鄂尔多斯盆地中东部奥陶系马家沟组米探1井天然气成因与来源

鄂尔多斯盆地中东部米探1井在奥陶系马家沟组四段钻获高产工业气流,实现了奥陶系盐下天然气勘探的重大突破,但目前对其成因来源存在争议。实测结果表明,米探1井天然气以烷烃气为主(95.18%),气体干燥系数(C₁/C_1-5)为0.947,非烃气体中H₂S含量为3.49%,还有少量的N₂和CO₂。天然气中甲烷、乙烷、丙烷的碳同位素值分别为-45.5‰、-26.4‰、-24.3‰。基于区域地质背景、潜在烃源岩特征和天然气地球化学特征,认为米探1井天然气为奥陶系盐下碳酸盐岩自生自储的油型气,但其存在甲烷碳同位素组成偏轻和乙烷碳同位素组成具有煤型气特征等地球化学异常。结合生烃热模拟实验和岩石残余气特征认为米探1井特殊的地球化学特征与普遍存在的膏岩关系密切：一方面,普遍存在的膏岩提供了良好的盖层使得很多早期生成的天然气得以留存;另一方面,膏岩的存在促进了H₂S和乙烷等重烃类气体的生成。此外,小于5%的H₂S含量和较高的重烃气体(C₂₊     

CO2、H2S对3Cr钢静态腐蚀的影响

为了研究3Cr钢在不同CO₂、H₂S腐蚀介质中耐蚀性，对3Cr钢分别在1 MPa CO₂、0.3 MPa H₂S及1 MPa CO₂+0.3 MPa H₂S腐蚀环境中的腐蚀速率和电化学性能进行测试，同时采用SEM、EDS和XRD等手段对上述三种腐蚀环境中的腐蚀产物进行分析对比。结果表明，3Cr钢在1 MPa CO₂环境下腐蚀速率最大，通过对腐蚀产物进行分析，发现其表面未形成连续分布且具有致密性腐蚀产物保护膜是其腐蚀速率高的主要原因。电化学测试发现3Cr钢EIS阻抗在1 MPa CO₂中呈现单容抗弧，而在0.3 MPa H₂S和1 MPa CO₂+0.3 MPa H₂S环境中呈现双容抗弧，进一步印证了其在1 MPa CO₂环境中耐蚀性较差的结果。     

TSR对气态烃组分及碳同位素组成的影响——高温高压模拟实验的证据

选用高含硫原油、Ⅱ型干酪根、Ⅲ型干酪根以及硫酸镁作为反应物,设计了3组共6个反应体系,以对比发生硫酸盐热还原作用(TSR)与否对烃类组分及碳同位素的影响。模拟实验利用黄金管—高压釜限定系统完成,6个反应体系具有完全相同的反应温度和压力,反应结果具有可对比性。模拟实验结果证实:①TSR反应导致气态产物中H₂S和CO₂含量的明显增加;②TSR反应导致气态天然气组分变干,即碳数越多的气态烃越容易发生TSR反应,甲烷很难作为反应物参与TSR反应;③TSR反应导致气态烃碳同位素变重,而CO₂碳同位素变轻;④TSR导致甲烷碳同位素变重最多,乙烷、丙烷碳同位素变重相对较小,即δ13C₂与δ13C₁差值变小。TSR反应导致的天然气组分及碳同位素的变化影响了油气源对比的经验公式及判断指标,因此在高含硫天然气区进行气源对比时应考虑TSR的影响。      

南海北部二氧化碳对天然气水合物形成与分布的影响

南海北部天然气富含CO₂等非烃气体,非烃气体对于水合物既有建设性,也有破坏性。含CO₂的天然气向上运移渗漏到浅层,条件适当时,CO₂可作为碳源,被还原成CH₄,在浅层形成水合物成藏。选取南海北部的几组不同CO₂、N₂含量的气体组分进行的实验表明,含CO₂的天然气形成水合物的温度比纯甲烷水合物要高,致使水合物的赋存深度增加,从而拓展了水合物稳定带的厚度。高含CO₂的天然气藏发生强渗漏并运移至上覆甲烷水合物层时,CO₂可能会置换甲烷水合物中的甲烷,使原有的水合物矿藏遭受破坏或甲烷饱和度下降。      

