热改质过程中渣油结构及其重组分溶剂化变化规律研究

刘朝仙; 郭爱军; 陈坤; 王宗贤; 储浚; 陈建涛

热改质过程中渣油结构及其重组分溶剂化变化规律研究

1.
中国石油大学(华东) 化学工程学院重质油国家重点实验室, 山东青岛 266580
2.
中国石油大学(华东) 理学院, 山东青岛 266580
3.
北海市北部湾经济区建设管理委员会办公室, 广西北海 536000

基金项目:

国家自然科学基金 U1362101

中央高校基本科研业务费专项资金 14CX02120A

山东省自然科学基金 ZR2014BQ030

青岛市自主创新计划应用研究专项 15-9-1-77-jch

中国石油重大专项 PRIKY15002

中国石油重大专项 PRIKY15008

中国石油重大专项 PRIKY15009

详细信息

通讯作者:
郭爱军, Tel: 0532-86980607, Fax: 0532-86981787, E-mail: ajguo@upc.edu.cn

中图分类号: TE624
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出版历程
- 收稿日期: 2015-10-12
- 修回日期: 2016-01-08
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-03-30

Changes in chemical structure and solvation of heavy oil components during thermal upgrading of a vacuum residue

1.
State Key Laboratory of Heavy Oil, College of Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, China
2.
College of Science, China University of Petroleum (East China), Qingdao 266580, China
3.
Construction and Management Commission Office of Beibu Bay Economic Zone, Beihai 536000, China

Funds:

National Natural Science Foundation of China U1362101

the Fundamental Research Funds for the Central Universities 14CX02120A

the Provincial Natural Science Foundation of Shandong ZR2014BQ030

the Application Research of Independent Innovation Foundation of Qingdao 15-9-1-77-jch

and the China National Petroleum Corporation (CNPC) Grant on Research and Development for Commercial Application of Novel Technologies in Processing Inferior Heavy Oil PRIKY15002

and the China National Petroleum Corporation (CNPC) Grant on Research and Development for Commercial Application of Novel Technologies in Processing Inferior Heavy Oil PRIKY15008

and the China National Petroleum Corporation (CNPC) Grant on Research and Development for Commercial Application of Novel Technologies in Processing Inferior Heavy Oil PRIKY15009

摘要

摘要: 以委内瑞拉减压渣油为原料, 采用微型反应釜, 研究了其在410℃、2.0MPa氮气初压下, 不同反应停留时间的热改质过程生成油的化学结构组成及其重组分溶剂化变化规律.通过¹H-NMR技术研究了热改质过程生成油中沥青质和重胶质不同化学位移归属氢的转化路径; 并结合改进的Brown-Ladner法分析了热改质过程生成油中沥青质和重胶质的平均分子结构参数变化; 采用蒸汽压渗透法考察了热改质过程生成油中沥青质和重胶质在甲苯溶液中所形成的复合超分子结构的平均相对分子质量.结果表明, 随着热改质程度的加深, 沥青质和重胶质的H/C原子比减小, 供氢能力逐渐下降, 沥青质和重胶质的芳香环共轭程度和f_A在体系生焦后(45min) 显著提高; 沥青质的聚集趋势相关值在热改质15min前变化不大, 15min后显著增强, 而重胶质在整个热改质过程中, 其聚集趋势相关值的增势较为缓和; 沥青质和重胶质的聚集趋势相关值差异逐渐增大, 15min时增加了1.5%、25min时增加了50.8%、45min时增加了142.3%, 表明沥青质和重胶质的结构差异越来越明显; 重胶质溶剂化沥青质的能力逐步减弱, 体系的溶剂化参数从0时的32.9%逐步降到15min时的29.5%、25min时的14.1%和45min时的9.6%;热改质生成油的斑点实验等级逐渐增加, 体系的胶体稳定性逐渐降低.
- 热改质 /
- 沥青质 /
- 重胶质 /
- 化学结构组成 /
- 溶剂化
Abstract: The Venezuelan vacuum residue was used as a feedstock for thermal upgrading experiments to investigate the changes in chemical structure and composition and the solvation interaction of heavy oil components in a micro-batch reactor at 410℃ with an initial pressure of nitrogen 2.0MPa. The ¹H-nuclear magnetic resonance measurement was applied to analyze the reaction pathway of hydrogen atoms with different chemical shift of the heavy oil components. The average molecular structural parameters of asphaltenes and heavy resins in the oil produced by thermal upgrading of the feedstock were calculated and analyzed by the modified Brown-Lander methods. The vapor pressure osmometry was used to determine the average molecular weights of supramolecular structures formed by asphaltenes and heavy resins in toluene. The results show that both H/C atomic ratio and hydrogen donating ability of asphaltenes and heavy resins decrease with reaction time, and the conjugate degree of aromatic ring system and f_A become greater clearly after 45min. The aggregation of asphaltenes rises slowly and increases sharply after 15 min, while there is a slight change of aggregation for the heavy resins during the whole reaction time, and the differences in aggregation correlation values between asphaltenes and heavy resins are increased by 1.5% at 15min, 50.8% at 25min, and 142.3% at 45min, respectively. The solvation interaction of heavy resins with asphaltenes weakens with time, and the solvation parameters decrease from 32.9% at the beginning to 29.5% at 15min, 14.1% at 25min, and 9.6% at 45min, respectively. The changes may contribute to the dropping of thermal colloidal stability of resins and the increasing of spot ratings.
- thermal upgrading /
- asphaltenes /
- heavy resins /
- chemical structure and composition /
- solvation

