油伴生CO2气的成因及其石油地质意义

以松辽盆地南部油伴生CO2气为研究对象,通过组分分析及碳、氧及氮同位素分析,结合中国已有伴生CO2气的含量及同位素数据,研究油伴生CO2气的成因及其意义.结果表明:中国油伴生气中CO2的含量为0～99.53%,大部分在5%以下;油伴生CO2气的δ13 CcO2值为-15.91‰+6.49‰,集中分布于-13‰～ -4‰,以无机成因气为主;松辽盆地南部油伴生CO2气的含量为1.43% ～54.22%,δ13CcO2值为-5.32‰～ -6.76‰,为幔源-岩浆成因;幔源-岩浆成因油伴生CO2气与气藏中的CO2气成因一致,注入时间一般晚于油气大规模充注时间,CO2充注驱油普遍存在;在幔源-岩浆CO2与油气混合成藏地区(如松辽盆地南部)寻找幔源-岩浆CO2充注驱油成因的次生油气藏将是一个新的勘探思路.     

新场地区上三叠统须五段陆相页岩层系非常规天然气特征与成因

除下古生界海相页岩具有页岩气开采的价值外,四川盆地陆相领域页岩层序也非常发育;其中川西坳陷须五段获得突破,但其非常规天然气地球化学特征十分复杂、成因类型多样,开展非常规天然气特征和成因的研究对于有效的认识四川盆地陆相页岩的勘探开发前景具有重要意义。在对川西坳陷上三叠统须五段陆相页岩层序天然气组分和同位素特征分析的基础上,结合该区实际地质条件的分析,研究了天然气的成因类型、天然气成熟度和天然气的赋存状态。结果表明:须五段天然气主要为烃类气体,甲烷含量、干燥系数变化大;但平均值较低,烷烃同位素具有δ13C1δ13C2δ13C3δ13C4的正常序列分布特点;但甲烷碳同位素值(δ13C1)变化大,在-44.4‰~-27.1‰之间;乙烷碳同位素值明显偏轻,介于-28.1‰~-22.9‰之间。须五段天然气为典型煤型气,具有成熟-中等成熟阶段热成因气的特征;天然气为吸附气与游离气的混合气体,但以吸附气为主,在生产过程中,由于同位素的分馏效应,导致天然气甲烷碳同位素偏重。     

松辽盆地CO2气藏的形成与分布特征

对松辽盆地已发现的10个CO2气藏气体组分、碳及氦同位素等地球化学特征进行了分析,认为松辽盆地CO2气藏主要为幔源成因,表现的特征主要为8δ>C<,co2>>-8‰,氦的同位素也比较重,R/Ra=1.9～7.2.盆地地质背景及包裹体分析显示,长岭、德惠及古龙等断陷CO2气藏主要为晚期成藏,CO2包裹体主要为晚期气包裹体...     

注CO2前置段塞+N2顶替提高采收率机理

SJ油田为一低渗透油藏,天然能量低。受CO2气源不足以及油井管柱抗腐蚀能力差的限制,持续的CO2-EOR不适合SJ油田的实际情况。鉴于此,一个改进的对策是用N2推动的CO2前置段塞驱代替持续的CO2驱油。本文根据SJ油田先导试验区的流体特征,对比了连续注入CO2驱油和N2推动的CO2前置段塞混相驱油的效果和机理。在注CO2、N2细管驱替效率及最小混相压力实验测试基础上,通过注CO2、N2与地层原油多级接触混相驱机理相态模拟,长细管前置CO2混相驱替+后续N2段塞顶替驱替机理一维数值模拟研究,分析了前置CO2段塞+后续N2顶替驱油时原油与注入气的互溶情况、气驱界面张力变化规律、气驱过程中C2—C6的中间烃组分在油气两相中的分布、气驱过程中油气两相的黏度以及密度变化。结果表明SJ油田实施前置CO2段塞+后续N2顶替驱油时,后续的N2与前置的CO2段塞不会出现严重的扩散弥散,注气前缘仍能保持CO2的富集并实现稳定的混相驱油即在注气总量相同的情况下,N2推动的CO2前置段塞驱可以获得与持续的CO2驱相同的驱油效果;同时减少了CO2的注入量,从而可减缓CO2长期注入对油井管柱产生的腐蚀。所得认识对CO2驱提高采收率技术的改进和发展具有一定的启发作用。     

