PRIMARY PETROLEUM MIGRATION BY MOLECULAR SOLUTION: CONSIDERATION OF NEW DATA

Previous criticisms of primary petroleum migration by molecular solution have been: (1) the large compositional and molecular weight differences between hydrocarbons most readily dissolved in water and those found in crude oils, and (2) previously-measured aqueous petroleum solubilities were not high enough to account for petroleum deposits using reasonable geologic assumptions. New crude oil aqueous solubility data remove both of these criticisms. Above 275° C, with both increasing gas content and temperature, the solute hydrocarbons become compositionally more and more similar to, and eventually exactly match, the starting material. Mass balance calculations, using experimentally-measured crude oil solubilities, show that between 275° and 375° C, under realistic geologic assumptions, crude oil aqueous solubility is high enough to account for petroleum deposits. These new data also show that molecular solution is not a viable agent of primary petroleum migration below 275° C.
Although the new data remove these two criticisms, three others are immediately raised: (1) there is inadequate water in sediments at temperatures between 275° to 375° C for migration by molecular solution, (2) sediment hydrocarbons will be thermally destroyed by these temperatures, and (3) these high temperatures are not present in most petroleum basins. Consideration of existing data suggests these criticisms can be satisfactorily answered. It is therefore concluded that a deep-hot origin of petroleum and its migration by solution could fall within the restraints of the natural system.
It is possible much or most of the world's oil has undergone primary migration by molecular solution; however two other mechanisms may also be viable: gaseous solution, and in the case of extremely rich source rocks, some form of a bulk phase migration.     

GAS EVOLUTION AND CHANGE OF OIL COMPOSITION DURING STEAM FLOODING OF OIL RESERVOIRS

The injection of steam into oil reservoirs is a technique commonly used for improving the production of heavy crude oils. Very often, a change in the composition of the oil and gas produced may be observed during steam flooding. In general, corrosive gases, such as H₂S and CO₂, are produced in increased quantities.
In laboratory experiments on sulphur-bearing reservoir minerals and crude oils the origin of the change in oil and gas composition was investigated. Temperatures up to 370°C were applied to study temperature- and rate-dependent phenomena. By means of X-ray fluorescence, gas chromatography and chemical precipitation methods, the change in the sulphur material balance was studied.
It was shown that gas evolution depends strongly on the temperature of the steam injected. Furthermore, it was possible to prove that the gases evolved during steam flooding (such as CO₂, H₂S etc.) originate from the decomposition of crude oil components. Besides these investigations, a drastic viscosity increase of the residual crude oil was observed after steam injection was applied.
It is concluded that the production of H₂S and CO₂ may be controlled by temperature adjustment of the steam being injected.     

DETERMINATION OF THE TEMPERATURE HISTORY FOR THE U THONG OILFIELD AREA (SUPHAN BURI BASIN, CENTRAL THAILAND) USING A REALISTIC SURFACE TEMPERATURE

The temperature history for the BPI-W2 well in the oil-producing Suphan Buri Basin, central Thailand, has been investigated using different surface temperatures (T_s). Two ID models using T_s values of 0°C and ∼22°C were able to fit the suppression-corrected vitrinite reflectance (VR) values and burial peak temperatures (T_peak) in the well. The geothermal gradient averaged over 3 km is ∼54°C/km for T_s= 0°C, whereas it is ∼42°C/km for T_s∼22°C. T_s= 0°C is, however, considered to be unrealistic and the ∼54°C/km gradient is therefore too high. Similarly, a previously determined geothermal gradient of 62°C/km is considered to be an overestimate. The geothermal gradient of ∼42°C/km is plausible compared to other geothermal gradients onshore and offshore Thailand, although it is at the low end. This may be due to a too low suppression correction for the measured VR values. The obtained temperature history can be used to predict measured present-day temperatures of T_s∼22°C and 77°C in the reservoir in the U Thong oilfield. The obtained temperature history associated with the geothermal gradient of ∼42°C/km seems realistic as it predicts that the onset of oil generation at 107°C will have post-dated reservoir and trap formation in Middle to Late Miocene times.     

