THE GENESIS OF THE ZOHAR GAS AS DEDUCED FROM ITS CHEMICAL AND CARBON ISOTOPE COMPOSITION

The hydrocarbon compositions (C₁/ΣC₁—C₄) = 0.96-0.98) and the carbon isotopes ratios of methane (—51.4 to—52.1%) studied in the Zohar Gas Field indicate that the generations of the gas was associated with an oil-generation process. Thus, gas and heavy oils found in the area could have formed simultaneously within one system.
The carbon isotope composition of the CO₂ is relatively heavy, with δ¹³ CO₂ value ofabout +7% which is probably the original value of the CO₂ generated by biodegradation of the cruded oil.
The dissimilarity in the organochemical characteristics of the Kidod shales, which cap the gas reservoirs and the oils found in the region, as well as the low degree of maturation of the Kidod, shales, negate the accepted hypothesis that these shales are the source rock of the heavy oils and the gas found in the Zohar area. The vitrinite reflectance of the reservoir rocks and of the underlying Jurassic sequences, which is only 0.5%, infers that the gas is not trapped near its site of generation.     

苏北盆地溱潼凹陷草舍油田CO2混相驱技术研究

苏北盆地溱潼凹陷草舍油田泰州组油藏是一个复杂断块油藏,边界断层遮挡性较好,内部小断层则基本不封闭,储层连通性较好。室内实验注入CO₂对泰州组地层原油起到了明显的膨胀降粘作用,满足CO₂混相驱的要求。注气前泰州组油藏水驱井网存在开发层系划分较粗、层间矛盾严重、局部地区井网不完善、平面开采不均衡、纵向油层动用程度差异等问题,注入CO₂后的动态监测表明,注气井吸气剖面得到明显改善,地层达到最小混相压力,原油重质组分被动用,整个区块产量稳定并初步见效。      

PETROGRAPHY AND GEOCHEMISTRY OF SOME JORDANIAN OIL SHALES FROM NORTH JORDAN

Twenty-two "oil shale" samples from north Jordan have been investigated. They are in fact all bituminous limestones, of ages ranging from Uppermost Cretaceous to Paleocene. Major elements, organic matter and trace elements, were determined, together with aspects of mineralogy and petrography. Although macrofossils are rare, trace fossils were encountered. These rocks are postulated to be normal limestones deposited in an oxygenated shallow marine environment. The H₂S/O₂ interface coincided or lay just below the water/sediment interface. The organic matter is indigenous and not related to migrating oil.     

烟道气强化蒸汽驱提高稠油油藏采收率实验

为了搞清烟道气与蒸汽混合注入稠油油藏进一步提高采收率机理,进行了烟道气强化蒸汽驱模拟实验研究。利用PVT装置研究了不同温度、压力条件下,烟道气在原油中的溶解特性及原油物性变化特征,开展了烟道气强化蒸汽驱一维管式驱替实验与三维物理模拟实验。通过一维驱替实验,可确定不同温度条件下烟道气强化蒸汽驱比单纯蒸汽驱的驱油效率增加值,并优选了最佳注入温度;利用三维物理模拟实验,对比了蒸汽驱转烟道气强化蒸汽驱的生产动态变化规律及温度场扩展特征,分析了厚层油藏内热采过程中不同流体组分的分布特征。基于三维物理模拟实验结果,利用数值模拟方法优化设计了厚层稠油油藏水平井热采开发的布井模式。结果表明:高温降黏助驱、CO_2溶解降黏和N_2分压增容是稠油油藏烟道气强化蒸汽驱提高稠油采收率的机理。     

水驱转CO2混相驱渗流机理及传质特征

CO₂混相驱作为三次采油技术一般在注水开发之后实施,其需要考虑水驱后残留在孔隙中的注入水对CO₂混相驱的影响。基于常规PVT多次接触实验,采用带多点取样孔的长填砂管,在不同含水阶段分别开展注气驱替实验和气水交替驱实验,研究多孔介质中可动水参与下的多相多组分渗流规律以及不同含水率对油、气两相组分传质的影响。研究结果表明：在不同含水率下CO₂与原油仍能发生混相,CO₂的注入形成了新的渗流通道,扩大了水驱波及体积。但高含水率对油相和气相间组分传质有一定的抑制作用。此外,不同含水率下转CO₂驱会在储层中形成不同的油、气、水三相渗流和分布特征,从而影响采出程度,而气驱最终采收率主要受注气驱油效率和水驱波及体积共同作用的影响。     

