THE EFFECTS OF HIGH PRESSURE ON OIL‐TO‐GAS CRACKING DURING LABORATORY SIMULATION EXPERIMENTS

The effects of high pressures on the yield and kinetics of gas generated by the cracking of crude oil were investigated in laboratory simulation experiments. Samples of a low‐maturity non‐marine oil were recovered from the Paleogene Shahejie Formation in the Dongying depression, Bohai Bay Basin, eastern China. The oils were cracked to gas under different pressure and temperature conditions in an autoclave. Initial temperatures of 300 °C were increased to 650 °C at rates of either 30 or 100 °C/h. Reaction products were analysed at the end of each 50 °C temperature increase. Pressure conditions were either 0.1 MPa (i.e. atmospheric) or 20 MPa. Results show that high pressures inhibit or delay oil‐to‐gas cracking and retard the initiation of the cracking process. The temperature at which oil was cracked and the activation energy of the formation of C_1–5 hydrocarbons increased under high pressure conditions, demonstrating the effects of pressure on the kinetics of the oil‐to‐gas cracking process. High pressures and high temperatures inhibited the conversion of C_2–5 hydrocarbons to methane during secondary cracking. In addition, high pressures retarded the generation of N₂, H₂ and CO during cracking of oil. The presence of water increased the yields of total cracked gas, C_2–5 hydrocarbons and CO₂ in high‐pressure conditions. The simulation results show that CO₂ and C_2–5 hydrocarbons have similar yields during oil‐to‐gas cracking. Using the kinetic parameters determined from the laboratory experiments, the yield and production rate of gas generated during the cracking of oil from Member 4 of the Paleogene Shahejie Formation in the Minfeng‐Lijin sag (Dongying depression) were calculated. The results indicate that only limited volumes of natural gas in this area were derived from the cracking of oil, and that most of the gas was derived from the thermal decomposition of kerogen.     

四川盆地威远气田水溶气脱气成藏地球化学证据

目前,对于四川盆地威远气田的形成过程和天然气来源在认识上还存在着较大分歧。为此,针对该气田天然气的甲烷碳同位素值异常偏重的现象,首先分析了气藏的地质特征和天然气的地球化学特征:气田主力气层是震旦系灯影组,天然气以甲烷为主,含微量乙烷和痕量丙烷;气藏含水饱和度较高,普遍含有保存很好的原生水。进一步根据天然气中H_2S含量与甲烷碳同位素值的关系,判断该区天然气甲烷碳同位素值偏重并非由硫酸盐热化学还原反应(TSR)造成。最后根据该区天然气的甲烷碳同位素值和邻区的对比结果,结合构造演化背景,判断认为,威远气田的天然气主要来自水溶气,并非过去认为的自邻区经侧向运移而来。结论认为:①由于水中释放出的甲烷碳同位素值较重,水溶气的脱气成藏造成了威远气田天然气甲烷碳同位素值偏重的现象;②伴随喜马拉雅期构造运动,威远地区大幅度抬升,形成构造圈闭,在高温、高压状态下溶解在水中的天然气发生减压脱溶,释放出的气体在圈闭中成藏,进而形成了威远气田;③经计算,威远气田圈闭下的水中释放出的天然气数量与该气田的探明储量相当,印证了该气田水溶气脱气成藏的观点。     

天然气水合物相平衡的实验研究

天然气水合物相平衡研究是天然气水合物勘探开发和海洋环境保护研究的基础,也是最重要的前缘问题。为此,对取自中国西部油田某2口井的分离器气气样1和气样2在纯水、地层水和配置水等3种水样,以及3 MPa、6 MPa、9 MPa、12 MPa等4个压力体系下对生成水合物的温度进行了实验研究。研究结果表明：随着实验压力的增加,同种气样生成天然气水合物的温度越高;随着水样矿化度的增加,同种气样生成天然气水合物的温度越低;在同一水样中,组分、组成不同的天然气,甲烷含量越高,其形成天然气水合物的温度越低。     