OCCURRENCE AND DISTRIBUTION OF n-ALKANESAND n-FATTY ACIDS IN SAUDI ARABIAN CRUDE OILS

Ten crude oil samples, covering wide range of maturity (API gravity = 18·5-36·1), were assembled from Safaniya, Abqiq, Ain Dar, Wafra. Marjan and Zuluf oil fields in the area of Arabian Gulf. n-Alkanes of were separated from the petroleum distillate ((150°C-450°C) of the crude oils by urea adduction. n-Fatty acids were separated from the fraction of n-alkanes by treatment with aqueous solution of KOH. Distribution of n-alkanes and n-fatty acids has been investigated by means of gas chromatography. The studied crude oils showed symmetrical distribution curves of n-paraffins and fatty acids of low molecular weight were abundant as compared with n-paraffins. The n-paraffins distribution curve of Wafra/Iucene biodegraded immature crude oil showed three maxima at C₁₇, C₁₉, and C₃₁ whereas the maxima of n-fatty acids are located at C₁₄,C₂₂and C₂₄. The results were interpreted in terms of origin, maturation and depositional environments of the crude oils.     

川东石炭系气藏中固体沥青形成机理探讨

针对四川盆地东部石炭系气藏储层中发现的大量固体碳质沥青,通过对其保存产状和碳同位素的分析,表明固体碳质沥青主要充填在碳酸盐岩储层的溶孔(粒间溶孔、粒内溶孔及晶间溶孔)、裂缝及溶洞系统中。固体沥青碳同位素值主要分布在-28.83‰~-23.99‰之间,与气藏中储层沥青抽提物中饱和烃、芳香烃、非烃及沥青质和志留系干酪根碳同位素值相比,其值最重;而甲烷碳同位素值为-37.7‰~-29.2‰,值最轻。固体碳质沥青和甲烷的碳同位素值居于两端,其差值为碳同位素热动力分馏的结果。固体碳质沥青形成机理是原油中芳香烃类富含芳香核的高分子物质缩聚为高碳固体物质的结果。      

GEOCHEMICAL CHARACTERISTICS OF NATURAL GAS AT GIANT ACCUMULATIONS IN CHINA

A total of six giant gasfields each with proven reserves of more than 100 billion cubic metres are present in the Ordos and Tarim Basins, China. The gasfields are Sulige, Yulin, Wushenqi, Da'niudi and Jingbian in the Ordos Basin, and Kela 2 in the Tarim Basin. In this paper, we report on the geochemical characteristics of the natural gas at these fields based on studies of gas composition (150 samples), together with stable isotope data (143 samples) and helium isotope data (21 samples). Results show that the gases have high contents of C_1-4 alkanes (generally over 90%) and minor contents of CO₂ (below 3%). The generally high δ¹³C values of C₁-C₄ hydrocarbons indicates a significant contribution from humic source rocks such as Permian-Carboniferous and Mid-Lower Jurassic coal measures. δ¹³ C₁, δ¹³C₂, δ¹³C₃ and δ¹³C₄ values for gases in Upper Palaeozoic reservoirs were -35 to -32‰, -28 to -24‰, -27 to -24‰, and -23.5 to -22‰, respectively. The δ¹³C_iC4 value is higher than that of the δ¹³C_nC4•
He³/He⁴ ratios vary from 10^-7 to 10^-8, indicating that the helium is of crustal (as opposed to mantle) origin. The CH₄/ He³ ratio is 10¹⁰ - 10¹¹, indicating that the CH₄ is of biogenic origin. None of the data is consistent with an abiogenic origin for gas in the Ordos Basin.     