辽河油田杜84块H2S成因探讨

辽河油田杜84块超稠油由蒸汽吞吐转为蒸汽辅助重力泄油（SAGD）开发后,产生了较高浓度的H₂S,导致脱硫设施投入和油气处理成本增加。通过原油、伴生气、地层水和储层矿物地球化学测试分析,H₂S产量与原油含硫量、地层水SO₄2-浓度无明显相关性,而与储层中黄铁矿含量一致性强,黄铁矿中的硫属于生物来源,同位素范围与原油基本一致,起源于原油稠化阶段,大量形成于稠油热采阶段。高温高压热模拟实验表明,注蒸汽热力采油过程中,除含硫有机质热裂解（TDS）和硫酸盐热化学还原反应（TSR）外,黄铁矿氧化分解也是H₂S形成途径之一,当注入低矿化度蒸汽对地层水稀释后,SO₄2-浓度下降,黄铁矿分解是H₂S的主要生成途径,H₂S的生成和分布受控于油藏地质条件、开发方式、开发时间和受热温度。      

重质油藏氮气辅助蒸汽驱注采参数敏感性分析及优化

为明确氮气辅助蒸汽驱中各注采参数对开发效果的影响,并优选最佳注采方案。以JY油田J2区块的11-12井组为例,采用CMG数值模拟软件的STAR热采模块,通过模拟各种氮气辅助蒸汽驱方案,分别评价了注气量、采注比、蒸汽干度、注汽(气)速度及油藏特征参数对最终采收率的影响,并结合正交试验方法对注采参数进行了优化研究,获得了最佳注采方案。结果表明:氮气辅助蒸汽驱过程中氮气注入段塞的体积应小于0.6HCPV,采注比以1.4左右为宜,氮气段塞注入前,蒸汽干度越高越好,而氮气段塞注入后,蒸汽干度控制在50%以上,提高注汽(气)速度以提高采油速度。最优注采参数组合为氮气注入体积0.2HCPV,注入速度为140 m³/d,采注比为1.6。试验井组开展氮气辅助蒸汽驱后单井平均产油量从1.8 m³/d提高至5.9 m³/d,单井平均含水率由97.2%下降至67.8,降水增油效果显著。研究成果为重质油藏开展氮气辅助蒸汽驱提供了参考依据。     

低渗透砂砾岩油藏二氧化碳驱提高采收率

焉耆盆地本布图油田低渗透砂砾岩油藏早期采用注水开发,储集层伤害严重,注水困难,采出程度低,亟需开展转换注驱研究,进一步提高采收率。为确定本布图油田低渗透砂砾岩油藏注CO₂提高采收率的可行性,开展了室内实验研究。结果表明,研究区地层原油膨胀性好,易降黏,易混相;最小混相压力为25 MPa,在目前地层压力下可达到近混相驱,驱油效率较高,具有大幅提高采收率的潜力。利用数值模拟对CO₂驱开发技术进行优化设计,采用五点法井网,连续注气开发,预计提高采收率13.37%,CO₂换油率0.330 t/t,为下一步矿场试验提供了理论依据。     

IMPROVING SANDSTONE MATRIX STIMULATION OF OIL WELLS BY GAS PRECONDITIONING

Experience has shown that for sandstone formations, oil wells respond to matrix acidizing in a different manner as compared to gas wells. For oil wells, the improvement in permeability resulting from the stimulation treatment peaks at a certain acid volume and then drops as the volume of acid injected increases. For gas wells, however, the resulting improvement in permeability is roughly proportional to the volume of acid injected, and is normally better than that obtained with oil wells. It is, therefore, expected that stimulation of oil wells in sandstone formations could be improved by displacing the oil in the zone to be treated with gas. Gas injection prior to acidizing is sought to minimize the formation of emulsions or sludge resulting from reactions between the spent acid products and the oil that otherwise would be contacted. This paper presents the results of an experimental investigation on the effect of gas pre-conditioning of the damaged oil-bearing sand on permeability improvement by matrix acidizing. Experiments were conducted on Berea sandstone cores saturated with 29.2°API crude oil at actual reservoir temperature of 180°F and pressure of 3000 psi. Carbon dioxide and nitrogen were separately used for pre-conditioning prior to stimulation and the results were compared against stimulation without gas pre-conditioning. It was found that with regular stimulation, improvement in permeability peaked at a certain acid volume. With gas (CO₂ or N₂) pre-conditioning, however, continuous improvement in permeability was obtained with increasing the volume of acid injection. Further, using gas pre-conditioning with a small volume of acid (that would otherwise not be sufficient to even recover the original permeability with regular acidizing) resulted in permeability improvements of up to 200% of the original pre-damage permeability. At an acid volume that would just restore the original permeability with regular stimulation, gas pre-conditioning resulted in permeability improvement close to 300% of the original permeability. Pre-conditioning with either CO₂ or N₂ provided superior results compared to regular stimulation. However, CO₂ was found to be more effective than N₂. This is attributed to the fact that CO₂ has better miscibility than N₂ and would, therefore, provide more efficient displacement of the oil out of the zone to be stimulated.     

