Gas source of the Middle Jurassic Shaximiao Formation in the Zhongjiang large gas field of Western Sichuan Depression:Constraints from geochemical characteristics of light hydrocarbons

The Zhongjiang gas field is a typical large gas field in terrigenous strata of the Western Sichuan Depression.It remains debatable which member of the Upper Triassic Xujiahe Formation served as the source rocks and how significant the member contributed to the gas accumulations in the Zhongjiang gas field.In this study,we analyzed the essential characteristics of the Lower Jurassic source rocks and the geochemical features of light hydrocarbons in natural gas from the 2nd(T3χ^(2))and 4th members(T3χ^(4))of the Upper Triassic Xujiahe Formation(T3χ),as well as the Middle Jurassic Shaximiao(J2s)and Qianfoya(J2q)formations.Based on this,we explored the sources of the natural gas in the Zhongjiang gas field and determined the natural gas migration patterns and their effects on the properties of light hydrocarbons in the natural gas.The results indicate that the Lower Jurassic lacustrine source rocks of the Zhongjiang gas field contain humic organic matter,with vitrinite reflectance(R_(0))values ranging from 0.86%to 0.98%.Samples meeting the criterion for effective source rocks[total organic carbon(TOC)content≥0.75%]exhibited an average TOC content of merely 1.02%,suggesting significantly lower hydrocarbon generation potential than source rocks in the underlying T3x,which show higher thermal maturity and TOC contents.For natural gas samples from T3χ^(2),T3χ^(4),J2s,and J2q reservoirs,their C_(5-7)iso-alkane content was significantly higher than their n-alkane content,and their methylcyclohexane(MCH)index ranged from 59.0%to 77.3%,indicating the predominance of methylcyclohexane in C_(7)light hydrocarbons.As indicated by the origin identification and gas-source correlation based on the geochemical features of light hydrocarbons,the natural gas in the Zhongjiang gas field is typical coal-derived gas.The gas from the primary pay zone of the Shaximiao Formation,with significantly high K_(1),(P_(2)+N_(2))/C_(7),and P_(3)/C_(7)values,predominantly originated from the 5th member of the T3x and migrated in the free phase,with a small amount possibly sourced from the Lower Jurassic source rocks.The dissolution and adsorption during gas migration led to a decrease in the aromatic content in C_(6-7)light hydrocarbons and an increase in the isoheptane values.Therefore,their effects must be considered when determining the gas origin and thermal maturity based on the aromatic content in C_(6-7) light hydrocarbons and iso-heptane values.

Tracing of natural gas migration by light hydrocarbons:A case study of the Dongsheng gas field in the Ordos Basin,NW China

Based on the analysis of light hydrocarbon compositions of natural gas and regional comparison in combination with the chemical components and carbon isotopic compositions of methane,the indication of geochemical characteristics of light hydrocarbons on the migration features,dissolution and escape of natural gas from the Dongsheng gas field in the Ordos Basin is revealed,and the effect of migration on specific light hydrocarbon indexes is further discussed.The study indicates that,natural gas from the Lower Shihezi Formation(Pix)in the Dongsheng gas field displays higher iso-C5-7contents than n-C5-7contents,and the C6-7light hydrocarbons are composed of paraffins with extremely low aromatic contents(<0.4%),whereas the C7light hydrocarbons are dominated by methylcyclohexane,suggesting the characteristics of coal-derived gas with the influence by secondary alterations such as dissolution.The natural gas from the Dongsheng gas field has experienced free-phase migration from south to north and different degrees of dissolution after charging,and the gas in the Shiguhao area to the north of the Borjianghaizi fault has experienced apparent diffusion loss after accumulation.Long-distance migration in free phase results in the decrease of the relative contents of the methylcyclohexane in C7 light hydrocarbons and the toluene/n-heptane ratio,as well as the increase of the n-heptane/methylcyclohexane ratio and heptane values.The dissolution causes the increase of isoheptane values of the light hydrocarbons,whereas the diffusion loss of natural gas in the Shiguhao area results in the increase of n-C5-7contents compared to the iso-C5-7contents.