天然气水合物生成的影响因素及敏感性分析

天然气水合物是由某些气体或它们的混合物与水在一定温度、压力条件下生成的一种冰状笼型化合物。进行水合物生成条件的敏感性研究对预防天然气水合物的生成有着重要意义。分析了温度、压力两个主导因素的影响,提出了临界温度的概念;验证了盐类对水合物生成的抑制作用;剖析了天然气各组分对水合物生成的敏感程度。得出:水合物生成温度随着压力的增加而升高,但是存在一个临界温度,当环境温度达到该值时,压力对水合物生成的影响很小;甲烷虽然是生成水合物的主要组分,但当其含量趋近100%时,却不易形成水合物;乙烷不是敏感组分;丙烷对水合物生成的影响较乙烷大;异丁烷这类重烃组分,由于其分子大小和Ⅱ型结构中的大洞穴尺寸相匹配,所以对Ⅱ型结构的稳定能力远大于其它分子,当其含量较小时,就易生成Ⅱ型结构水合物;CO2和HS这类酸性气体,易溶水从而能促进水合物的生成。     

活性炭上天然气湿储方法研究

天然气湿储技术是强化天然气低压存储的有效手段。研究了载水量、温度、吸附剂孔径分布和填充密度、存在较重碳氢化合物等因素对储气容量和储气压力的影响。结果发现孔径在3nm~5nm、具有中等比表面积和较大孔容的活性炭吸附剂用于天然气湿储是比较适宜的,最佳水含量与所用炭材料的孔结构性质密切相关,温度对充放气量影响不大。在实验的基础上可确定该方法的最佳存储条件。     

Investigation of methane adsorption on chlorite by grand canonical Monte Carlo simulations

In this paper, the methane adsorption behaviours in slit-like chlorite nanopores were investigated using the grand canonical Monte Carlo simulation method, and the influences of the pore sizes, temperatures, water, and compositions on methane adsorption on chlorite were discussed. Our investigation revealed that the isosteric heat of adsorption of methane in slit-like chlorite nanopores decreased with an increase in pore size and was less than 42 kJ/mol, suggesting that methane adsorbed on chlorite through physical adsorption. The methane excess adsorption capacity increased with the increase in the pore size in micropores and decreased with the increase in the pore size in mesopores. The methane excess adsorption capacity in chlorite pores increased with an increase in pressure or decrease in pore size. With an increase in temperature, the isosteric heats of adsorption of methane decreased and the methane adsorption sites on chlorite changed from lowerenergy adsorption sites to higher-energy sites, leading to the reduction in the methane excess adsorption capacity. Water molecules in chlorite pores occupied the pore wall in a directional manner, which may be related to the van der Waals and Coulomb force interactions and the hydrogen bonding interaction. It was also found that water molecules existed as aggregates. With increasing water content, the water molecules occupied the adsorption sites and adsorption space of the methane, leading to a reduction in the methane excess adsorption capacity. The excess adsorption capacity of gas on chlorite decreased in the following order: carbon dioxide > methane > nitrogen. If the mole fraction of nitrogen or carbon dioxide in the binary gas mixture increased, the mole fraction of methane decreased, methane adsorption sites changed, and methane adsorption space was reduced, resulting in the decrease in the methane excess adsorption capacity.     

天然气二次运移组分变化机理研究

天然气的烃类组成并不单一,但成藏天然气一般以甲烷为主,除了与烃源岩母质类型及其演化有关以外,二次运移也是一个重要的作用因素。通过天然气二次运移物理模拟实验,研究了天然气二次运移特征,注意到天然气二次运移是一种断续流运移,主要包括2种基本运移方式——活塞流和优势流,两者交替就形成了天然气的断续流运移;结合有机质热演化生烃过程以及气、水、岩的相互关系分析,探讨了天然气二次运移过程中组分变化的机理,认为二次运移会导致成藏天然气组分中甲烷含量增高,其主要原因包括二次运移过程中的组分分异作用,断续流运移导致重组分在岩石孔隙中的封闭滞留作用,以及二次运移路径上残留原油的溶解作用。     