鄂尔多斯盆地延长探区页岩气

通过对中生界页岩气、中生界浅层气、上古生界天然气和周边盆地的生物成因气等多种成因气的地球化学特征(包括组分和碳同位素)对比,探讨鄂尔多斯盆地中生界页岩气的成因.鄂尔多斯盆地中生界页岩气甲烷体积分数为46.08%~94.56%,重烃体积分数为2.86%~37.61%,甲烷碳同位素为-52.0‰~-46.4‰.通过天然气组分及碳同位素对比分析,确定鄂尔多斯盆地延长组页岩气的成因既不是来自上古生界煤型气,也不是生物成因气,而是和盆地浅层气地球化学特征相似,属于偏腐泥型源岩热解形成的原油伴生气,源岩为延长组腐泥型烃源岩.考虑到热演化成熟度特征,认为吴旗—庆阳—富县一带中生界烃源岩热演化程度高,为页岩气勘探有利区.     

钢铁企业能源消耗与CO2减排关系

建立了钢铁企业长流程CO2过程排放模型,给出总排放和工序排放的计算方法.计算发现:国内某800万t产量规模的典型钢铁企业CO2总排放在2007年达到1561.64万t,吨钢排放1.85t CO2;工序排放从大到小依次为炼铁、焦化、烧结、轧钢、炼钢、熔剂焙烧和球团工序,其中炼铁和焦化工序排放分别占总排放的58.83%和11.25%.为了评价钢铁企业能源消耗和CO2减排关系,提出钢铁企业CO2综合排放因子和能耗碳饱和指数评价方法.研究表明,为了减少CO2排放,钢铁企业不仅需要降低总体能耗,还需要降低能耗的碳饱和指数,能耗碳饱和指数与能源结构相关,能源结构中CO2总影响系数大的能源种类消耗量越大(例如焦炭),碳饱和指数越高,越不利于CO2的减排.这说明实现钢铁生产的生态园区化、优化能源结构以及加强钢铁生产的能源转换功能对钢铁企业减排有显著作用.     

百色盆地第三系浅层气成因类型与形成机制

在分析百色盆地第三系浅层气地球化学特征的基础上，利用天然气的化学组成和稳定碳同位素比值关系对该盆地浅层气的成因类型进行鉴别，同时根据浅层气的赋存状态与空间展布规律，从浅层气的化学组成和碳同位素组成变化特征入手，结合其它地质、地化资料，探讨盆地浅层气的形成机制。认为百色盆地浅层气以烃类气体为主，其中甲烷占优势；甲烷碳同位素组成偏轻，具有生物成因气的碳同位素组成特征。随气藏埋深增加，浅层气中甲烷含量降低，Cz 重烃增多；甲烷碳同位素组成变重；天然气密度升高。盆地浅层气可划分为三种成因类型：生物气、生物气-低熟混合气、油层菌解气。提出盆地具有沉积、成岩过程中的早期成气作用、抬升之后的后期成气作用和晚期复合成藏三种形成机制。     

煤层气地球化学研究现状与发展趋势

概述了煤层气作为新资源的研究及开发状况,全面评述了煤层气地球化学研究的现状:其组分以CH4为主,δ13C1值约为-80‰--10‰,有限的δD1值数据为-333‰--117‰,CO2的δ13C值为-29.4‰- 18.6‰,其他组分的同位素则极少研究;煤层气目前仅主要识别出热成因气和次生生物气两种类型,还有其他划分标准;与常规天然气相比,煤层气CH4和CO2的δ13C值的分布范围很宽,尤其存在特高值.目前煤层气地球化学存在并需解决的主要问题为:甲烷碳、氢同位素组成变化的机理、影响因素及其应用;δ13C1值与Ro值的关系;煤层气成因类型的系统划分方案和指标以及煤层气地球化学在煤层气选区评价中的应用等.     

氨法脱硫脱碳富液解析CO2研究

基于氨溶液能同时吸收烟气中CO2和SO2可以降低烟气净化成本,对氨溶液吸收CO2和SO2后的富液CO2进行解析研究,以了解其解析特性。研究结果表明:富液中存在的高浓度硫酸铵对CO2解析有抑制作用,与碳酸氢铵溶液解析率相比降低18%以上;将碳酸氢钠作为添加剂加入溶液中解析时,能够显著提高解析率并且可以抵消硫酸铵的抑制作用;解析气中逸氨含量为9.5%左右,解析化学反应能耗约为30.8 kJ/mol。     

