U1862107);国家重点研发计划项目(2018YFE0183600);中国石油大学（北京）科研基金(20200127)

Fundamental study on the fluid coking behavior of Dagang oil slurry and preparation of aromatic-rich oil

Yuming ZHANG¹(),Lifeng WAN^1,²,Juntao GUAN¹,Haipeng SONG³,Hang YANG³,Shiqiu GAO²

^1.State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China
^2.State Key Laboratory of Multi-Phase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
^3.PetroChina Petrochemical Research Institute, Beijing 102206, China

Received:2020-12-09 Revised:2021-01-27 Online:2021-08-05 Published:2021-08-05
Contact: Yuming ZHANG

摘要/Abstract

摘要：

以大港油浆为原料，流化焦化焦粉为载体，考察其转化反应特性，为油浆高价值利用技术的开发提供指导。首先采用热重分析仪对大港油浆和焦粉的热分解特性进行研究，之后分别以石英砂和焦粉作为热载体，探究大港油浆流化热转化反应规律。温度为500℃时，石英砂裂解液体和气体收率分别为85.54%和1.24%，相应的焦粉裂解液体和气体收率分别为84.02%和1.77%，说明与石英砂相比，焦粉具有促进热转化的作用。综合红外及GC-MS对油浆及其液体产物的分析结果，流化热转化实现了油浆中芳烃组分的富集，且焦粉裂解液体中芳烃富集效果更好。最后焦粉循环利用实验结果表明，焦粉裂化效果的稳定性较好，验证了焦粉作为油浆改性接触剂的可行性。

关键词: 油浆, 流化焦化焦粉, 热载体, 流化热转化

Abstract:

Using Dagang oil slurry as the raw material and fluidized coking powder as the carrier, the investigation of its conversion reaction characteristics provides guidance for the development of high-value utilization technology of oil slurry. First, a thermogravimetric analyzer was used to study the thermal decomposition characteristics of Dagang slurry oil and fluid coke. Afterwards, quartz sand and fluid coke were used as heat carriers to explore the thermal conversion reaction law of Dagang slurry oil at different temperatures. When the temperature was about 500℃, the quartz sand cracked oil yield was 85.54%, and the gas yield was 1.24%. Correspondingly, the oil and gas yield over fluid coke was 84.02% and 1.77%, respectively, indicating that the fluid coke had the effect of promoting thermal conversion. Combining FTIR and GC-MS to analyze the slurry oil and its pyrolysis oil, the results show that fluidized thermal conversion had achieved the enrichment of the aromatics components of the oil slurry, and the pyrolysis oil obtained from fluid coke as the heat carrier was richer in aromatics than that of silica sand. Finally, the circulation characteristics of fluid coke were investigated and verified the feasibility of fluid coke as a heat carrier due to its catalytic stability.

Key words: oil slurry, fluid coke, heat carrier, fluid thermal conversion

中图分类号:

TQ 546

张玉明, 万利锋, 管俊涛, 宋海朋, 杨行, 高士秋. 大港油浆流化焦化行为及其富芳烃油制备基础研究[J]. 化工学报, 2021, 72(8): 4325-4335.

Yuming ZHANG, Lifeng WAN, Juntao GUAN, Haipeng SONG, Hang YANG, Shiqiu GAO. Fundamental study on the fluid coking behavior of Dagang oil slurry and preparation of aromatic-rich oil[J]. CIESC Journal, 2021, 72(8): 4325-4335.

图/表 17

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项目	大港油浆	项目	大港油浆
密度（20℃）/(g/cm³)	1.032	康氏残炭/%(质量)	18.61
运动黏度（80℃）/(mm²/s)	131.31	固含量/(μg/g)	3100
元素组成分析 /%(质量)		n(H)/n(C)	1.17
C	88.6	馏程分布/℃
H	8.62	初馏点	371
S	1.34	10%	416
N	0.25	30%	447
四组分分析/%(质量)		50%	473
饱和分	23.46	70%	500
芳香分	59.85	90%	538
胶质	14.20	终馏点	600
沥青质（正戊烷）	2.49

项目	大港油浆	项目	大港油浆
密度（20℃）/(g/cm³)	1.032	康氏残炭/%(质量)	18.61
运动黏度（80℃）/(mm²/s)	131.31	固含量/(μg/g)	3100
元素组成分析 /%(质量)		n(H)/n(C)	1.17
C	88.6	馏程分布/℃
H	8.62	初馏点	371
S	1.34	10%	416
N	0.25	30%	447
四组分分析/%(质量)		50%	473
饱和分	23.46	70%	500
芳香分	59.85	90%	538
胶质	14.20	终馏点	600
沥青质（正戊烷）	2.49