川东北飞仙关组-长兴组天然气几个地球化学问题探讨

基于川东北地区大普光、元坝和通南巴构造带百余个飞仙关组-长兴组天然气样品的分子和碳同位素组成数据,结合烃源岩和储集岩分析资料,就原油裂解气与烃源岩裂解气的区分、烷烃气碳同位素的反序分布和CO₂与H₂S的成因关系等问题进行了探讨。研究结果表明,大普光、元坝区块富含固体沥青的孔洞型气藏的原油裂解气中,丙烷相对较多,以较低的ln（C₂/C₃）值（<3.0）为识别标志。而通南巴等区块裂缝型气藏的烃源岩裂解气（可溶沥青和干酪根的高温裂解气）,具有ln（C₁/C₂）和ln（C₂/C₃）同步升高的组成特征,以较高的ln（C₂/C₃）值（>3.0）与典型的古油藏原油裂解气相区别。各构造带的飞仙关组-长兴组烷烃气存在碳同位素反序分布,可能有多种原因。其中,通南巴构造带河坝场气田飞仙关组烷烃气中的该现象,是由于龙潭组过成熟干气混入志留系气源气所致。飞仙关组-长兴组发生过TSR（硫酸盐热化学还原反应）作用的天然气中,多呈高CO₂、低H₂S和低CO₂、高H₂S两种分布模式,两种非烃气的相对含量受气藏流体-岩石相互作用体系的控制。在高含H₂S的气藏中,CO₂主要来源于烃类的氧化,并经流体-岩石交换作用,其δ¹³C值相对较负;而在CO₂异常丰富的天然气中,CO₂主要由碳酸盐岩的化学分解而来,δ¹³C较重。     

柴达木盆地北缘块断带原油的地化特征及油源问题

柴达木盆地北缘断层纵横交错,控制着本区的构造格局和中新生界地层的岩性和厚度,故称北缘块断带。其范围西起昆特依凹陷,东至旺尕秀地区,北界阿尔金山—祁连山山前断裂带,南邻葫芦山、埃姆尼克山一线,面积约三万平方公里(图1)。      

高含水油藏CO_2驱油机理

CO_2驱油能够有效提高原油采收率,但在高含水油藏中,水能够溶解CO_2,并影响CO_2与原油接触,从而影响驱油效果。针对这一问题,开展了CO_2在油、水中的浓度分配实验,通过建立CO_2在油、水中扩散的数学模型,使用核磁共振研究CO_2驱替实验,探索了CO_2在高含水油藏中的溶解扩散机理以及对综合驱油效果的影响。结果表明,在高含水油藏中,CO_2在水中溶解损失的比例不高,同时CO_2能够快速渗透水膜,与被水屏蔽的剩余油接触,波及水驱未波及区域内的剩余油。由于水膜阻隔了原油与CO_2的直接接触,在CO_2驱替过程中会首先驱出水膜,使油、气直接接触,再驱出剩余油。其宏观表现为注气早期含水率较高、采油速度较低,当CO_2突破后,含水率急剧下降,采油速度升高。研究明确了高含水油藏CO_2驱油机理,解释了其见效特征,并为改善高含水油藏CO_2驱油效果提供了参考。     

