The correlation of sulfur content and other characteristics of crude oil. The abiogenic contribution to oil and gas formation

The reaction of endogenous methane with sulfur is one of the hypothetical methods of formation of the abiogenic constituent of oil and gas systems. It could be the initial stage of condensation transformations of methane and be responsible for correlations between the concentration of sulfur and many of the physicochemical characteristics of crude oil. The key role of these transformations is confirmed by the effect of the sulfur content of crudes on the scales of oil pools. This dependence is manifested on both the continental and on the local levels. __________ Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 4, pp. 3–6, July–August, 2007.     

控制冷凝法对烟气中三氧化硫冷凝分离效率研究

目的研究不同操作参数和烟气工况对控制冷凝法分离烟气中SO₃效率的影响,以避免因烟气中SO₃质量浓度过高导致装置腐蚀穿孔并产生高盐污水。 方法利用自主研发的烟气中SO₃控制冷凝效率评价装置研究了不同操作参数和烟气工况对烟气中SO₃冷凝分离效率的影响。 结果烟气流量和烟气中SO₃质量浓度变化对SO₃冷凝分离效率有明显影响,冷凝系统末端引入石英过滤棉可以明显地消除烟气中SO₃质量浓度变化对SO₃冷凝分离效率的影响。在烟气取样管路的温度高于酸雾露点并且冷凝管温度介于酸雾露点和水蒸气露点之间时,烟气取样管路保温温度、冷凝管温度变化对烟气中SO₃冷凝分离效率几乎没有影响。烟气中SO₂质量浓度变化对烟气中SO₃冷凝分离效率几乎没有影响。 结论建立的SO₃冷凝分离方法对烟气中SO₃的分离效率大于95%。      

考虑液硫析出的超深酸性气藏数值模拟技术

超深酸性气藏开采时在储层中发生液硫析出现象,阻碍气体流动,降低气井产能。为研究液硫析出对气井生产的影响,建立考虑了液硫析出、气-液硫两相同流的酸性气藏数值模拟模型。基于上述模型开发了相应的数值模拟器,并将该模拟技术应用于四川盆地元坝长兴组气藏气井动态研究中。结果表明：液硫析出后在井壁附近聚集,并且自始至终仅局限于井筒附近。相较固硫析出而言,液硫析出对气井生产的影响较小,但仍能明显降低气井稳产期。在非均质地层中,析出的液硫主要聚集在储层物性较好的区域,如裂缝或溶孔等高渗区,造成气藏渗透性降低,气井产能下降。该模拟技术实现了对酸性气藏液硫析出的定量预测,为该类气藏的开发提供了可靠的决策依据。     

Sulfur and metal contents – genetic aspects of crude oils

Increased sulfur content, condensation, and amount of vanadium (V > Ni) observed in real crude oil systems are explained from the standpoint of formation of abiogenous constituents of crude oil systems, which is a part of the overall process of oxidative transformations of endogenous fluids as they move toward the earth’s surface and is caused by oxidative dehydrocondensation effect on the hydrocarbon component of elemental sulfur S0 present in the fluids. These mechanisms arise from oxidation of deep-earth (plutonic) hydrogen sulfide to S⁰ and SO₄²⁻ due to intensification of oxidative conditions in the process of ascending movement of the fluid and acceleration of oxidative processes by vanadium present in the system.     

New developments and implementations in the field of hydrocarbon-stock desulfurization

Processes involving the removal of sulfur compounds from gases and liquid petroleum products are analyzed. Economic expediency of the implementation of low-waste methods of demercaptanization of gases, gasoline and kerosene cuts, gas condensates, and light crudes with the polymeric catalyst KSM is substantiated. A complex desulfurization flow plan, which permits maximum extraction of natural sulfur-organic compounds, lowering of the content of total sulfur in the light cuts, and improvement of hydrofinishing conditions of the heavy cuts is proposed. Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 6, pp. 3–8, November–December, 2008.     