南盘江盆地秧1井天然气地球化学特征及成因分析

经测试,南盘江盆地秧1井天然气可分为2类:一类为高含N₂天然气,N₂含量为54.92%~73.89%;另一类为高含CO₂天然气,CO₂含量大于96%。认为高N₂天然气是秧1井乃至南盘江地区具有地质意义的天然气。指出该类天然气甲烷含量一般小于2.5%,几乎不含大于乙烷的烃类组分,CO₂含量2.2 7%~9.5 4%;1δ3C1值为-3 3.1 9‰~-3 3.9‰,CO2的1δ3C值为-2 9.3‰~-30.93‰。认为该类天然气不是原油裂解气,也不是源自上二叠统龙潭组的煤成气,而主要是源自中泥盆统泥质烃源岩的干酪根裂解气;中泥盆统泥质烃源岩的“晚期阶段聚气”是造成该地区天然气高含N₂、烃类组分碳同位素偏重的主要原因。     

奈曼凹陷九佛堂组非烃流体地质意义及控制因素

奈曼凹陷的非烃流体主要指 CO₂,H₂S 和 N₂。 通过伴生气组分分析,结合区域构造发育史、非烃流体含量及碳同位素分析资料,对奈曼凹陷非烃流体成因、进入油藏时间、保存及分布的控制因素进行了深入探讨。研究认为：奈曼凹陷 CO₂ 和 H₂S 均来自幔源成因岩浆喷发,先于烃类进入储层;CO₂ 的富集程度与地层水中的 HCO₃^- 浓度呈正比;H₂S 性质不稳定,目前以痕量 H₂S、含硫有机化合物及黄铁矿结核的形式存在,H₂S 和含硫有机化合物的富集程度与 SO₄^2- 浓度呈正比;N₂ 来自大气成因,燕山晚期进入储层,浅部地层及浅层断裂附近 N₂ 富集。 砂体的展布特征控制非烃流体的平面展布规律,泥岩厚度及泥岩与砂岩的配置关系控制非烃流体的保存条件。该研究成果为奈曼凹陷下一步油气勘探部署提供了一定的理论依据。     

三水盆地气态烃的地球化学特征和成因

本文根据三水盆地天然气的组分和碳、氢同位素特征,探讨了气态烃的成因。下第三系(土布)心组含500多米的生油岩,干酪根以Ⅱ型为主。富烃天然气含不等量的 N₂、He、CO₂,不含 H₂S;干湿指数变化范围为2.1-196;iC₄/nC₄值为0.42-0.87;δ¹³C₁和δD₁值分别为-61.0至-44.6‰和-237至-174‰,δ¹³C₂值在-33.4‰到-30.2‰之间。烃类气体属热解成因的油型气与次生生物成因气。     

酸性气井关井后重组分沉降对井筒组分变化的影响

目前经典的井筒稳态多相流流动模型没有考虑关井后重组分沉降作用,可能导致井筒压力-温度预测不准。针对酸性气井井筒复杂流动特征,基于热动力学平衡原理和热扩散理论,考虑酸性气井关井后H₂S及CO₂重组分在重力、化学势变化以及热扩散作用下向下沉降,建立了重组分沉降过程中组分梯度方程和扩散模型,模拟计算了井筒压力分布和组分变化。研究表明：关井后井筒中H₂S和CO₂重组分沉降导致流体密度、H₂S、CO₂摩尔浓度从井口到井底逐渐增大,而C₁、C₂组分含量逐渐减少。实例井5 000 m井深井口样和井底样H₂S含量差别近10%,建议酸性气井流样分析宜采用井底样。这也解释了为什么酸性气井井底一般腐蚀更为严重。     