HTML全文

图 1 VNVR热改质过程生成油中甲苯不溶物含量

Figure 1 Contents of toluene-insolubles in the oil produced by thermal upgrading of VNVR

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图 2 VNVR热改质过程生成油中沥青质和重胶质的含量

Figure 2 Contents of asphaltenes and heavy resins in the oil produced by thermal upgrading of VNVR

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图 3 VNVR热改质过程生成油中沥青质(a) 和重胶质(b) 的核磁共振氢谱谱图

Figure 3 ¹H-NMR spectra of asphaltenes (a) and heavy resins (b) in the oil produced by thermal upgrading of VNVR

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图 4 VNVR热改质过程生成油中沥青质和重胶质的聚集趋势相关值

Figure 4 G_A values of asphaltenes and heavy resins in the oil produced by thermal upgrading of VNVR

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图 5 VNVR改质过程生成油中重胶质对沥青质的溶剂化作用

Figure 5 Solvation of heavy resins on asphaltenes in the oil produced by thermal upgrading of VNVR

(a): 0 min; (b): 15 min; (c): 25 min; (d): 45 min

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图 6 VNVR热改质过程生成油斑点实验照片

Figure 6 Spot pictures of oil from thermal upgrading of VNVR

(a): 0 min; (b): 15 min; (c): 25 min; (d): 45 min

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表 1 委内瑞拉减压渣油性质

Table 1 Properties of the Venezuelan vacuum residue

ρ²⁰/ (g·cm^-3)	μ¹⁰⁰/ (mm²·s^-1)	Conradson carbon residue w/%	w/%				H/C (atomic ratio)	n-C₇Asp. w/%	w/(μg·g^-1)
ρ²⁰/ (g·cm^-3)	μ¹⁰⁰/ (mm²·s^-1)	Conradson carbon residue w/%	C	H	S	N	H/C (atomic ratio)	n-C₇Asp. w/%	Ni	V
1.053 2	58 530	25.57	83.74	9.58	4.65	0.90	1.36	17.48	40.34	33.66

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表 2 VNVR热改质过程生成油中沥青质和重胶质的元素组成及其不同归属氢含量

Table 2 CHSN elemental composition and ¹H-NMR analysis of asphaltenes and heavy resins in the oil produced by thermal upgrading of VNVR