四川盆地安岳气田龙王庙组气藏天然气有水溶气贡献的迹象

通过有机地球化学手段对四川盆地安岳大气田龙王庙组天然气和储层沥青进行了系统研究,发现天然气甲烷碳同位素较储层沥青明显偏重。这用目前大家普遍认为的油裂解气的观点难以解释,因根据歧化反应碳同位素分馏原理,油裂解生成的甲烷和沥青,甲烷碳同位素会明显轻于沥青。另外,甲烷碳同位素值与H₂S含量也没有明显的相关性,用TSR作用也很难解释气藏中甲烷碳同位素偏重的现象。从气田水中释放出的水溶气甲烷碳同位素较气藏游离天然气的甲烷碳同位素偏重或者重,推断可能是由于地层水水溶相天然气的脱溶,造成龙王庙组气藏中的天然气甲烷碳同位素较储层沥青碳同位素偏重。同时,经激光拉曼测试分析发现大部分烃类包裹体具有液相甲烷特征峰,进一步证实水溶相天然气的存在。通过对气源、地层水、温压环境、构造演化、盖层等地质条件进行分析,提出龙王庙组气藏具有良好的水溶气形成、保存以及晚期随构造抬升水溶气脱气成藏的条件。对比龙王庙组埋深最大时与现今气藏条件下甲烷在地层水中的溶解度,估算出龙王庙组1m³的地层水可释放出6m³的天然气。     

吐哈盆地雁木西油田天然气的选择性生物降解作用

对吐哈盆地雁木西油田原油与原油溶解气地球化学特征进行了对比和分析,探讨了微生物对天然气降解作用的选择性.雁木西油田的天然气均为湿气,不同组分的相对含量和烃类组分碳同位素比值都有较大的变化范围,部分天然气的烃类组分碳同位素比值明显地变大.生物降解作用的选择性与这些变化有极为密切的关系.由于不同的微生物对不同组分的降解能力和强度不同,因而造成了不同剩余烃类组分的碳同位素比值不同,部分烃类碳同位素比值甚至发生倒转.烃类碳数越小,越易发生生物降解作用,较容易发生生物降解作用的组分是甲烷、乙烷和丙烷等较轻的烃类,其次是正丁烷、正戊烷等较重烃类,发生生物降解作用的烃类最高碳数可以达到14.异丁烷、异戊烷等异构烷烃抵抗生物降解作用的能力较强.     

和田河气田天然气东西部差异及原因

塔里木盆地和田河气田天然气是成熟度较高的干气，二氧化碳和氮气含量高，天然气来自寒武系海相高-过成熟烃源岩，属油型气，气田呈近东西向展布，西部井区的埋深小于东部井区，西部井区天然气二氧化碳含量和干燥系数明显高于东部，西部井区甲烷碳同位素重于东部，导致东西部天然气的地球化学特征有明显差别的原因是，天然气自东向西动移造成了组分的东西部差异；西部井区的压力释放使水中溶解的CO2大量释放，导致CO2含量增加；扩散作用导致了甲烷碳同位素的西重东轻。     

Solubility of Methane in Water at the Presence of β-Cyclodextrin,SDS, and Multi Wall Carbon Nanotubes at Low Temperatures

In this research, the solubility of methane in water at presence of β-cyclodextrin (CD), sodium dodecyl sulfate (SDS), and multiwall carbon nanotubes (NTs) have been investigated. The tests were performed at the pressures 3 and 5 bars and temperatures of 1–3°C. For any solution, data of vessel pressure versus time and the total absorption capacity were collected. NTs were dispersed in water by using SDS solution with a concentration of 1 wt% and applying ultrasonic agitation for 25 min. Addition of 0.5 wt% cyclodextrin increased the capacity of methane absorption as much as 14.63% at temperature 1°C and primary pressure of 3 bar. Dissolution capacity increased up to 5.26% by using NT along with SDS at the pressure of 5 bar and low temperatures. Simultaneous usage of CD, SDS, and NT (the solution containing 1 wt% CD, 0.1 wt% SDS, and 1 wt% NT) had the highest effect on the increase of amount and rate of dissolution. The amount of dissolution increases for this solution was 14.63% at temperature 1°C and the primary pressure 3 bar. Utilization of CD, SDS, and NT and their mixture improved the initial dissolution rate of methane at low temperatures.     