塔里木盆地原油C5—C13轻馏分组成及其地球化学意义

原油 C₅—C₁₃轻馏分中C₈以上组成一直是油气地球化学研究中的薄弱环节。对塔里木盆地40个海相油、湖相油与煤成油样品的C₅—C₁₃轻馏分进行了全烃气相色谱定量分析,在前人研究的基础上,结合C₇轻烃组成,对比分析了不同成因类型原油C₅—C₁₃轻馏分族组成特征。大涝坝油气田湖相油的环烷烃含量较高,雅克拉油气田海相油的支链烷烃含量较高,轮台地区和库车坳陷部分煤成油则具有较高的芳烃含量,塔东地区寒武系来源油与上述特征差异迥然,自成一体。优选出的C_7-C₉ 轻烃族组成参数可较好地区分大涝坝(N/I较高)、雅克拉(I/P较高)、轮台和库车(A/P较高)与塔东(最大I/P和N/P)等地区的原油。针对单体化合物建立的 C₈轻烃新指标 11DMCYC₆/(ctc124TMCYC₅+ctc123TMCYC₅ +cct124TMCYC₅)值与(m-+p-)Xyl/nC₈值可较好区分塔里木盆地海相油、湖相油与煤成油。     

CH4、CO2与稀有气体溶解度的估算模型及其地质应用

CH₄、CO₂、稀有气体的溶解度模型在地球科学领域应用广泛。它们的溶解度模型在研究流体包裹体的均一化压力、古气温变化、天然气运移与聚集规律、富氦天然气成藏、储层中气—水体积比等方面发挥着重要作用。主要综述了纯水与NaCl水溶液中CH₄、CO₂、稀有气体溶解度研究的新进展。重点介绍了精度高且适用性广的模型的建立过程及其适用范围,并给出了部分模型的计算结果。包括：①0~250 °C、0.1~200 MPa、0~6.0 mol/kg NaCl溶液中CH₄的溶解度模型;②0~450 °C、0.1~150 MPa、0~4.5 mol/kg NaCl溶液中CO₂的溶解度模型;③0~80 °C范围内大气稀有气体溶解度与亨利常数的计算模型;④纯水中稀有气体亨利常数计算模型;⑤0.1 MPa、0~65 °C、0~5.8 mol/kg NaCl溶液中稀有气体的溶解度模型。CH₄与CO₂的溶解度模型复杂,但精度高,适用范围广。稀有气体溶解度模型的精度相对较低,适用范围相对较小,有待进一步提高与改进。CO₂—稀有气体—水体系中,低密度的CO₂对稀有气体溶解度的影响较小,而高密度的CO₂对稀有气体的溶解度有较大的影响。目前还无法判断CH₄—CO₂—稀有气体共存时对彼此溶解度的影响程度,其混合气的溶解度模型需要加强研究。     

EFFECT OF PRECIPITATION TEMPERATURE ON THE COMPOSITION OF N-HEPTANE ASPHALTENES

Petroleum asphaltenes were separated from Boscan and Kuwait crude oils by n-heptane at constant temperatures ranging from -2 to 80 ° C. A decreased yield with increase in temperature was observed. The precipitated material was characterized using infrared spectroscopic functional group analysis, HPLC-size exclusion chromatography, vapor pressure osmometry, and elemental analysis. The change in vanadium porphyrin content was estimated for Boscan using UV-Vis. With elevated temperature the asphaltenes are more aromatic (lower H/C) and have higher apparent molecular weight, whereas the pattern of changes in functional groups and heteroatoms (NSO) are more complex and apparently dependent on the crude oil. Porphyrins and low molecular weight types were seen to stay in solution at increased temperature, and a specific extraction of these takes place above 40 ° C. Asphaltene solubility is seen to approximate the Flory-Huggins theory as small molecules go into solution before large molecules. Several other mechanisms may, however, be involved in the phase separation. The molecular size distribution curves obtained by HPLC-SEC were found to explain the trends found in the molecular weights by VPO.     