天然气运移轻烃地球化学示踪--以鄂尔多斯盆地东胜气田为例

基于天然气中轻烃化合物组成分析和区域性对比,结合组分和甲烷碳同位素组成特征,揭示轻烃地球化学特征对鄂尔多斯盆地东胜气田上古生界天然气运移和水溶及逸散等示踪作用,探讨运移作用对特定轻烃指标的关联效应。研究表明:①东胜气田二叠系下石盒子组天然气C5−7异构烷烃含量高于正构烷烃,C6−7轻烃组成呈链烷烃优势分布且芳香烃含量明显偏低(小于4.0%),C7轻烃主体呈甲基环己烷优势分布,整体表现出煤成气特征且受到了水溶等作用影响;②东胜气田天然气经历了自南向北的游离相运移,并在充注后发生不同程度的水溶作用,其中泊尔江海子断裂以北什股壕地区天然气在聚集后具有明显的散失;③长距离的游离相运移导致天然气C7轻烃中甲基环己烷相对含量和甲苯/正庚烷值降低、正庚烷/甲基环己烷值和庚烷值增大,水溶作用导致轻烃异庚烷值增大,天然气散失导致什股壕地区天然气中C5−7正构烷烃相对异构烷烃含量增加。

4-Pyrazolecarboxylic Acid-based MOF-5 Analogs Framework with High Adsorption and Separation of Light Hydrocarbons

One porous framework [Zn4（μ4-O）（μ4-4-pca）3]·2（DEF）·2（H2O）（1, 4-H2Pca = 4-pyrazolecarboxylic acid, DEF = N,N-diethylformamide） with MOF-5 type topology has been synthesized solvothermally. Significantly, this compound exhibits high capacity of C2 hydrocarbons. C2H2 capacity could compare with the highest value of the reported MOFs, far exceeding that of MOF-5, as well as the high selectivity adsorption of C2s over C1.

Compositional and geochemical characteristics of light hydrocarbons for typical marine oils and typical coal-generated oils in China

Different types of crude oils have different light hydrocarbon compositional and geochemical character-istics. Based on the light hydrocarbon data from two kinds of oils,i.e.,coal-generated oils and marine oils in China,light hydrocarbons in marine oils in the Tazhong area are generally relatively enriched in n-heptane,and coal-generated oils from the Turpan Basin are enriched in methylcyclohexane . The K1 values,reported by Mango (1987),range from 0.97 to 1.19 in marine oils,basically consistent with what was reported by Mango on light hy-drocarbons in terms of the majority of the crude oil data. But the K1 values of coal-generated oils are particularly high (1.35-1.66) and far greater than those of marine oils; heptane values in marine oils,ranging from 32.3% to 45.4%,and isoheptane values,ranging from 1.9 to 3.7,are respectively higher than those of coal-generated oils,in-dicating that the oils are in the high-maturity stage. In addition,expulsion temperatures of coal-generated oils from the Turpan Basin are obviously lower than those of marine oils from the Tazhong area.

Origin of hydrocarbon fluids and discussion of abnormal carbon isotopic compositions in the Lishui-Jiaojiang Sag,East China Sea Shelf Basin