Reasons for low heavy vacuum gas oil yield in vacuum distillation of residual fuel oil

Calculations are made of the heat balance of the vacuum column K-101 of the VDM-2 plant of LUKOIL Neftokhim Burgas AD, which made it possible to disclose the reasons for decline in heavy vacuum gas oil yield with increase in plant load and to discard the hypothesis that the reason for this is perforating of the plate from which the gas oil is withdrawn. It is shown that the reflux yield cannot be increased and the heat required for condensation of the heavy vacuum gas oil contained in the residual fuel oil cannot be removed if there is hydraulic resistance in the lower circulating reflux line. Translated from Khimiya i Tekhnologiya Topliv i Masel, No.3, pp. 19 – 22, May – June, 2009.     

沸腾床加氢过程重油分子结构变化规律

考察了沸腾床加氢过程中,渣油转化率对杂质脱除率和未转化油(UCO)性质及其分子结构的影响,并探讨了加氢过程中重油分子结构的变化规律.结果表明:渣油转化率增加,UCO中杂质(硫、氮、金属)脱除率增加,密度、残炭值、氮质量分数升高,硫质量分数和含金属量降低;胶质沥青质转化率与渣油转化率呈现良好的线性关系,随着渣油转化率增大...     

Experimental study into the effectiveness of the partial gas cycling process in the gas-condensate reservoir development

In this study a laboratory study was carried out with the purposes of estimating the effectiveness of the gas cycling process during gas-condensate reservoir development. Specific laboratory equipment was constructed to carry out an experimental investigation by modelling the gas injection and reservoir depletion process. Volumetric properties, fog up, liquid drop-out condition, and retrograde dew point pressures of gas-condensate fluids were investigated. The reservoir fluid was recombined based on samples from Azerbaijan natural gas-condensate reservoir. Results are describing gas injection effect on condensate/gas ratio and condensate recovery in each pressure step. These have provided an understanding on the influence of the retrograde dew point pressure on optimum gas injection stage. The analyses also assure that as condensate/gas ratio decreases continually during the gas injection process, which causes the reservoir fluid PVT characteristics to be changed accordingly furthermore the reservoir pressure can be depleted in order to vaporize the liquid phase and to maintain the reservoir fluid to be in a single phase state during the reservoir exploitation. It was seen to be closely related with retrograde dew point pressure and fog up pressures. Therefore, in terms of incorporating colloidal systems into the subject focusing more on the region between fogging up and retrograde condensation gave interesting results.     

硫磺回收装置液硫池废气回收技术及应用

为了节能减排,降低天然气净化厂排放烟气中SO_2质量浓度,利用中压蒸汽作为动力,通过抽射器将液硫池废气抽入克劳斯炉,并通过低压蒸汽对废气进行预热,防止硫蒸气冷凝。研究了克劳斯系统在不同负荷下,液硫池废气进入克劳斯炉后,对降低排放烟气中SO_2质量浓度的影响。通过技术改造的实施应用,达到降低排放烟气中SO_2质量浓度的目的,同时对联合装置平稳生产未产生影响,为同类硫磺回收工艺装置降低SO_2排放提供了参考。     

高含硫气藏气-固两相多组分数值模型

高含硫气藏属于一类特殊高危性气藏,在开发过程中,伴有元素硫的析出、沉积、气相组成变化和沉积硫堆积在孔隙喉道污染地层等特殊现象。一般气藏数值模型没有考虑这些因素的影响,使得基于一般气藏数值模型的数模软件在模拟中不能反映高含硫气藏的开发特性。因此,文章在综合考虑这些因素的基础上,假设析出的固态硫不随气流运移,建立三维气-固两相多组分数学模型,利用Carman Kozeny沉积伤害模型描述硫沉积对地层孔隙度和渗透率的伤害;使用Roberts所提出的硫溶解关系式描述硫在酸气中溶解度变化;应用IMPES方法将数学模型转换为隐式求解压力、显式求解饱和度的数值模型。在模型中,元素硫的质量守恒关系是从“组分”角度来分析的,因为元素硫在单一的气相或固相中不满足质量守恒。该模型能反映高含硫气藏中元素硫的沉积、气藏流体组分随开发的变化以及沉积硫对储层的伤害等     

硫磺回收装置液硫池废气回收技术及应用

为了节能减排,降低天然气净化厂排放烟气中SO_2质量浓度,利用中压蒸汽作为动力,通过抽射器将液硫池废气抽入克劳斯炉,并通过低压蒸汽对废气进行预热,防止硫蒸气冷凝。研究了克劳斯系统在不同负荷下,液硫池废气进入克劳斯炉后,对降低排放烟气中SO_2质量浓度的影响。通过技术改造的实施应用,达到降低排放烟气中SO_2质量浓度的目的,同时对联合装置平稳生产未产生影响,为同类硫磺回收工艺装置降低SO_2排放提供了参考。     

