Effect of asphaltene contents on hydrogen solubility in heavy oils

doi:10.11949/0438-1157.20190612

Abstract

Abstract:

Hydrogen is an important reaction component in the oil hydrogenation process, and its solubility in petroleum fractions is a key factor affecting the hydrogenation process. Nevertheless, the sets of data for hydrogen solubility in heavy oils are scarce in literatures, and especially no attention has been paid on the influence of asphaltene on the hydrogen solubility in heavy oils. The solubility of hydrogen in four heavy oil feedstocks was systematically studied by high pressure stirred tank. The variation of hydrogen solubility in heavy oil with temperature and pressure was obtained. The effect of asphaltene content on hydrogen solubility was investigated. It was found that hydrogen solubility in certain oil increased with temperature and pressure under the present measurement conditions. The hydrogen solubility was influenced more significantly by temperature under higher pressure and pressure under higher temperature. The Flash module in Aspen Plus is combined with the PR state equation to establish a hydrogen solubility calculation model, and the hydrogen solubility under high temperature conditions is predicted. The results indicate the contradiction between hydrogen solubility and hydrogen consumption in vacuum residue of Canadian oil sand bitumen is much serious under conventional hydrogenation conditions. The hydrogen solubility of the deasphalted oil is greatly improved, and the removal of resin and asphaltene alleviates the contradiction between hydrogen dissolution and hydrogen consumption.

Key words: hydrogen solubility, heavy oil, asphaltene, PR equation of state

摘要：

氢气是油品加氢工艺中重要的反应组分，其在石油馏分中的溶解性能是影响加氢工艺过程的关键因素。重油中氢气溶解度的数据较为匮乏，尤其是重油中沥青质组分对氢气溶解度的影响并未受到关注。采用高压搅拌釜对氢气在四种重油原料中的溶解度进行系统研究，获得了氢气在重油中溶解性能随温度和压力的变化规律，并考察了沥青质含量对氢气溶解性能的影响。结果表明，氢气在相同重油原料中的溶解度随温度和压力的升高而增大，并且在较高温度或压力条件下，压力或温度变化对氢气溶解性能的影响更加显著。利用Aspen Plus中的Flash模块结合PR状态方程建立氢气溶解度计算模型，并进行高温条件氢气溶解度的预测，表明常规加氢条件下加拿大油砂沥青减渣中氢气溶解度与氢耗之间的矛盾极为尖锐，其脱沥青油的氢气溶解性能得到较大改善，胶质和沥青质的脱除缓解了氢气溶解和氢耗之间的矛盾。

关键词: 氢气溶解性, 重油, 沥青质, PR状态方程

CLC Number:

TE 624

Xiang BAI, Run GUO, Zhaopeng ZENG, Zhentao CHEN, Linzhou ZHANG, Zhiming XU, Chunming XU, Suoqi ZHAO. Effect of asphaltene contents on hydrogen solubility in heavy oils[J]. CIESC Journal, 2019, 70(10): 4012-4020.

白翔, 郭润, 曾招朋, 陈振涛, 张霖宙, 许志明, 徐春明, 赵锁奇. 沥青质含量对重油中氢气溶解度影响的研究[J]. 化工学报, 2019, 70(10): 4012-4020.

Figures/Tables 12

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原料油	饱和分/% (质量)	芳香分/% (质量)	胶质/%(质量)	沥青质/% (质量)
VR	9.5	38.4	30.7	21.4
DO	14.1	59.4	25.8	0.8
BO-1	12.8	53.8	23.4	10.2
BO-2	11.4	47.9	20.8	20.1

原料油	饱和分/% (质量)	芳香分/% (质量)	胶质/%(质量)	沥青质/% (质量)
VR	9.5	38.4	30.7	21.4
DO	14.1	59.4	25.8	0.8
BO-1	12.8	53.8	23.4	10.2
BO-2	11.4	47.9	20.8	20.1

T/℃	密度/(g/ml)
T/℃	DO	BO-1	BO-2	VR
110	1.008	1.019	1.030	1.037
120	1.001	1.011	1.024	1.030
130	0.994	1.007	1.017	1.024
140	0.988	0.998	1.010	1.017
150	0.983	0.995	1.004	1.011

T/℃	密度/(g/ml)
T/℃	DO	BO-1	BO-2	VR
110	1.008	1.019	1.030	1.037
120	1.001	1.011	1.024	1.030
130	0.994	1.007	1.017	1.024
140	0.988	0.998	1.010	1.017
150	0.983	0.995	1.004	1.011

原料油	150℃		200℃		250℃		300℃
原料油	P/MPa	溶解度/(mol/kg)	P/MPa	溶解度/(mol/kg)	P/MPa	溶解度/(mol/kg)	P/MPa	溶解度/(mol/kg)
DO	2.537	0.045	2.328	0.047	2.386	0.066	2.571	0.077
	4.266	0.070	4.167	0.076	4.144	0.089	4.631	0.11
	6.386	0.096	6.285	0.11	6.288	0.12	6.129	0.13
	8.098	0.12	8.497	0.14	8.405	0.16	8.121	0.16
	10.266	0.15	10.613	0.17	10.484	0.19	9.96	0.19
	13.082	0.19	12.512	0.20	12.546	0.22	11.951	0.23
	15.257	0.20	14.846	0.23	14.454	0.25	14.356	0.27
	16.062	0.22	18.814	0.28	16.127	0.27	16.632	0.32
BO-1	2.311	0.037	2.312	0.048	2.121	0.059	2.121	0.071
	4.524	0.059	4.204	0.070	4.392	0.085	4.518	0.097
	6.465	0.089	6.141	0.098	6.414	0.11	6.399	0.13
	8.253	0.11	8.567	0.13	8.491	0.15	8.377	0.16
	10.155	0.14	10.468	0.16	10.401	0.17	10.113	0.20
	12.396	0.16	12.313	0.18	12.527	0.20	12.304	0.23
	14.408	0.18	14.016	0.20	14.261	0.24	14.653	0.26
	17.172	0.21	16.143	0.23	16.941	0.27	16.681	0.30
BO-2	2.334	0.024	2.115	0.040	2.333	0.055	2.133	0.066
	4.238	0.041	4.478	0.066	4.888	0.082	4.594	0.097
	6.393	0.063	6.294	0.090	6.193	0.11	6.672	0.13
	8.509	0.087	8.377	0.11	8.503	0.13	8.386	0.16
	10.223	0.11	10.324	0.14	10.435	0.16	9.837	0.18
	12.433	0.14	12.558	0.17	12.252	0.19	12.206	0.21
	14.555	0.17	14.534	0.19	14.372	0.22	14.365	0.25
	16.166	0.18	17.444	0.22	16.577	0.25	17.033	0.29
VR	2.144	0.017	2.147	0.033	2.334	0.046	2.251	0.053
	4.324	0.036	4.333	0.058	4.137	0.069	4.134	0.080
	6.162	0.050	6.156	0.079	6.158	0.092	6.113	0.12
	8.098	0.074	8.147	0.093	8.288	0.12	7.813	0.13
	10.067	0.088	10.085	0.11	9.736	0.15	10.438	0.17
	11.795	0.11	11.954	0.14	12.043	0.17	11.666	0.20
	13.930	0.12	14.173	0.16	14.093	0.19	14.632	0.24
	18.046	0.18	17.758	0.20	17.263	0.23	17.722	0.28