THERMAL DECOMPOSITION OF SAUDI CRUDE OIL ASPHALTENES

Asphaltenes precipitated by the use of pentane, heptane and decane solvents from Saudi Arabian Light (AL) and Saudi Arabian Heavy (AH) crude oils 370^°C + residua have been investigated by thermal gravimetric analysis and pyrolysis - gas chromatographic analysis at 350^°C and 520^°C. Gas chromatographic analysis of the gases evolved during pyrolysis has shown that CO, CO₂ and CH₄ constitute the major portion of the gases evolved at 350^°C from pentane and heptane asphaltenes of AH residue and from pentane asphaltenes of AL residue. Whereas gases evolved from decane asphaltenes are dominated by CO₂ and C₂-C₄ hydrocarbon gases. At 520^°C, hydrogen and methane represent 56-80 vol %of the gases evolved from all the four asphaltenes. The amounts of C₁-C₄ hydrocarbon gases increased with an increase in the carbon number of the precipitating solvent at 350^°C and decreased at 520^°C. The presence of up to C₃₆ normal alkane hydrocarbon has been indicated in the maltenes produced from these asphaltenes. The loss of nitrogen from AH asphaltenes during pyrolysis remained low (1-6 wt %), whereas the losses of oxygen and sulphur ranged from 58 to 74 wt % and 10 to 29 wt %, respectively.     

AQUEOUS SOLUBILITY OF CRUDE OIL TO 400°C AND 2,000 BARS PRESSURE IN THE PRESENCE OF GAS*

This study reports aqueous solubilities of crude oil distillation fractions over the carbon number range C₁- C ₃₄ as a function of: temperature (100° to 400° C), pressure (100 to 2,000 bars), NaCl concentration, and gas in solution (N ₂, CO ₂, CH ₄). Experimental parameters were designed so that conditions within a petroleum basin would be duplicated. Increases in temperature increased crude oil solubility, and the higher molecular weight species were affected more positively than lower molecular weight species. Increases in pressure or salinity decreased solubility. The presence of gas in solution increased the solubility of high molecular weight hydrocarbons (> C ₂₄) over all temperatures, and increased the solubility of lower molecular weight hydrocarbons at high temperatures (> 180–260°C). Gas decreased the solubility of low molecular weight hydrocarbons at low temperatures.
Hydrocarbon solute compositional changes were also examined as a function of the above parameters. At high temperatures, both increasing gas concentration and increasing temperature caused hydrocarbon solutes to become compositionally more similar and eventually identical to the original distillation fraction. The high molecular weight hydrocarbons and saturated hydrocarbons, especially the n-paraffins, were taken into solution in progressively greater concentrations over the aromatic and low molecular weight hydrocarbons. Thus, the strong preferential uptake of low molecular weight and aromatic hydrocarbons into solution at lower temperatures was reversed.     

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膨胀试验作为单井吞吐工艺试验的重要评价手段之一,在油田注ＣＯ２混相驱试验中已得到应用,然而关于注气后原油物性参数的变化规律虽然已作了些研究,但目前还不是很清楚。文章在ＣＯ２注气膨胀实验的Ｐ－Ｘ图,膨胀系数和原始相态参数进行拟合后,计算出注气后原油的密度、分子量、泡点处气液相偏差因子和界面张力、原油粘度等的变化规律,同时研究了ＰＶ关系和多级脱气的主要特征变化规律。     

酸气回注技术发展现状及其在中国的应用前景

零排放的酸气回注技术是一种替代硫磺回收工艺的经济可行的酸气处理方法,同时也是一个减少温室气体排放的环保方法。为此,总结了酸气回注技术的发展和应用现状,结合实例对酸气回注和硫磺回收进行了经济技术和环保对比分析,结果表明：酸气回注方案的硫处理费用为1 270美元/t;而硫磺回收的硫处理费用为1 400美元/t,若进一步考虑CO₂排放、硫磺销售等因素,其综合处理费用将超过1 779美元/t。同时,分析了酸气回注在中国的应用需求及条件,展望了该技术在中国的应用前景,指出在下述几种情况下,为了取得最好的经济和环保效益,酸气回注会是一个不错的选择：①老气田气质变化后,硫磺回收装置已不适应生产需要而需改造;②新开发气田太偏远或H₂S含量太低,硫磺回收不经济或工艺技术不好解决;③部分新开发气田的天然气组成不稳定,进行硫磺回收投资大、风险高;④部分碳酸盐岩开发油田伴生气含H₂S,但含量变化大,进行硫磺回收工艺选择难度大;⑤火驱开发油田和采用蒸汽辅助重力泄油开发的稠油油田,其伴生气中H₂S含量大,但气量小,回收不经济;⑥低渗透油田用CO₂提高采收率等。     