The hydrocarbon gases in the L1 gas field of the Lishui-Jiaojiang Sag have been commonly interpreted to be an accumulation of pure sapropelic-type thermogenic gas.In this study,chemical components,stable isotopic compositions,and light hydrocarbons were utilized to shed light on the origins of the hydrocarbon fluids in the L1gas pool.The hydrocarbon fluids in the L1 gas pool are proposed to be a mixture of three unique components:mid-maturity oil from the middle Paleocene coastal marine Lingfeng source rock,oil-associated(late oil window)gas generated from the lower Paleocene lacustrine Yueguifeng source rock,and primary microbial gas from the paralic deposits of the upper Paleocene Mingyuefeng source rock.Here,for the first time,the hydrocarbon gases in the L1 gas pool are diagnosed as mixed oil-associated sapropelic-type gas and microbial gas via four pieces of principal evidence:(1)The abnormal carbon isotopic distributions of all methane homologues from C_(1)(CH_(4)or methane)to C_(5)(C_(5)H_(12)or pentane)shown in the Chung plot;(2)the diagnostic~(13)C-depleted C_(1)compared with the thermogenic sapropelic-type gas model,whileδ^(13)C_(2)(C_(2)H_(6)or ethane)andδ^(13)C_(3)(C_(3)H_(8)or propane)both fit perfectly;(3)the excellent agreement of the calculated carbon isotopic compositions of the pure thermogenic gas with the results of the thermal simulated gas from the type-II1 kerogen-rich Yueguifeng source rock;and(4)the oil-associated gas inferred from various binary genetic diagrams with an abnormally elevated gas oil ratio.Overall,the natural gases of the L1 gas pool were quantified in this study to comprise approximately 13%microbial gas,nearly 48%oil-associated sapropelic-type gas,and 39%of nonhydrocarbon gas.The microbial gas is interpreted to have been codeposited and entrained in the humic-kerogen-rich Mingyuefeng Formation under favorable lowtemperature conditions during the late Paleocene-middle Eocene.The microbial gas subsequently leaked into the structurally and stratigraphically complex L1 trap with oil-associated sapropelic-type gas from the Yueguifeng source rock during the late Eocene-Oligocene uplifting event.A small amount of humic-kerogen-generated oil in the L1 gas pool is most likely to be derived from the underlying Lingfeng source rock.The detailed geological and geochemical considerations of source rocks are discussed to explain the accumulation history of hydrocarbon fluids in the L1 gas pool.This paper,therefore,represents an effort to increase the awareness of the pitfalls of various genetic diagrams,and an integrated geochemical and geological approach is required for hydrocarbonsource correlation.

Permeation Characteristics of Light Hydrocarbons Through Poly（amide-6-β-ethylene oxide） Multilayer Composite Membranes

In this paper, poly(amide-6-β-ethylene oxide) (PEBA1657) copolymer was used to prepare multilayer polyetherimide (PEI)/polydimethylsiloxane (PDMS)/PEBA1657/PDMS composite membranes by dip-coating method. Permeation behaviors of ethylene, ethane, propylene, propane, n-butane, methane and nitrogen through the multilayer composite membranes were investigated over a range of operating temperature and pressure. The permeances of light hydrocarbons through PEI/PDMS/PEBA1657/PDMS composite membranes increase with their increasing condensability, and the olefins are more permeable than their corresponding paraffins. For light hydrocarbons, the gas permeances increase significantly as temperature increasing. When the transmembrane pressure difference increases, the gas permeance increases moderately due to plasticization effect, while their apparent activation energies for permeation decrease.

ZSM-5浸渍Zn催化甲醇耦合轻烃改质芳构化反应研究

采用等体积浸渍法,对ZSM-5分子筛进行了4种不同质量分数Zn的负载改性,并对浸渍Zn的ZSM-5分子筛样品进行了XRD、N2-吸脱附和NH3-TPD表征和催化甲醇耦合轻烃改质芳构化反应研究。研究结果证明:ZSM-5分子筛样品浸渍Zn后比表面积、孔体积和酸量减少,并且随着浸渍Zn质量分数的增大,比表面积、孔体积和酸量减少越大,这可能是由于分子筛引入锌物种后,锌物种堵塞孔道,导致其比表面积和孔体积缩小;400℃,0.4 MPa(N_(2)),质量空速为1.0 h-1(甲醇:抽余油=1:1)时,负载Zn后ZSM-5分子筛催化剂的催化性能得到提高,在负载量为2.0%时,ZSM-5分子筛催化剂具有最优的催化性能,此时甲醇转化率100%,芳烃选择性34.18%,辛烷值91(RON),证实浸渍Zn后有利于甲醇耦合轻烃改质芳构化反应的发生。

The Variance of Mango's Light-Hydrocarbon Parameter K

The analyses of light hydrocarbons in oils from the Tarim Basin show that the Man-go’s parameter K is about unity except those oils trapped in the eastern part of the Tazhong (Central Tarim) Fault Uplift. The regular variance of K may indicates the accumulation and admixture of the oil populations in the eastern part of the Tazhong Fault Uplift.