PYROLYSIS OF SUNNYSIDE (UTAH) TAR SAND: CHARACTERIZATION OF VOLATILE COMPOUND EVOLUTION

Sunnyside (Utah) tar sand was subjected to programmed temperature pyrolysis and the volatile products were detected by tandem on-line mass spectrometry (MS/MS) in real time analyses. A heating rate of 4°C/min from room temperature to 900°C was employed.

Evolution of hydrogen, light hydrocarbons, nitrogen-, sulfur-, and oxygen-containing compounds was monitored by MS or MS/MS detection. Evolution of volatile organic compounds occurred in two regimes: 1) low temperature (maximum evolution at 150 to 175°C), corresponding to entrained organics, and 2) high temperature (maximum evolution at 440 to 460°C), corresponding to cracking of large organic components. Alkanes and alkenes of two carbons and higher had temperatures of maximum evolution at approximately 440°C, and methane at approximately 474°C. Aromatic hydrocarbons had temperatures of maximum evolution slightly higher, at approximately 450° C. Some nitrogen-, sulfur-, and oxygen-'ccntaining compounds were also detected in the volatile products.

Comparing the Sunnyside pyrolysis to the pyrolysis of other domestic tar sands indicated the following for hydrocarbon evolution: 1) the evolution of entrained organics relative to the total evolution was much less for Sunnyside tar sand, 2) the temperatures of maximum evolution of hydrocarbons due t o cracking reactions were slightly lower, and 3) the temperatures of maximum evolution for benzene and toluene are slightly higher than observed for other tar sands.

In general, the noncondensible gases, H₂, CO, and CO₂, exhibited evolution associated with hydrocarbon cracking reactions, and high temperature evolution associated with mineral decomposition, the water-gas shift reaction, and gasification reactions. Pyrolysis yields were dominated by the evolution of carbon oxides and water. The CO₂ primarily appeared t o cane from the decomposition of carbonate minerals. Compared t o other domestic tar sands, the gas evolution reflected more mineral decomposition character for Sunnyside tar sand.     

准噶尔盆地上三叠统泥页岩解析气特征

在准噶尔盆地上三叠统泥页岩地质与有机地球化学特征分析基础上,对准噶尔盆地达9井上三叠统泥页岩岩心含气量进行了测定,分析了页岩气的成分组成与碳同位素特征。泥页岩中有一定的含气量,主要在0.18～0.24m 3/t之间,气体成分以烃类气体为主,二氧化碳、氮气等非烃气体含量较低。甲烷为烃类气体的主要成分,重烃含量较低,相同分子量的异构烷烃占优势,烃类气体具干气特征。非烃气体中的氮气含量明显高于二氧化碳。烃类气体碳同位素值较低,显示出常规低成熟原地腐泥型天然气特征,这种特征可能与短时间解析和烃源岩演化程度有关,具体原因有待进一步深入研究。     

GEOCHEMICAL CHARACTERIZATION OF A BIODEGRADED CRUDE OIL, ASSRAN FIELD, CENTRAL GULF OF SUEZ

A crude oil sample from the Assran field in the Central Gulf of Suez (Egypt) was analysed geochemically and characterized in terms of a variety of source and maturity dependent biomarkers. Biodegradation was indicated by increasing concentration ratios of Pr/n-C₁₇ and Ph/n-C₁₈. However, biodegradation was only slight as GC-MS analyses of the saturate and aromatic fractions showed that hopanes, steranes, aromatic steroids and polycyclic aromatic compounds including sulphur heterocycles remained intact. The sterane and hopane distributions showed a predominance of C₂₇ steranes, a low diasterane index, an abundance of gammacerane, a high homohopane index and an oleanane index < 0.2. The results indicate that the Assran-10 crude oil was derived from a marine carbonate source deposited in a highly reducing saline environment with a high bacterial contribution, consistent with the Upper Cretaceous Brown Limestone or Lower Eocene Thebes Formation containing Type IIS kerogen. Maturity parameters based on changes in the stereochemistry at chirality centres in hopane and sterane nuclei, such as C₃₀βα/(βα+αβ) and C₃₁ 22S/(22S+22R) hopanes and C₂₉ββ/(ββ+αα) and C₂₉ 20S/(20S+20R) steranes, together with triaromatic sterane cracking ratios, indicate that the oil sample was marginally mature. The results also suggest that biodegradation is probably due to sulphate-reducing anaerobic bacteria.     