CHANGE OF PHYSICAL AND THERMAL DECOMPOSITION PROPERTIES OF IN SITU HEAVY OIL WITH STEAM TEMPERATURE

Ikiztepe crude oil was subjected to four different steam temperatures during steam injection which was applied as an enhanced oil recovery process on a linear limestone model saturated with oil. Produced oils were characterized using density, viscosity measurements, pyrolysis experiments utilizing TGA and elemental analysis runs. Results showed that produced crude oils change in measured characteristics as compared to the original oil. These changes include an increase in H/C, and cracking activation energy, decrease in density, viscosity and amount of residue remaining after cracking (coke). Also, decrease in asphaltene amount, changes in the elemental composition of asphaltenes and increase in the cracking activation energies were observed at 225 °C run. These measurements show that the produced oils get lighter and differ compositionally from the original oil as steam temperature increases. Decrease in elemental sulphur amount is one of the major changes when environmental considerations are concerned. Residual oil left in the limestone pack on the other hand shows an increase in the low temperature oxidation (LTO), fuel deposition (FD) and high temperature oxidation (HTO) activation energies as determined from TGA combustion experiments on the samples taken from the pack after steam injection experiments.     

注气对固溶物沉淀影响的研究与应用

注气采油是提高原油采收率的主要方式之一,在此过程中准确描述含有沥青质等高分子有机固相物质的油气体系相平衡十分必要。为此,将沉淀的沥青质视为固相,假设标准状态下必须有沥青质沉淀,将标准状态压力和温度引入沥青质固相逸度计算,并同时考虑了标准状态压力和温度对沥青质固相逸度的影响,建立了能模拟沥青质沉淀的气、液、固三相相平衡热力学模型。据该模型计算的结果表明:①能通过比较液相沥青质逸度和固相沥青质逸度大小来判断固相沥青质沉淀的出现。②当注入某油的气体为烃类混合气体时,烃类混合气体的添加使得含沥青质原油的组分发生变化;温度相同时,注气浓度越高,沉淀的压力越大;浓度相同时,温度越低,沉淀的压力越大;当沉淀量一定时,随着注气浓度增加,油品的饱和压力随之增大;相同注气浓度下,当压力高于饱和压力时,随着压力增大,沉淀量减少。③在温度不变的情况下,注入某油的气体为CO2时,其沥青质沉淀量是注CO2浓度的函数且随着CO2浓度的增加,固相(沥青质)的沉淀量不断增大。④在注气驱油过程中,气体的注入极易引发含沥青质原油中沥青质等重质有机物的沉积。     

油藏CO2驱过程中最小混相压力的动态变化及其影响因素分析

为了进一步研究CO₂驱过程中最小混相压力(MMP)的动态变化,为油气CO₂驱产出伴生气回注提供理论依据,针对吉林油田CO₂驱示范区的油藏工况,利用经验模型法和PVT方法分析计算MMP,进行了CO₂驱过程中油气组分及MMP变化的动态分析,研究了MMP的变化规律及其影响因素。结果表明,2种方法所得MMP差值为4%～8%,与实验值的误差为5.36%。在油藏CO₂驱生产过程中,由于CO₂的抽提作用使原油中的中轻质组分(C₂～C₆)减少,导致MMP增大。注入气的组分对MMP也有较大影响,纯CO₂中加入C₂H₆等轻质组分会降低MMP。CO₂驱油藏产出气中含有CO₂,CH₄和(C₂～C₄)等轻质组分,可以将其与纯CO₂混合后回注,当...     

不同硫酸盐引发的热化学还原作用对原油裂解气生成的影响

由于反应途径或机制不同于裂解反应,硫酸盐热化学还原作用(TSR)很可能会改变油藏中原油的热稳定性和裂解气产量。为了阐明TSR作用对原油裂解气生成的影响,利用黄金管热模拟装置开展了一系列不同硫酸盐和原油的升温热解实验。非烃气体,包括H₂S的大量生成表明,石膏和硫酸镁的加入引发了原油的TSR反应,其中,石膏参与的TSR作用对烃类气体的产量和生成活化能无明显影响;相对而言,硫酸镁参与的TSR反应引起了最终甲烷产量约13.1% 的降低和大分子气态烃(C₂₊)稳定性的明显降低;氯化镁的加入导致了硫酸镁体系中H₂S产量进一步的增加和烃类气体产量进一步的降低。可以证实,在硫酸镁热解体系中,C₂₊与活性结构HSO₄^-发生了氧化还原反应,这也是导致烃类气体产量降低的重要原因。因此,TSR作用对裂解气生成的影响很大程度上受控于地层水中的硫酸盐类型和活性结构的浓度。