硫微粒在多孔介质中运移沉积模型

高含硫气藏开发过程中,伴有元素硫的析出沉积、气相组成变化和沉积的硫堆积在孔隙喉道污染地层等特殊现象,其中硫沉积是影响高含硫气藏开发的重要原因。在分析硫微粒在多孔介质中的运移和滞留的基础上,引入宏观气固流体力学中描述颗粒在气体中运移的流体力学模型,建立了硫微粒在多孔介质中的运移沉积模型。该模型考虑了硫微粒的产生、在气流中的悬浮运移以及在孔隙表面的沉淀、吸附等。     

牙哈凝析气藏二次注气抑制反凝析机理及相态特征

为解决凝析气藏天然气回注率不足,地层压力低于露点压力而出现的反凝析损失等问题,以塔里木盆地牙哈凝析气藏反凝析损失监测井地层流体取样器(MDT)取样为基础,运用高温高压PVT相态实验测试和模拟技术,建立了牙哈凝析气藏二次循环注气抑制反凝析损失机理的相态特征研究方法,对提高牙哈凝析气藏凝析油采出程度的可行性和有效性做出了评价。通过目前地层压力下反凝析油和剩余凝析气体系的实验室再现,分别测定了其色谱组成、相态特征和p-丁相态图;分别针对反凝析油和地层剩余凝析气,开展了注气增溶膨胀实验、多次接触抽提实验和注气抽提实验,对地层剩余平衡凝析气还开展了加注干气传质扩散过程非平衡相态行为实验;分析了二次循环注气抑制反凝析损失、降低其反凝析油饱和度、使凝析油产生相态反转的相行为机理;给出了二次循环注气开发时应尽量使其注气压力高于露点压力的建议,当注入0.82 PV时,凝析油累积采出程度将提高13.55%。该研究成果为牙哈凝析气藏的增产提供了重要技术支撑。     

我国硫磺回收装置排放烟气中SO2达标方案探讨

针对硫磺回收装置烟气中SO_2排放问题,指出烟气中SO_2主要有液硫脱气、加氢还原吸收尾气及其他非共性原因3个来源,提出了根据不同来源分别处理以降低排放烟气中总SO_2质量浓度的对策,形成了天然气研究院硫磺回收及加氢还原吸收尾气升级达标核心技术,主要包括H2S深度脱除溶剂CT8-26、钛基硫磺回收催化剂CT6-8和新型加氢还原吸收尾气水解催化剂CT6-11B,适用于现有带加氢还原尾气处理的硫磺回收装置,特别是具有独立加氢还原溶剂再生的装置,可将硫磺回收及尾气处理装置排放尾气中SO_2质量浓度降至100mg/m3以下,为解决硫磺回收装置尾气达标排放问题提供了新的实施方案。     

硫磺回收装置超低负荷开工运行及应用研究

介绍了广西石化6×104 t/a硫磺回收装置2014年的超低负荷首次开工过程,在酸气量少、只达到设计负荷13%的条件下,通过采用氢气伴烧、控制夹套伴热温度、优化硫冷器操作等多项超低负荷开工措施,实现装置的低负荷顺利开工,解决一期1×104 t/a向二期6×104 t/a硫磺回收装置切换过程的生产难题。     

高含硫裂缝性气藏储层伤害数学模型

在高含硫裂缝性气藏气体开采过程中,地层压力不断降低,导致硫微粒在气相中的溶解度逐渐减小,在达到临界饱和态后从气相中析出,并在储层孔隙及喉道中运移、沉积,导致地层孔隙度和渗透率降低。地层压力的降低导致裂缝逐渐闭合,也会导致地层孔隙度和渗透率的降低,从而影响气井的产能和经济效益,严重时可导致气井停产。针对高含硫裂缝性气藏复杂渗流特征,基于空气动力学气固理论描述硫微粒在多孔介质中的运移和沉积,建立了一个全新的、能够综合描述多孔介质中硫微粒的析出、运移、沉积、堵塞以及应力敏感的高含硫裂缝性气藏储层伤害数学模型,并以L7井为例进行了实例分析。研究结果表明：在定产量生产条件下,硫沉积对气井生产动态的影响主要表现为气井的稳产时间缩短及气井产量在递减期内的递减速度加快。     

