Ma Qiang, Yang Zhengda, Zhang Liqiang, Lin Riyi, Wang Xinwei
College of New Energy, China University of Petroleum (East China) Qingdao 266580 P. R. China
China Petroleum Pipeline Engineering Co., Ltd Langfang Hebei 100044 China.
RSC Adv. 2019 Oct 23;9(58):33990-33996. doi: 10.1039/c9ra07735a. eCollection 2019 Oct 18.
During the thermal enhanced oil recovery (EOR) process, the hazardous hydrogen sulfide (HS) gas among the produced gases causes significant difficulty in the exploration and development of petroleum. In this study, the effects of superheat degree on the HS generation by heavy oil aquathermolysis were explored through simulated experiments. The crude and residual oils before and after the reaction were separated into saturate, aromatic, resin and asphaltene fractions (SARA). The oil samples were analyzed from various perspectives by various characterization methods including Fourier transform infrared (FTIR) spectroscopy, elemental analysis, and X-ray photoelectron spectroscopy (XPS). The results showed that HS generation was favored by larger superheat degree at the same temperature, and it increased from 0.178 to 0.345 mL g oil with an increase in the superheat degree from 62.19 to 89.42 °C. The contents of the sulfur-containing substances, which were supposed to be the main sources of HS generation, in the saturate and aromatic fractions decreased significantly with an increase in the superheat degree; the increase in the superheat degree led to a slight reduction in the contents of the methylene, methyl and carboxyl/carbonyl groups. Moreover, the analysis of the main sulfur existing forms before and after the reaction suggests that sulfur in the forms of sulfides, sulfones and sulfates is more likely to generate HS under superheated steam conditions. This study provides an understanding of the mechanism of HS generation during the process of injecting superheated steam for heavy oil recovery.
在热法强化采油(EOR)过程中,采出气体中的有害硫化氢(HS)气体给石油勘探开发带来了巨大困难。本研究通过模拟实验探究了过热度对稠油水热裂解生成HS的影响。将反应前后的原油和渣油分离为饱和烃、芳烃、胶质和沥青质馏分(SARA)。采用傅里叶变换红外(FTIR)光谱、元素分析和X射线光电子能谱(XPS)等多种表征方法,从多个角度对油样进行了分析。结果表明,在相同温度下,过热度越大越有利于HS的生成,当过热度从62.19℃增加到89.42℃时,HS生成量从0.178 mL/g油增加到0.345 mL/g油。饱和烃和芳烃馏分中被认为是HS主要生成来源的含硫物质含量随过热度增加而显著降低;过热度增加导致亚甲基、甲基和羧基/羰基含量略有降低。此外,对反应前后主要硫存在形式的分析表明,硫化物、砜和硫酸盐形式的硫在过热蒸汽条件下更易生成HS。本研究有助于理解注过热蒸汽开采稠油过程中HS的生成机理。