惰性及特种可燃气体对甲烷爆炸特性的影响实验及分析

天然气开采和集输过程中的防爆问题一直是安全控制的重点,常见的特种可燃气体（H₂、H₂S和CO）及惰性气体（CO₂和N₂）对天然气的爆炸特性有很大影响。为此,通过实验和理论模型,分析了惰性气体和特种可燃气体对CH4爆炸特性的影响规律。结果表明：①随着惰性气体含量的增加,CH₄爆炸极限范围变窄,爆炸的临界氧含量值增大,爆炸的危险性降低,其中CO₂比N₂具有更好的爆炸抑制效果;②随着特种可燃气体含量的增多,混合可燃气的爆炸极限会向所添加特种气体的爆炸上下限逼近,明显扩大了CH₄的爆炸极限范围,降低了发生爆炸的临界氧含量,增加了爆炸风险;③在有惰性气体存在的条件下,温度、压力的上升也会增加CH₄的爆炸风险。该研究成果可应用于气田、煤田开发和天然气集输过程中的防爆工艺,预防和降低天然气爆炸风险,保证安全生产。     

我国高含H2S/CO2气藏安全高效钻采的关键问题

我国高含H₂S/CO₂气藏天然气探明地质储量已经超过5000×10⁸m³，由于国内在高含H₂S/CO₂天然气藏钻探与开采方面缺乏系统的理论和成熟的工程技术，经常遇到系统失稳、压力失控、硫堵塞、工具失效及测试失败等棘手问题，不仅造成了巨大的直接经济损失，而且还严重制约了这类天然气藏的勘探开发与产能建设。为此，系统阐述了高含H₂S/CO₂气藏安全高效钻采的若干关键问题，包括：高含H₂S/CO₂气藏流体相态特征与渗流规律、元素硫积机理与防治、天然气水合物形成与防治、基于超临界流体相态与压力传递规律的井控及预报、高含H₂S/CO₂气藏安全开发模式等，以期为这类气藏的安全、高效生产提供帮助。     

Increase in gas separation selectivity during physical aging of OH-containing polyimide

Gas transport characteristics of new polyimide (PI) containing hydroxyl groups in the diamine moiety for seven permanent gases have been investigated: H₂, He, O₂, N₂, CO, CO₂, and CH₄. Changes in the gas separation properties of polyimide during its physical aging over a year have been experimentally revealed. It has been shown that a slow decrease in the permeability coefficients of H₂, He, and O₂ in the polyimide physical aging process and a sharp decrease in those of N₂, CO, CO₂, and CH₄ lead to an exponential increase in the selectivity of gas separation and a displacement of values in the permeability-selectivity plot beyond the upper limit in the case of the O₂/N₂ gas pair.     

The Effects of Multi-component Thermal Fluids on the Viscosity of Offshore Heavy Oil

Multi-component thermal fluids stimulation is a feasible way to recover offshore heavy oil reservoir. As a new technology, its mechanism of enhanced oil recovery should be understood through systematic simulation experiments and quantitative analysis. Laboratory experiments were carried out to investigate the effects of temperature, natural gas, and various gases (N₂, CO₂, or N₂+CO₂) on the viscosity of heavy oil from Nanbao block of Bohai offshore oilfield. The results show that in the range of 56°C (reservoir temperature) to 120°C, natural gas saturated and degassed oils are all very sensitive to temperature, and the viscosity is reduced by more than 90% when heated to 120°C; under lower temperature condition, injection of 5MPa N₂, N₂+CO₂, or CO₂ can significantly reduce the viscosity of natural gas saturated heavy oil, with a viscosity reduction ratio of about 20%, 50%, and 80%, respectively, at 56°C. Therefore, heavy oil production by viscosity reduction can be achieved by raising temperature or through gas injection. Taking into account the equipment, heat loss, and cost of steam injection, the technology of moderate heating, auxiliary gas injection is very promising for the recovery of Nanbao heavy oil.     