工业分析/%(质量)				元素分析/%(质量)					HHV/(MJ/kg)
M_ad	A_ad	V_ad	FC_ad	C_daf	H_daf	S_daf	N_daf	O_daf^①	HHV/(MJ/kg)
0.54	5.17	7.63	86.66	85.38	2.31	3.53	1.94	6.84	32.15

工业分析/%(质量)				元素分析/%(质量)					HHV/(MJ/kg)
M_ad	A_ad	V_ad	FC_ad	C_daf	H_daf	S_daf	N_daf	O_daf^①	HHV/(MJ/kg)
0.54	5.17	7.63	86.66	85.38	2.31	3.53	1.94	6.84	32.15

项目	500℃	550℃	600℃
收率
油收率/%(质量)	85.54	83.33	81.66
焦炭收率/%(质量)	12.52	13.03	14.51
气体收率/%(质量)	1.24	1.84	3.01
总产物收率/%(质量)	99.31	98.21	99.18
液体产物分布
汽油馏分/%(质量)	0.12	0.61	1.01
柴油馏分/%(质量)	4.41	5.24	7.22
VGO馏分/%(质量)	65.49	66.39	66.47
重油馏分/%(质量)	29.98	27.76	25.31
液体产物固含量
裂解油品固含量/(μg/g)	214	199	191
脱固率/%	93.10	93.58	93.84

大港油浆流化焦化行为及其富芳烃油制备基础研究

Fundamental study on the fluid coking behavior of Dagang oil slurry and preparation of aromatic-rich oil

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参考文献 34

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项目	实验1	实验2	实验3	平均值	相对误差
反应温度/^oC	500	500	500	500
油收率/%(质量)	84.38	83.35	84.32	84.02	0.80
焦炭收率/%(质量)	13.93	14.82	13.89	14.21	4.29
气体收率/%(质量)	1.69	1.83	1.79	1.77	4.52
总收率/%(质量)	100.00	100.00	100.00	100.00

参数	油浆	石英砂裂解油	焦粉裂解油
A₁₆₀₀	0.944	0.647	0.448
A₁₄₆₀	0.795	0.468	0.276
A₁₃₈₀	0.895	0.637	0.444
P	0.739	0.745	0.754
f_a	0.448	0.452	0.457

分类	组分性质	含量/%(质量)
分类	组分性质	Slurry oil	Sand-500	Sand-600	Coke-500	Coke-600
烷烃类		20.61	15.33	16.36	12.47	17.59
2~3环芳烃	萘系（带侧链）	0.26	0.00	0.00	0.00	0.00
	菲系（带侧链）	3.60	3.42	3.97	1.47	1.04
	蒽系（带侧链）	0.72	1.40	2.16	0.48	0.00
	其他	9.51	9.34	10.16	11.63	10.90
4环芳烃	芘系（带侧链）	8.67	9.73	11.20	8.04	6.00
	?系（带侧链）	5.28	12.84	12.53	2.55	3.46
	苯并菲（带侧链）	2.73	2.74	2.91	2.24	2.12
	苯并蒽（带侧链）	36.72	23.19	23.22	46.47	44.57
	其他	0.48	1.50	1.30	0.48	0.44
5环芳烃		9.17	12.00	11.72	12.15	12.21
2~5环占比		77.14	77.42	79.16	85.48	80.74

项目	原始焦	循环1次	循环2次	循环3次
温度/℃	500	500	500	500
油收率/%(质量)	84.02	84.18	83.98	85.77
焦炭收率/%(质量)	14.21	14.06	14.21	12.51
气体收率/%(质量)	1.77	1.76	1.82	1.72
总收率/%(质量)	100.00	100.00	100.00	100.00

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项目	500℃	550℃	600℃
收率
油收率/%(质量)	84.02	82.05	80.50
焦炭收率/%(质量)	14.21	16.10	16.23
气体收率/%(质量)	1.77	1.85	3.27
总物料收率/%(质量)	100.00	100.00	100.00
液体产物分布
汽油馏分/%(质量)	0.21	0.42	0.74
柴油馏分/%(质量)	5.01	5.60	6.58
VGO馏分%(质量)	68.28	68.30	67.99
重油馏分/%(质量)	26.51	25.69	24.69
液体产物固含量
裂解油品固含量/(μg/g)	167	162	161
脱固率/%	94.61	94.77	94.81

项目	500℃	550℃	600℃
收率
油收率/%(质量)	84.02	82.05	80.50
焦炭收率/%(质量)	14.21	16.10	16.23
气体收率/%(质量)	1.77	1.85	3.27
总物料收率/%(质量)	100.00	100.00	100.00
液体产物分布
汽油馏分/%(质量)	0.21	0.42	0.74
柴油馏分/%(质量)	5.01	5.60	6.58
VGO馏分%(质量)	68.28	68.30	67.99
重油馏分/%(质量)	26.51	25.69	24.69
液体产物固含量
裂解油品固含量/(μg/g)	167	162	161
脱固率/%	94.61	94.77	94.81