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轻烃芳构化是采用油气加工后生成的液态烃（Ｃ３～Ｃ９），在Ｚｎ改质的ＺＳＭ－５沸石分子筛催化剂的作用下（５００℃，常压）发生脱氢、芳构化反应，生成苯（Ｂ）、甲苯（Ｔ）、二甲苯（Ｘ）等混合芳烃，实现低碳烷烃改质的过程。这些混合芳烃既可作高辛烷值汽油的调合剂又可作为化工原料，反应后的副产物还可以综合利用，因此可以显著提高轻烃的应用价值。这种用低碳烷烃制取芳烃的工艺过程不仅为芳烃合成探索了一条新路子，而且也为油田轻烃的高附加值综合加工利用拓宽了途径。为此测试了催化剂的基本物理性质，在１００ｍｌ试验装置上评价了轻烃（Ｃ３～Ｃ９）在Ｚｎ／ＺＳＭ—５上的芳构化，并进行了反应条件的试验，找出了适宜的工艺条件。     

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??Yancheng(oil)gas field is the first discovery in Yanfu Depression of Subei Basin.Through a comprehensive organic geochemical analysis and correlation between the high evolution crude oil(its samples taken from well Yancheng 1 were named for YC₁)of Lower Tertiary in Yancheng region and the regional marine Mesozoic Paleozoic hydrocarbons(their samples taken from well Huangyan 1,etc.,were named for HY₁),and between the continental Mesozoic Cenozoic hydrocarbons and source rocks,it is considered that the hydrocarbon source rocks belong to the continental Taizhou Formation and Fu 1 and Fu 2 members of Cenozoic.Because of the limited distribution of the continental Mesozoic(except Pukou Formation)in Subei Basin,its very undeveloped source rocks(including the ones in Pukou Formation),low organic matter abundance and limited hydrocarbon generating potential as well as its hydrocarbon′s being originated from the marine Mesozoic(including the ones found in Sunan region)according to the organic geochemical properties of crude oil,the possibility of the YC₁′s being originated from the continental Mesozoic source rocks is eliminated.In addition,the C₂9 in cholestane series of the YC₁ is high and the fingerprint curve of tricyclic terpane is similar to that of the source rocks of Taizhou Formation and Funing Formation and dissimilar to that of the marine hydrocarbons(HY₁)and that of the oil bearing rock samples of the continental Mesozoic.The degree of evolution of the YC₁ is close to that of the HY₁,the isoparaffin content,however,in the saturated hydrocarbon of the latter is higher than that of the former,which indicates that the geological gas of the latter is older than the former,which indicates that the geological age of the latter is older than the former.The full oil carbon is older than the former.The full oil carbon isotopic value of the YC₁ is 28.59‰,showing a property of continental crude oil.The source rocks of Fu2 member and Taizhou Formation in the gas field area are developed with high organic matter abundance and the types of kerogen belong in the humic sapropelic type and humic type(with Roof over 1%)respectively,so they are the major hydrocarbon sources for the oil and gas fields.In comparison with Dongtai Depression,the Lower Tertiary in Yancheng Sag and Yanfu Depression is of the same hydrocarbon generation and reservoir formation conditions.Various types of gas reservoirs(with different evolution stages and degrees)found in Dongtai Depression could be grown in Yanfu Depression and the reservoir formation conditions of the "Uplift in Sag"drape structural trap of Yancheng gas field were excellent with an early formed trap,a sufficient hydrocarbon source and a good reservoir seal assemblage.It is the major exploration target in the future,such as the deep concave part in Qintong Sag.In addition,the higher zone on the other side of the deep concave part,as Jianhu uplift,etc.,is of the conditions of forming"Zhou zhuang like"gas reservoirs.     