CO2在页岩中的吸附解吸性能评价

利用自主设计的页岩中气体吸附解吸实验装置,在不同温度和压力条件下研究CO2在不同页岩中的吸附解吸性能。结果表明:CO2在页岩上的等温吸附曲线属于典型的Ⅰ型等温曲线,可采用Langmuir模型对吸附及解吸数据进行拟合;相同温度下,CO2在页岩中的吸附量随着压力的升高而增大;相同压力下,CO2在页岩中的吸附量随着温度的升高而减小;相同温度压力条件下,CO2解吸过程中存在解吸滞后现象,且解吸附曲线表征的最大吸附能力低于吸附曲线表征的最大吸附能力;CO2在页岩上最大吸附量随有机碳含量增加而增大,随石英含量增加而减小。     

Research progress in studies on the coalbed gas geochemistry

The current situation of geochemical studies on coalbed gas is reviewed in this paper. Generally, coalbed gas is compositionally dominated by methane with δ¹³C₁ values ranging approximately from -80‰ to -10‰. However, few isotopic studies have been carried out on other components of coalbed gas except for hydrogen and carbon dioxide, whose δD_CH4 values available for utilization vary from -333‰ to -117‰, and δ¹³C_CO2 values from -29.4‰ to +18.6‰. Two major types of coalbed gas, thermogenic gas and secondary biogenic gas, have been identified, and there are also some other classification criteria. Compared with conventional natural gases, coalbed gas has a wide distribution range of δ¹³C₁ and δ¹³C_CO2 values, especially possessing some extremely heavy values. Current problems that remain unsolved in the coalbed gas geochemistry include the variation mechanism, controlling factors and application of carbon and hydrogen isotopes of methane, the relation between the values of δ¹³C₁ and Ro, the systematic classification scheme and criterion of genetic types, and the application of the coalbed gas geochemistry in evaluating target districts of the coalbed gas exploration.     

松南营城组火山岩气藏成藏模式

松南气田营城组火山岩天然气的δ13C1值大于-30‰,具有δ13C1＞δ13C2＞δ13C3负序列或同位素倒转,甲烷同位素偏重,表明松南气田营城组火山岩天然气不仅具有煤型气与油型气混合特性,还具有多期次成藏特征,煤型气充注早,为89～83 Ma;油型气和幔源气充注晚,为78～68 Ma.松南气田营城组天然气中无机气体主...     

Carbon and sulfur isotopic compositions of basal Datangpo Formation, northeastern Guizhou, South China: implications for depositional environment

Isotopic compositions of Mn-carbonate and organic carbon from the same individual samples and sulfur isotopic compositions of pyrites in the basal Datangpo Formation were analyzed. Highly 34S-enriched pyrites （834Spyrite =31.7-59.4‰） were precipitated in rel- atively occlusive pore water under anoxic condition in sediments, which is consistent with the observation of large and scattered pyrite framboids. The sulfidic deep ocean was not ＂oxidized＂ in the early Datangpo interglacial interval, thus the level of seawater sulfate remained low and marine δ34Ssulphate remained high. Low δ13Ccar （average -7.4‰） and abnormal relationship between δ13Ccar and fractionation （ΔCar-ors） imply that the negative δ13CCar excursion may have resulted from oxidation of part of a large organic carbon reservoir. High Δcar-org （average 25.1‰） implicates high CO2 level in the atmosphere. Small standard deviation （1.0‰） of δ13CCar values indicates the Mn-carbonate was precipitated near the water-sediment interface under dysoxic conditions rather than in occlusive pore water in sediments.     

Determination of carbon isotopic composition of individual light hydrocarbons evolved from pyrolysis of source rocks by using GC-IRMS

The carbon isotopic composition of individual light hydrocarbons generated from source rocks that had been pyrolysed in vacuum glass tube were determined by using the GC-IRMS techniques. The results indicate that abundant CO2 in the pyrolysates has a remarkable effect on the determination of CH4δ13C. Running cryogenically with an initial temperature of -40℃can effectively eliminate the effect. In addition, it conduces to measuring the δ13C of C2+ hydrocarbons by increasing the injection volume and/or absorbing CO2 with the solution of sodium hydroxide.The above measures will help to get the carbon isotopic composition of C1-C7 components, which is of great significance for gas/source rock correlation and for study on the genesis of natural gas.     

商都坳陷浅层CO_2气藏成因与典型气藏分析

商都地区CO2气藏的气体组分主要为CO2,体积分数为87.0%～99.9%,碳同位素δ13C值分布在-5.2‰～-6.5‰之间,氦同位素3He/4He体积比分布在(1.69～3.35)×10-6之间,为典型幔源CO2气.乌兰哈达-高勿素断裂是一条长期活动的超深断裂,不仅控制着盆地沉积和演化,而且输导了多期次岩浆活动,提供了幔源CO2运移通道.商都坳陷新生代沉积演化有利于储盖组合的发育,具有良好的CO2气藏形成条件.通过对典型CO2气藏解剖,其具有气藏浅、产量高的特点.SZ5井累计产气量是容积法计算储量的2.23倍,认为存在幔源CO2的不断补充.     