块状甲烷水合物分解动力学特征及其影响因素

与冷泉相关的块状甲烷水合物是非常规天然气资源开发的重点目标之一。为了了解其分解动力学特征以便于制订合理的开发方案，利用高压差示扫描量热仪实验测试了块状甲烷水合物的生成与分解过程，将分解的吸热效应与分解速度相关联，分析不同环境下块状甲烷水合物分解瞬时速度和平均速度的变化特征，然后，基于实验结果采用经典的甲烷水合物分解动力学模型计算得到不同压力下甲烷水合物分解活化能，进而评价分解表面积、温度、压力和矿化度等因素对甲烷水合物分解速度的影响。研究结果表明：①随着压力升高，甲烷水合物分解活化能逐渐增大，在此次实验测试条件下其数值介于27.5～28.5 kJ/mol；②在去离子水溶液中，甲烷水合物的分解瞬时速度呈现先增加后减小的趋势，在分解早中期其累计分解物质的量随时间的变化关系呈指数函数形式增长，后期则呈缓慢线性增长；③在孔隙水溶液中，甲烷水合物的分解瞬时速度也呈现先增加后减小的变化趋势，但较之于去离子水溶液，孔隙水溶液中甲烷水合物的分解瞬时速度峰值出现的时间较晚，孔隙水溶液矿化度对水合物分解速度的促进作用弱于温度的影响；④对影响去离子水溶液中块状甲烷水合物分解速度的因素按照影响程度由大到小排序，结果依次为分解表面积、温度、压力。结论认为，在储层改造的基础上，热激法是块状甲烷水合物开采的合理方式。     

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??The thermal simulation experiment of coal rock can provide a scientific basis for understanding the evolution of hydrocarbon generation in coal??bearing basin and the geochemical characteristics of coalbed methane and its resource prediction. The thermal simulation experiments of gas generation of the upper Paleozoic coal rock samples collected from Qinshui Basin were carried out at the temperatures of 336.8-600 ?棬 the pressure of 50 MPa and the temperature??rising rates of 20 ??/h and 2 ??/h. The results indicated that the gaseous products (relative percent content) were mainly composed of methane?? C_2-5 hydrocarbon gases and carbon dioxide?? the bydrogen content and hydrogen sulfide content being extremely low?? along with the increase in simulation temperature?? the methane and hydrogen increased but carbon dioxide decreased?? and the C_2-5 hydrocarbon gases and hydrogen sulfide increased first and decreased afterwards?? the low temperature??rising rate was favourable to the generation of methane?? C_2-5 hydrocarbon gases?? hydrogen and carbon dioxide?? their formation being stage?? the relative productivity of carbon dioxide or hydrogen was positively correlated with that of methane at the same temperature??rising rate?? which reflects that they and the methane were the products of simultaneous parallel reaction in the process of the pyrolysis of coal rocks?? and the ability of generating methane and C_2-5 hydrocarbon gases of Shanxi Formation coal rocks was higher than that of Taiyuan Formation coal rocks at the same simulation temperature and temperature??rising rate?? which means that the Shanxi Formation coal rocks were more beneficial to coalbed methane formation in natural conditions. Finally?? the significance tracing coalbed methane formation is discussed in the paper according to the experimental results. (Financed by the National Basic Research Program Project??No. 2002CB211701)     

天然气水合物抑制过程中甲醇用量的影响

采用可视化高压流体测试装置,考察了甲醇含量对陕北某气田天然气水合物生成条件的影响。实验结果表明,气体组成对其水合物的生成条件有较大的影响,大分子气体或液态烃的存在可显著降低水合物的生成压力;甲醇含量对水合物生成的温度降有较大影响,甲醇含量越高,水合物生成温度降越大;水合物生成压力的对数(lgp)与温度(t_e)呈线性关系,不同甲醇含量时水合物生成条件的lgp～t_e曲线相互平行;甲醇质量分数小于30%时,Hammerschmidt方程和Nielsen-Bucklin方程对水合物生成温度降的预测偏差较小,但甲醇质量分数大于30%时,预测偏差较大;采用Nielsen-Bucklin修正式,预测甲醇用量的偏差小于2%。     

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.     

Water Content of Natural Gas in Equilibruim with Water

A new model for predicting water content of natural gas in equilibrium with water is obtained. This formula is a function of pressure and temperature and is applied within a wide range of temperatures and pressures. This new formula shows good data fit, with an average absolute error of 4.2 for 164 data points.     