Origin of condensate oil and natural gas in Bozhong 19-6 gas field,Bohai Bay Basin

The discovery of the Bozhong 19-6 gas field has opened a new frontier for deep gas exploration in the Bohai Bay Basin,with a great potential for further gas exploration.However,poor understanding of oil and gas origin has been limiting the exploration progress in this area.To clarify the origin of condensate oil and gas in Bozhong 19-6 gas field,this study adequately utilized the organic geochemical analysis data to investigate the composition and geochemical characteristics of condensate oil and natural gas,and analyzed the relationship between condensate oil and the three sets of source rocks in the nearby subsags.Results show that the lighter components dominate the condensate oil,with a forward type predominance.The parent material of crude oil was primarily deposited in a shallow,clay-rich,low-salinity,weakly reducing aquatic environment.The condensate and natural gas have similar parent source characteristics and maturity,with Ro ranging from 1.4%to 1.6%.Both are products of high maturity stage,indicating that they are hydrocarbon compounds produced by the same group of source rocks in the same stage.Oil-sources correlation shows that condensate oil and gas mainly originate from the source rocks of the third member of Shahejie Formation in the nearby subsags of the Bozhong 19-6 structural belt.

反应压力对HZSM-5催化正癸烷裂解反应性能影响

以HZSM-5分子筛为原料,制备具有微米及纳米尺寸的HZSM-5/MCM-41微孔-介孔复合分子筛催化剂。通过调节反应压力,探究催化剂在不同反应条件下对正癸烷催化裂解反应的影响。结果表明,在低压条件下,反应流体密度随系统压力升高而增大,有利于低碳烯烃芳构化,从而使得低碳烯烃选择性降低;当压力进一步增至高压时,主要裂解产物均位于近临界或超临界状态,进而降低低碳烯烃芳构化程度,提高低碳烷烃含量。

Calculation and application of partition coefficients of light hydrocarbons in oil-based mud system

To find out the relationship between the oil-based mud,the formation fluid and the extracted gas,we use a thermodynamic approach based on static headspace gas chromatography technique to calculate the partition coefficients of 47 kinds of light hydrocarbons compounds between nC5 and nC8 in two kinds of oil-based mud-air systems,and reconstruct the original formation fluid composition under thermodynamic equilibrium.The oil-based drilling mud has little effect on the formation fluid compositions in the range of nC5-nC8(less than 1%for low-toxicity oil-based mud and less than 10%for oil-based mud).For most light hydrocarbon compositions,the partition coefficients obtained by vapor phase calibration and the direct quantitative methods have errors of less than 10%,and the partition coefficients obtained by direct quantitative method are more accurate.The reconstructed compositions of the two kinds of crude oil have match degrees of 91%and 89%with their real compositions,proving the feasibility and accuracy of reconstructing the composition of original formation fluid by using partition coefficients of light hydrocarbon compositions between nC5 and nC8.

ZIF-8纳米流体天然气乙烷回收工艺的产品纯度关键影响因素分析

天然气乙烷回收可为乙烷裂解制乙烯提供优质的原料。多孔纳米流体吸收-吸附耦合分离是一种新兴的气体分离技术,基于ZIF-8/水-乙二醇纳米流体,利用传统的吸收-解吸流程,可高效低耗地回收天然气中的乙烷。利用平衡级法对多孔纳米流体天然气乙烷回收工艺建模,提高乙烷产品纯度是流程模拟的一个重要目标,而模拟结果表明吸收-吸附塔理论板数和闪蒸压力是影响乙烷产品纯度的关键因素。随着吸收-吸附塔理论板数增加,乙烷产品纯度先明显升高,后趋于稳定。通过绘制y-x图可知,乙烷产品纯度难以持续升高的原因是操作线趋近了相平衡线。随着闪蒸压力降低,乙烷产品纯度升高,其原理为闪蒸压力影响了吸收-吸附塔的闪蒸再沸比,而闪蒸再沸比与乙烷产品纯度呈正相关。

Correction Method of Light Hydrocarbons Losing and Heavy Hydrocarbon Handling for Residual Hydrocarbon (S_1) from Shale

In China, hot researches on shale oil were raised by the important breakthrough of shale oil in America. Obviously, the first important issue is the actual shale oil resource potential of China, and the selection of the key appraisement parameter is vital to the shale oil resource amount. Among the appraisement parameters, the oil content parameter（S1） is the key one, but the evaluation result is generally lower because of light hydrocarbon losing and heavy hydrocarbon handling. And the more important thing is that the light hydrocarbon with small molecular weight is more recoverable, and therefore its amount is important to the total shale oil yields. Based on pyrolysis experiments and the kinetic model of hydrocarbon generation, correction factors and a model of light hydrocarbon losing and heavy hydrocarbon handling were established. The results show that the correction factor of heavy hydrocarbon handling is 3.2, and that of light hydrocarbon losing is controlled by kerogen type, maturity and hydrocarbon generation environment（closed or open）.