An inverse solution methodology for estimating the diffusion coefficient of gases in Athabasca bitumen from pressure-decay data

An inverse solution methodology is developed for the estimation of diffusion coefficient of gases in highly viscous, oil-sands bitumens from isothermal, pressure-decay measurements. The approach involves modeling the rate of change in pressure using the diffusion equation for the liquid phase coupled with a mass balance equation for the gas phase. The inverse solution framework is utilized to arrive at two graphical techniques for estimating the diffusion coefficient. Both techniques involve the determination of the slope of a straight line resulting from plotting the experimental data in accordance with the developed model. An advantage of the proposed techniques is that the diffusion coefficient is estimated directly, i.e. without making it an adjustable parameter. The novelty of the proposed method is in its simplicity as well as its ability to isolate portions of the pressure-decay data affected by experimental fluctuations. The effect of the initial pressure on the predicted diffusion coefficient and pressure-decay profile was also investigated. The diffusion coefficients of CO₂, CH₄, C₂H₆ and N₂ in Athabasca bitumen at 50–90 °C and about 8 MPa were estimated and compared with literature values.     

Gas separation characteristics of new membrane materials based on poly(ethylene glycol)-crosslinked polymers and ionic liquids

Gas transport characteristics (permeability and diffusion and solubility coefficients for CO₂, O₂, N₂, H₂) of new crosslinked membrane materials synthesized by copolymerization of poly(ethylene glycol) dimethacrylate and poly(ethylene glycol) methyl ether methacrylate in the presence of various ionic liquids have been studied. Comparison of the characteristics of specimens with and without ionic liquids has revealed that the presence of ionic liquids enhances the permeability of the membranes, especially to CO₂. It has been shown that the enhancement of the CO₂ permeability of films incorporating ionic liquid is due to an increase in CO₂ solubility and the increase in selectivity for pairs of gases containing CO₂ is determined by thermodynamic selectivity of separation.     

Synthesis and gas transport properties of polypentafluorostyrene

Polypentafluorostyrene (PPFS) (M _w = 1.7 × 10⁵ Da, M _w /M _n = 1.6, and Т _g = 110°С) has been synthesized by radical polymerization of pentafluorostyrene. The chemical structure of the polymer has been confirmed by ¹H and ¹⁹F NMR data. The permeability and diffusion coefficients of gases (He, H₂, O₂, N₂, CO₂, and CH₄) have been measured on a barometric setup. The permeability, diffusion, and solubility coefficients of gases have been shown to increase with the increases in the fluorine content in the repeat unit of the polymer in the polystyrene–poly(p-fluorostyrene)–PPFS series. Such behavior of transport parameters in the polymer series is associated with the growth in the fractional free volume and decrease in the cohesive energy density. The investigated polymers on the basis of styrene and its derivatives including PPFS are located in the middle of clouds of Robeson diagrams for N₂/CH₄, CO₂/CH₄, and O₂/N₂ and are not of interest for their separation.     

EFFECTS OF SUPPORTS ON THE ACTIVITY OF NICKEL CATALYST FOR CH4 REFORMING WITH CO2

ABSTRACT

Nickel catalyst is an effective catalyst for reforming CH₄ with CO₂. The reaction between CO₂ and CH₄ at 1073 K. in the pressure of 0·1 MPa has been studied over different materials supported nickel metal in a fixed-bed reactor. Different catalysts before and after reaction were characterized by SEM, XRD, XPS. Results shows that CO and H₂ are basically produced at the same ratio. When the feed ratio CO₂/CH₄ is less than 0·5, less C₂?C₄ hydrocarbons are detected. When the feed ratio CO₂/CH₄ is 1, Ni/a- Al₂O₃ catalyst has the highest activity. However, when the feed ratio CO₂/CH₄ is greater than 1, Ni/y- A1/O₃, Ni/a- A1₂O₃, Ni/SiO₂ and Ni/HZSM-5 had higher activity; Ni/clinoptilolite basically no activity. Different kinds of carbon deposit are established.     