NEW TECHNIQUES AND METHODS FOR THE STUDY OF AGGREGATION, ADSORPTION, AND SOLUBILITY OF ASPHALTENES. IMPACT OF THESE PROPERTIES ON COLLOIDAL STRUCTURE AND FLOCCULATION

The solubility of Furrial asphaltene in toluene was 57g L^-1. However, using a new technique, based on the precipitation of this sample by the phenol PNP, we found that a fraction [2], comprising 47% of the asphaltene, is of low solubility. This suggested that this material constitutes the colloidal phase, and the rest acts as the dispersing fraction. This technique allowed the fractionation of asphaltenes in fractions A₁, A₂, and A₃ according to solubility, going from practically insoluble (A₁) to low (A₂, 1 g L^-1) to high (A₃, around 57 g L^-1). The adsorption isotherms of asphaltenes on glass and silica in toluene consist of a sequence of steps or step-wise adsorption. The first layer or first step is formed by the adsorption of free asphaltene molecules and by small aggregates (aggregation number between 3 and 6) which saturate the glass or silica surface in the usual manner (L-type or H-type isotherms). However, we suggest that the second, third, and other asphaltene layers adsorb sequentially according to the above differences in solubility. The very slow changes with time and the negligible desorption from the surface measured for the above isotherms were interpreted as the effect of packing or the building up of a well packed layer. This would be achieved by the slow formation and rupture of bonds between neighboring molecules at the surface. Thus, molecules with difficulties to pack, adsorbed by a kinetically controlled process, are either rejected or relocated in a thermodynamic controlled process. The above results and ideas were used to improve the models for asphaltene and petroleum colloids and to underscore the importance of surfaces and colloid dispersants in asphaltene precipitation during the production of crude oils. For instance, the results described below suggest that colloids are constituted by a well packed and insoluble asphaltene core, impervious to the solvent, and by a loose packed periphery which, by allowing solvent penetration, keep the colloid in solution. According to this model, desorption of compounds in the above loosely packed periphery, such as the one promoted by a surface, would be the main cause of asphaltene precipitation from crude oils. In this case, solubility reductions caused by pressure drops during oil production would have a minor effect. Also, preliminary number average molecular weights M_n for four asphaltenes, obtained using a new procedure, are presented here. The M_n values obtained ranged from 780 to 1150 g/mol.     

DIAGENETIC HISTORY OF LATE PALAEOCENE POTENTIAL CARBONATE RESERVOIR ROCKS, KOPET-DAGH BASIN, NE IRAN

The Upper Palaeocene (Thanetian) Chehel-Kaman Formation in the Kopet-Dagh Basin of NE Iran is principally composed of carbonates with minor siliciclastics and evaporites. Six stratigraphic sections were measured and more than 1,000 samples were collected for petrographic analysis, together with analyses of carbon and oxygen isotopes and trace element content. Four major carbonate lithofacies (and 13 subfacies) have been identified in previous studies and are interpretd in terms of deposition in a shallow-marine environment.
The petrographic analyses indicate that the Chehel-Kaman Formation carbonates have undergone a complex diagenetic history which includes compaction, cementation, micritization, dissolution, silicification, dolomitization, neomorphism and fracturing. δ¹⁸O and δ¹³C values in Chehel-Kaman Formation limestones range between +0.8 and -15.1%₀ PDB, and -2.82 and +3.5%₀ PDB, respectively. These variations are interpreted to reflect meteoric and burial diagenetic processes. Variations in trace-element concentrations (Fe and Mn increased while Na decreased) also indicated the effects of meteoric flushing. The limestones appear to have been formed at about 28°C.
Chehel-Kaman Formation dolomites were divided into d1 (finely-crystalline) and d2 (coarsely-crystalline) types. Petrographic and geochemical results indicated that the d1 dolomites formed under sabkha conditions from a parental solution at around 26°C, while d2 dolomites formed during burial diagenesis with much hotter pore fluids (around 72°C). The paragenetic sequence indicates that primary porosity decreased during early stages of diagenesis, although secondary porosity was subsequently created improving the reservoir quality of the carbonates.     