The effect of slight to minor biodegradation on C_6 to C_7 light hydrocarbons in crude oils: a case study from Dawanqi Oilfield in the Tarim Basin,NW China

Light hydrocarbons(LHs) are one of the main petroleum fractions in crude oils, and carry much information regarding the genetic origin and alteration of crude oils. But secondary alterations—especially biodegradation—have a significant effect on the composition of LHs in crude oils. Because most of the LHs affected in oils underwent only slight biodegradation(rank 1 on the biodegradation scale), the variation of LHs can be used to describe more the refined features of biodegradation. Here,23 crude oils from the Dawanqi Oilfield in the Tarim Basin, NW China, eleven of which have been biodegraded to different extents, were analyzed in order to investigate the effect of slight to minor biodegradation on C_6–C_7 LHs.The study results showed that biodegradation resulted in the prior depletion of straight-chained alkanes, followed by branched alkanes. In slight and minor biodegraded oils,such biodegradation scale could not sufficiently affect C_6–C_7cycloalkanes. For branched C_6–C_7 alkanes, generally,monomethylalkanes are biodegraded earlier than dimethylalkanes and trimethylalkanes, which indicates that branched alkanes are more resistant to biodegradation, with the increase of substituted methyl groups on parent rings.The degree of alkylation is one of the primary controlling factors on the biodegradation of C_6–C_7 LHs. There is a particular case: although 2,2,3-trimethylbutane has a relative higher alkylation degree, 2,2-dimethylpentane is more resistant to biodegradation than 2,2,3-trimethylbutane. 2,2-Dimethylpentane is the most resistant to biodegradation in branched C_6–C_7 alkanes. Furthermore, the 2-methylpentane/3-methylpentane and 2-methylhexane/3-methylhexane ratios decreased steadily with increasing biodegradation,which implies that isomers of bilateral methyl groups are more prone to bacterial attack relative to mid-chain isomers. The position of the alkyls on the carbon skeleton is also one of the critical factors controlling the rate of biodegradation. With increasing biodegradation, Mango's LH parameters K1 values decrease and K2 values increase,the values of n-heptane and isoheptane decrease, and the indices of methylcyclohexane and cyclohexane increase.LH parameters should be applied cautiously for the biodegraded oils. Because biodegraded samples belong to slight or minor biodegraded oils, the values of n-heptane and isoheptane from Dawanqi Oilfield can better reflect and determine the ‘‘Biodegraded'' zone. When the heptane value is 0–21 and the isoheptane value is 0–2.6, the crude oil in Dawanqi Oilfield is defined as the ‘‘Biodegraded'' zone.

Light Hydrocarbons in Fluid Inclusions and Their Constraints on Ore Genesis:A Case Study of the Songxi Ag(Sb)Deposit,Eastern Guangdong,China

The Songxi deposit is a newly discovered large Ag (Sb) deposit. By using a suite of high-vacuum quadrupole gas mass spectrometer systems, the authors have recognized many kinds of light hydrocarbons in fluid inclusions of minerals. These hydrocarbons are mainly composed of C1-C4 saturated alkanes, while the contents of C2-C4 unsaturated alkenes and aromatic hydrocarbons are quite low, suggesting that the metallogenic processes have not been affected by magmatic activities. Chemical equilibrium studies show that these hydrocarbons may be a mixture of organic gases generated by microorganism activity and those by thermal cracking of type-n kerogens (kukersite) in sedimentary host rocks, and the former may constitute more than two-thirds, implying that microorganism might have played an important role in the metallogenesis. The equilibrium temperature of the latter is about 300℃, which is much higher than the geothermal temperature at the estimated depth of metallogenesis. Thus, the light hydrocarbons generated by thermal cracking of kerogens probably originated in the deep part of the sedimentary basins and then migrated through a long distance to shallower horizons of the basin. Based on the composition of light hydrocarbons in fluid inclusions, the authors infer that the Songxi deposit was formed in a continental rift. The analytical data presented in this paper support from one aspect the genetic model that the Songxi deposit may be a sedimentary hot brine transformed deposit instead of a submarine basic volcanic exhalation and low-medium temperature volcanic hydrothermal fluid filling deposit proposed by most previous researchers.