川西坳陷新场气田须家河组五段流体赋存状态

川西坳陷新场气田上三叠统须家河组五段气藏试采均表现出气水同产,天然气究竟是以水溶气还是游离气为主尚无定论。为此,对该区须五段地层水开展了不同温压条件下的甲烷溶解度实验,并与1 mol/kg NaCl溶液中甲烷的溶解度进行对比,并结合现今产出流体气水比和理想气体状态方程,明确了须五段中流体的赋存状态。研究结果表明,在现今平均埋深和历史最大埋深状态下,新场须五段地层水中甲烷的溶解度分别为2.260 m³/m³和3.194 m³/m³。受白垩纪末以来地层抬升影响,新场须五段水溶气脱溶主要是地层抬升减压降温脱溶。在不同埋深状态下,游离气和地层水在孔隙中所占体积比例分别普遍低于和高于50%,白垩纪末以来地层温压降低使得须五段中游离气体积发生膨胀,所占体积比例略有增大,而地层水被驱替排出,所占体积比例有所降低。地层温压降低导致部分水溶气脱溶出来,在总的天然气中游离气所占比例增大而水溶气所占比例降低,须五段天然气以游离气为主,水溶气所占比例不足5%。在地层抬升过程中,新场须五段有约29.3%的水溶气脱溶成为游离气,地层水共脱溶出了约1.8×10⁹ m³的天然气。     

The Effect of Multi-walled Carbon Nanotubes on Solubility of Methane in Water

In this research, the effects of multi-walled carbon nanotubes (NTs) on dissolution of methane in water have been investigated. The tests were performed in a 370 CC vessel at pressures 3 and 5 bar and temperatures of 1–5°C. The solution volume was 300 CC. For any solution data of vessel pressure versus time and the total absorption capacity were collected. NTs were dispersed in water by using the sodium dodecyl sulfate (SDS) solution with a concentration of 1 wt% and applying ultrasonic agitation for 25 min. Utilization of 0.1 wt% SDS at a pressure of 3 bar reduced the dissolution capacity, while at the pressure of 5 bar a negligible increase was observed. Dissolution capacity increased up to 5.26% by using of NT along with SDS at the pressure of 5 bar and low temperatures. Utilization of SDS, NT, and their mixtures improved the pressure reduction slope of methane at low temperatures.     

石英吸附甲烷的蒙特卡罗研究

利用巨正则蒙特卡罗模拟方法对甲烷在石英中吸附行为进行了研究,并讨论了不同孔径、不同温度、不同含水量和不同组成对甲烷在石英中吸附行为的影响。研究结果表明：甲烷超额吸附量随着压力的增大而先上升后下降,且随着孔径增大逐渐减小;甲烷与石英相互作用能随着压力增大或孔径减小而减小,说明甲烷在孔中吸附逐渐由能量较高的吸附位向能量较低的吸附位转移;随着温度升高,甲烷等量吸附热减小,甲烷在孔中吸附逐渐由能量较低的吸附位向能量较高的吸附位转移,造成甲烷在石英孔中吸附能力降低,导致甲烷吸附量减小;水分子在孔中以定向方式占据着石英孔壁面,且受到范德华力和静电能共同作用在孔中以堆积形式存在;随着含水量增加,甲烷分子在孔中吸附位并没有随着发生变化,即水分子只占据甲烷分子吸附空间,造成甲烷吸附量减小;气体与石英间相互作用能量大小顺序为氮气>甲烷>二氧化碳,则石英上吸附能力大小的顺序为二氧化碳>甲烷>氮气;多组分竞争吸附中,甲烷在气相中摩尔分数降低、甲烷分子吸附位变化以及甲烷吸附空间减小,综合作用导致了甲烷吸附量减小。     

二氧化碳含量对天然气性质影响的实验研究

采用室内研究的方法,对CO2含量分别为10%,30%,50%,70%,90%,100%的天然气样品做了3个不同温度(20℃,30℃,40℃)下的恒组成膨胀实验测试研究。结果表明:随CO2含量由10%增大到100%,天然气样品的临界温度由-69.86℃增高到31.4℃,临界压力由4.85MPa增高到7.38MPa;温度不变,压力一定时,随着天然气中CO2含量的增高,天然气样品的相对体积呈增大的趋势,不同CO2含量的天然气样品随压力降低其体积膨胀规律表现出了类似CO2超临界状态的特征。以上认识对CO2和天然气混合气体驱油施工及今后更进一步的研究具有一定的借鉴意义。