An investigation of different gas injection scenarios as enhanced condensate recovery method in a naturally fractured gas-condensate reservoir

In gas condensate reservoirs, when the bottom hole pressure falls below the dew point pressure condensates are formed. This causes hydrocarbon liquid saturation around the well bore region. This phenomenon is called condensate blockage or condensate banking. Condensate recovery reduction due to condensate banking near the well bore region is an important problem in gas condensate reservoirs. The common method to prevent the condensate banking is gas cycling (reinjection of produced dry gas) into the reservoir that can contribute to the condensate vaporization, thus increasing the condensate recovery factor. The objective of this study was to find a suitable replacement for gas cycling. For this purpose, an investigation on the effects of injection of different types of gases (CO₂, N₂, and C₁) on enhance condensate recovery factor and pressure maintenance were performed. This research was done on one of the Iranian gas condensate reservoirs through a compositional simulator. The two-parameter Peng-Robinson equation of state (EOS) and Lohrenz-Bray-Clark correlation were used to model reservoir fluid properties through regression on the pressure-volume-temperature (PVT) experimental data. A fracture network was distributed over the reservoir, so a dual porosity/dual permeability model was selected for better evaluation of the fracture system. Then, various scenarios of natural depletion and CO₂, N₂, C₁, and gas cycling injection were studied. The results showed that CO₂ injection scenario being associated with the highest efficiency compared to that of other gases.     

基于CPA状态方程的高压含硫天然气压缩因子计算方法研究

对于压力高于70 MPa的含H_2S天然气,其分子之间间距缩小,极性H_2S分子之间缔合作用增强,传统SRK、PR状态方程计算高压含硫天然气的压缩因子准确性有待进一步改进。基于压力3.72～97.58 MPa、H_2S体积分数0%～70.03%的154组压缩因子修正CPA(Cubic-Plus-Association)状态方程中H_2S与CH_4、CO_2分子间二元交互作用系数,综合评价SRK、PR、CPA状态方程对压缩因子的计算精度。结果表明,对于中低压含硫天然气(p35 MPa),采用PR方程精度最高,平均相对偏差为1.12%;对于高压及超高压含硫天然气(p35 MPa),CPA方程精度最高,平均相对偏差为-1.46%。进一步采用法国ST抗硫高压PVT仪测试了4种含硫天然气在70～131 MPa条件下的138组压缩因子实测值,验证了采用CPA状态方程对于高压含硫天然气压缩因子的计算精度。     

AN EXPERIMENTAL STUDY OF THE EFFECT OF PARAFFINIC SOLVENTS ON THE ONSET AND BULK PRECIPITATION OF ASPHALTENES

ABSTRACT

Asphaltene onset concentration and bulk deposition were measured for a typical live reservoir oil titrated with n-C₆H₁₄, n-C₅H₁₂, n-C₄H₁₀, C₃H₈, C₂H₆, CH₄ and CO₂ at 100° C (212 ° F) and 29.9 MPa (4340 psia). The concentration of titrant at asphaltene onset was observed to decrease approximately in a linear fashion with decreasing molecular weight of the paraffinic solvent; CH₄ did not induce any asphaltene precipitation. Bulk deposition experiments were performed using a solvent: oil volume ratio of 10:1; the results indicated that the weight percent of asphaltenes precipitated increased exponentially with decreasing molecular weight of the paraffinic solvents. More importantly, the asphaltene molecular weight showed a maximum for n-C₄H₁₀ precipitated asphaltenes. Possible explanations for this unusual result are presented.     

CH4/N2在Zr-MOFs上的吸附分离研究

以H_4L为配体,与金属离子Zr~(4+)自组装得到棒状晶体Zr基金属有机框架材料(ZrMOFs),并借助X射线单晶衍射、N_2吸附脱附、X射线粉末衍射、热重等对其结构进行表征,利用气体吸附仪测量了CH_4和N_2的吸附等温线,采用克-克(Clausius-Clapeyron)方程计算CH_4的吸附热,并运用Ideal Adsorbed Solution Theory(IAST)理论来计算CH_4/N_2的分离因子(SCH_4/N_2)。结果表明:在273K、0.1MPa时,晶体Zr-MOFs对CH_4有较好的吸附效果,吸附量为8.2cm3/g,对CH_4/N_2的选择性分离因子(S)为6.3,且具有较好的分离效果;对吸附热力学的研究表明,CH_4的吸附热在20kJ/mol左右,相对分子筛类吸附剂吸附热较小,易于吸附剂的再生。