Compositional characteristics and geochemical significance of light hydrocarbons for crude oils in Tarim Basin, China

Light hydrocarbons, especially C-7 isoalkanes, cyclopentanes, cyclohexanes and n-heptane in 540 oils from the Tarim Basin were studied systematically. The results suggested the K-1 values [(2-MH+2,3-DMP)/(3-MH+2,4-DMP)] of crude oils vary from a lowest value of {0.78}, to a highest value of {1.54}, but the K-1 values of the majority of oil samples (80%) range from {0.90} to {1.20}. However, the absolute contents of (2-methylhexane+ 2,3-dimethylpentane) and (3-methylhexane+2,4-dimethylpentane) in the total light hydrocarbons (C-4-C-7) show a similar variation trend. The variation of K-1 values of crude oils can suggest a typical sedimentary environment for source rocks. Therefore, according to the compositional characteristics of C-7 light hydrocarbons in light of the steady-state catalytic hypothesis, non-marine oils from the Yingmaili area and marine oils from the Tazhong uplift in the Tarim Basin were genetically classified.

轻烃蒸汽重整制氢催化剂RSR-101/RSR-102的工业应用

中石化石油化工科学研究院有限公司开发的轻烃蒸汽重整制氢催化剂RSR-101/RSR-102在中国石化洛阳分公司4×10^(4)m^(3)/h制氢装置首次实现工业应用。工业标定结果表明,在反应压力为2.65 MPa、水碳摩尔比为3.33、转化炉入口温度为508.9℃、转化炉出口温度为772.5℃的条件下,轻烃折合成甲烷的转化率为79.7%,制氢装置单位产品的能耗较设计值降低了12.8%,每生产1 t H_(2)的CO_(2)排放量为8.01 t。制氢装置换装RSR-101/RSR-102催化剂组合后的各项运行参数均达到技术协议要求。

Synthesis of light hydrocarbons from CO hydrogenation over Co_xMn_(0.06)/SiO_2

A series of CoxMn0.06/SiO2 catalysts were prepared by an impregnation method for catalytic hydrogenation of CO to Light Hydrocarbons(LHCs).The catalysts were characterized by XRD,SEM,N2 adsorption and NH3-TPD techniques.Catalyst activities were evaluated in a high-pressure micro reactor.The results show that the performance of the catalysts was significantly affected by the amount of Co loaded onto the substrate.The activity of the Co0.10Mn0.06/SiO2 catalyst was stable with time-on-stream.The CO conversion and LHCs selectivity were 95.3% and 98.1%,respectively,for this catalyst at 400 °C.

LIGHT、IFN-γ基因转染人肝癌HepG2细胞凋亡及其Caspase-3和survivin表达

目的观察LIGHT、IFN-γ基因转染人肝癌细胞HepG2的凋亡及其Caspase-3和survivin的表达变化。方法用LIGHT、IFN-γ真核细胞表达质粒pcDNA4C-LIGHT-cDNA、pcDNA4C-IFN-γ-cDNA及其转化的E.coliJM-109感受态大肠杆菌,经质粒提取后,转染人肝癌细胞HepG2,同时设对照组(未转染)。分别于转染后12、24、48 h收集HepG2细胞。流式细胞仪检测细胞凋亡和Caspase-3、survivin。结果转染后细胞凋亡及Caspase-3表达量在对照组、LIGHT单转组、联合转染组呈逐渐递增趋势,survivin表达量呈递减趋势。结论LIGHT转染后能通过调节HepG2细胞Caspase-3及survivin的表达来发挥促细胞凋亡作用,INF-γ能增强LIGHT诱导的HepG2细胞凋亡,且显著上调其Caspase-3的表达。