裂解热模拟实验中碳同位素变化特征及其地球化学意义

采用高温模拟技术,对原油、氯仿沥青“A”、烃源岩、干酪根和原油族组分样品进行热模拟实验,分析不同样品在裂解过程中产物碳同位素组成的变化特征,研究其地球化学意义。原油、氯仿沥青“A”、干酪根、烃源岩和饱和原油族组分随热演化温度的增加,热模拟气态烃碳同位素演化规律是由重变轻再变重的演化趋势,700℃以前碳同位素分布呈正碳同位素系列分布,750℃以后出现丙烷碳同位素倒转,芳烃馏分和沥青质馏分的碳同位素值和正碳同位素系列分布出现差异;各样品随热模拟温度的增加,Δδ¹³C_2-1值都呈增大的趋势;Δδ¹³C_3-1、Δδ¹³C_3-2对原油、氯仿沥青“A”、饱和烃馏分与芳烃馏分和沥青质馏分随模拟温度的变化有差异;δ¹³C₂ -δ¹³C₃ 值和LN（C₂/C₃）值随模拟温度的增加呈正相关性。     

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.     

四川盆地二叠系不同类型烃源岩生烃热模拟实验

通过对四川盆地二叠系不同类型烃源岩（泥质灰岩、沥青灰岩、泥岩和煤）在加水封闭体系下的热模拟实验,结果表明不同类型干酪根之间产气率明显不同。Ⅰ型干酪根的泥质灰岩总产气率最高（4 226m³/t_TOC）,其次为沥青灰岩（2 445.5 mm³/t_TOC）,煤岩总产气率最低（459.3m³/t_TOC）,Ⅲ型干酪根的泥岩总产气率高于煤岩。泥质灰岩烃类气体产率仍然最高（765 m³/t_TOC）,其次为泥岩（606.1 m³/t_TOC）,[沥青灰岩最低。泥岩烃类气体产率高于沥青灰岩,可能与沥青灰岩中除去烃类遭受热裂解外,碳酸盐分解生成大量非烃气体（CO₂）有关,从而造成总产气率高,而烃类气体产率却偏低的现象。这样,沥青灰岩生成的烃类主要来源于分散有机质热裂解,而不是灰岩本身。不同类型气源生烃对比结果表明,Ⅰ型干酪根的泥质灰岩或Ⅲ型干酪根的泥岩有利于低温生烃,而煤岩和分散有机质生烃历程长,有利于后期天然气生成与聚集保存。     

CPA方程对CO2-水体系相态研究

CO₂作为酸性气体之一,其热力学性质对石油、天然气开发至关重要。水通常在地层中与烃类共生,由于地层盐水的存在使得与烃类混合的气体量减少,并且这种效应将随着压力和水相量的增加而增加（随盐度的降低而减小）。因此,弄清CO₂-水体系的热力学性质将对理解这些过程具有重要的指导意义。通过运用SRK-CPA状态方程结合CR-1混合规则对CO₂-水体系的相平衡特征进行计算,研究CO₂在水中的溶解度和水在CO₂气相中的溶解度,并对308 K,373 K和473 K等3种温度下,CO₂-水体系不同缔合模型相互作用的模拟结果与实验数据进行分析,结果表明：在CO₂的临界温度和临界压力附近,由于发生了由气-液到液-液的相态转变,CO₂和水的溶解度在此温度和压力点将发生显著的变化;当CO₂作为非缔合物与缔合模型为4 C的水发生溶剂化交叉缔合时,运用CPA方程计算的溶解度结果与实验数据拟合较好。CPA方程在工程应用中能够满足含CO₂和水体系的热力学性质预测需求。