Carbon isotopic composition of mantle xenoliths in alkali basalt from Damaping, Hebei

The carbon isotopic composition of CO-2, CO and CH-4 extracted by pyrolysis from spinel lherzolite and black pyroxenolite xenoliths in alkali basalt from Damaping has been measured with GC_MS. The results show that, at heating temperatures from 400 to 1 140℃, the δ 13C of CO-2 and CO is -22‰--27‰, and that of CH-4 -30‰--50‰. The data imply that the magma which was generated in the upper mantle by partial melting in the area has experienced the multistage degassing process, and the δ 13C values represent the carbon isotopic composition of CO-2, CO and CH-4 remaining in it, respectively.     

Secondary biogenic coalbed gas in some coal fields of China

The secondary biogenic coalbed gas, a new genetic and energy source type of coalbed gas in China, has been found in Xinji, Liyazhuang and Enhong areas. The essential characteristics of this type of gas are: (i) the major component of the gas is methane, with C1/C1-5 value higher than 0.99, indicating that the gas is part of dry gas; (ii) theδ13C1 value is in the range of -61.7‰to -47.9‰, mostly lower than -55‰, which is much lower than the estimatedδ13C1 value of thermogenic methane according to the thermal evolution degree of the coal rocks (with R0 value from 0.87% to 1.43%), showing the characteristics of the secondary biogenic gas; (iii) theδ5D value of methane ranges from -244‰to -196‰; (iv)δ13C 2 value ranges from -26.7‰to -15.9‰andδ13C 3 value ranges from -10.8‰to -25.3‰, indicating that the heavier hydrocarbons have a thermogenic origin; (v) the content of CO2 is very low, andδ13CCO2 value changes greatly, reflecting a characteristic of secondary change; (vi)δ15N2 value ranges mainly from -1‰to +1‰, indicating N2 derived significantly from air. The negative linear correlation between the contents of N2 and CH4 reflects the activity of bacteria bearing surface water infiltrating into coal beds. The comprehensive tracing indices show that the coalbed gas in the studied areas is the mixed gas of primarily secondary biogenic gas and a part of remnant thermogenic gas. The uplift of coal beds and the development of faults in the studied areas create favorable conditions for the formation of the secondary biogenic gas.     

Kinetic modeling the effects of primary migration, diffusion and waterwashing on Upper Paleozoic coal-derived gas at the center of Ordos Basin

Gold reactor pyrolysis system is used to model the gas formation from the Upper Paleozoic coal measures and the results show coal-derived gas characterized with δ13C1 of-33.46‰, δ13C2 of-23.1‰, dryness(C1/C1-4) 85.6%. And then, effects of the post-genetic processes on coal- derived gas are analyzed in turn: (i) About 27% coal-derived gases constituted with more methane are calculated to be lost during diffusion. The residual in reservoir are characterized with almost the same compositions as the original, which suggests faint influence by diffusion (the residual, δ13C1 of -32.78‰, δ13C2 of-23.1‰, C1/C1-4 83%); (ii) Water washing made about 8% coal-formed gases lost and their components and stable carbon isotopes are stable; (iii) In the final, it is speculated that primary migration makes much more wet gas (C2-4) leave in coal measures. The variance of gas dryness induced by this factor is estimated to be about 10%.     

Multi-origin alkanes related to CO2-rich, mantle-derived fluid in Dongying Sag, Bohai Bay Basin

With the newly obtained carbon isotope data for the natural gas, a pilot study of multiple-sourced alkanes related to the mantled-derived fluid is presented. The carbon isotope values of alkanes in the Dongying Sag possess thefea tures indicating a general organic origin. However, there are two sub-populations in the isotopic data set, which reflect two specific types of origins. In gene ral, the sub-population with high δ13CCH4 values is related to the CO2-rich, mantle-derived fluid, and it is distributed in the belts where mantle-derived fluid flow and basic volcanic activities have occurred. Geological and geochemical studies demonstrate that this variation of methane carbon isotope values in the Dongying Sag is unrelated with the basin bury and thermal histories, types of source rocks, and reactions between basin fluid and rocks. Mixing of mantle-derived fluid and organic sourced hydrocarbons is probably the cause for the variation .