Photochemical oxidation of thiophene by O<Subscript>2</Subscript> in an organic two-phase liquid-liquid extraction system

Photochemical oxidation products and the kinetics of thiophene in an n-octane/acetonitrile extraction system using O₂ as an oxidant was studied. The results could be used as a reference for the oxidative desulfurization of gasoline because thiophene is one of the main components containing sulfur in a fluid catalytic cracking (FCC) gasoline. Thiophene dissolved in n-octane was photodecomposed and removed into the water phase at an ambient temperature and atmospheric pressure. A 500-W high-pressure mercury lamp (main wavelength 365 nm, 0.22 kW m⁻²) was used as the light source for irradiation and air was introduced by a gas pump to supply O₂. Thiophene could be photooxidized to SO₄ ²⁻ and CO₂. The desulfurization yield of thiophene in n-octane is 65.2% for a 5-h photoirradiation under the conditions of air flow at 150 m min⁻¹ and V(n-octane): V(acetonitrile) = 1:1. It can be improved to 96.5% by adding 1.5 g L⁻¹ artificial zeolite, which is an absorbent for O₂. Under such conditions, the photooxidation kinetics of thiophene with O₂ is of the first order with an apparent rate constant of 0.6297 h⁻¹ and a half time of 1.10 h. The sulfur content can be depressed from 800 to 28 ppm. The text was submitted by the authors in English.     

HCHO-H2SO4缩合-萃取脱除汽油中噻吩硫化物

 缩合-萃取脱硫是利用 FCC 汽油中的噻吩类硫化物与 HCHO 在 H₂SO₄存在下发生缩合反应,生成的噻吩缩合物被抽提至水相,从而达到脱硫的目的。考察了 HCHO-H₂SO₄体系对 FCC 汽油缩合 萃取脱硫的效果。当 HCHO-H₂SO₄体系中 HCHO 占模拟汽油的体积分数为1.5%、H₂SO₄ (质量分数55%)占模拟汽油的体积分数为10%、反应温度70℃、反应时间60 min 时,缩合 萃取脱硫后模拟汽油的硫质量分数由1163 μg/g 降至139 μg/g,脱硫率为87.96%;但是对硫质量分数为652 μg/g 的 FCC 汽油的脱硫率仅为10.74%;固定 HCHO 与 H₂SO₄的体积比,增加二者的用量有助于提高 FCC 汽油的脱硫率。该体系对硫含量低的 FCC 汽油以及 FCC 重汽油脱硫效果较好,当 HCHO-H₂SO₄占 FCC 汽油的体积分数为40%时,FCC 中汽油硫质量分数由164 μg/g 降至65 μg/g,脱硫率达到60.37%。     

Using gas ducts made of glass-reinforced plastic for drawing off sulfur dioxide

A gas duct for sulfur dioxide in a unit for preparing sulfuric acid is studied under production conditions. A multilayer construction for the gas duct wall is considered and results are provided for examination of the gas duct inner and outer surfaces. Favorable experience is noted for the first year of controlled operation, i.e., the glass-reinforced plastic gas duct retains safety and reliability, and this guarantees a life (up to 19 years) predicted from the results of laboratory tests. __________ Translated from Khimicheskoe i Neftegazovoe Mashinostroenie, No. 6, pp. 48–49, June, 2007.     

天然气凝析液管道射流清管器清管效果分析

对万州天然气净化厂硫磺回收单元的蒸汽与凝结水构成进行了分析,并对蒸汽引射器重新选型以实现蒸汽梯级利用,以及采用凝结水罐排空蒸汽回收、凝结水循环利用、凝结水分压回收、蒸汽疏水阀优化选型以实现凝结水密闭式回收等优化措施作了详细的分析探讨。实施各项优化措施后,每处理1×10^4 m^3原料天然气（H2S质量分数为1%）,综合能耗由1 303.38MJ降为最低约1 188.23MJ,与每处理1×10^4 m^3原料天然气（H2S质量分数为1%）综合能耗为2 010MJ的设计值相比,节能效果明显。