Items	Asphaltenes				Heavy resins
Items	0 min	15 min	25 min	45 min	0 min	15 min	25 min	45 min
H w /%	7.32	7.16	6.84	6.15	8.85	8.11	7.84	7.12
C w/%	81.77	82.69	83.06	83.45	82.22	83.53	83.71	84.04
N w/%	2.01	1.97	1.94	2.00	1.52	1.58	1.74	1.79
S w/%	5.50	5.08	4.86	4.67	4.66	4.77	4.59	4.82
O_di w/%	3.40	3.10	3.30	3.73	2.75	2.01	2.12	2.23
H/C (atomic ratio)	1.08	1.04	0.99	0.89	1.29	1.17	1.12	1.02
H_A/H_T	0.122	0.134	0.145	0.197	0.097	0.144	0.162	0.196
H_α/H_T	0.199	0.214	0.235	0.227	0.215	0.219	0.225	0.262
H_β/H_T	0.487	0.483	0.471	0.425	0.516	0.471	0.455	0.406
H_γ/H_T	0.192	0.169	0.149	0.151	0.172	0.166	0.158	0.136
O_di: estimated by difference; H_A: hydrogen attached to aromatic ring with chemical shift between 6.0 and 9.0; H_α: hydrogen on naphthenic ring or alkyl chain adjacent to aromatic ring with chemical shift between 2.0 and 4.0; H_β: hydrogen on naphthenic ring or alkyl chain with two or more positions from an aromatic ring with chemical shift between 1.0 and 2.0; H_γ: terminal methyl protons of paraffins or of alkyl side-chains three or more positions from an aromatic ring with chemical shift between 0.5 and 1.0; H_T: hydrogen in total of H_A, H_α, H_β and H_γ

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表 3 VNVR热改质过程生成油中沥青质和重胶质的平均分子结构参数

Table 3 Average molecular structural parameters of asphaltenes and heavy resins from reaction oil during thermal upgrading of VNVR

Items	Asphaltenes				Heavy resins
Items	0 min	15 min	25 min	45 min	0 min	15 min	25 min	45 min
f_A	0.55	0.57	0.59	0.66	0.44	0.52	0.55	0.61
f_N	0.19	0.20	0.21	0.20	0.20	0.19	0.19	0.20
f_P	0.26	0.23	0.20	0.14	0.36	0.29	0.26	0.19
H_AU/C_A	0.41	0.42	0.42	0.40	0.58	0.55	0.54	0.53
usw	933.1	857.1	833.9	821.2	594.3	554.7	535.1	509.3
C_T^*	63.5	59.0	57.7	57.1	40.7	39.6	37.3	35.7
H_T^*	68.3	61.4	57.0	50.5	52.6	44.9	41.9	36.3
S_T^*	1.6	1.4	1.3	1.2	0.8	0.8	0.8	0.8
N_T^*	1.3	1.2	1.1	1.1	0.6	0.6	0.7	0.7
O_T^*	2.0	1.7	1.7	1.9	1.0	0.7	0.6	0.7
R_T^*	15.1	14.4	14.8	15.6	7.7	8.2	8.2	8.7
R_A^*	10.8	10.3	10.6	11.7	4.8	5.6	5.7	6.2
R_N^*	4.3	4.1	4.1	3.9	2.9	2.6	2.5	2.5
R_N^/R_A^	0.40	0.40	0.39	0.33	0.59	0.46	0.44	0.40
C_A^*	36.5	35.0	35.7	39.1	18.4	20.8	21.2	22.5
f_A: ratio of aromatic carbon to total carbons; f_N: ratio of naphthenic carbon to total carbons; f_P: ratio of paraffinic carbons to total carbons; H_AU/C_A: condensation degree parameter of aromatic ring system; usw: unit sheet weight

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表 4 VNVR热改质过程生成油斑点实验等级

Table 4 Spot ratings of oil from thermal upgrading of VNVR

Reaction time t /min	Spot ratings
0	2
15	2
25	4
45	5

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