The controlling factors and distribution prediction of H2S formation in marine carbonate gas reservoir, China

Generally, there are some anhydrites in carbonate reservoir, as H2S is also familiar in carbonate oil and gas reservoirs. Nowadays, natural gas with high H2S concentration is usually considered as TSR origin, so there is close relationship between H2S and anhydrite. On the contrary, some carbonate rocks with anhydrite do not contain H2S. Recently, researches show that H2S is only a necessary condition of H2S formation. The reservoir porosity, sulfate ion content within formation water, reservoir temperature, oil/gas and water interface, hydrocarbon and some elements of reservoir rock have great controlling effects on the TSR occurrence. TSR deoxidizes hydrocarbon into the acidic gas such as H2S and CO2, and the H2S formation is controlled by TSR occurrence, so the relationship among reaction room, the contact chance of sulfate ion and hydrocarbon, the reservoir temperature has great influence on the TSR reaction. H2S has relatively active chemical quality, so it is still controlled by the content of heavy metal ion. Good conditions of TSR reaction and H2S preservation are the prerequisite of H2S distribu- tion prediction. This paper builds a predictive model based on the characteristic of natural gas reservoir with high H2S-bearing. In the porosity reservoir with anhydrite, the formation water is rich in sulfate and poor in heavy metal ion. Oil and gas fill and accumulate in the gas reservoir with good preservation conditions, and they suffered high temperature later, which indicates the profitable area of natural gas with high H2S-bearing.     

The controlling factors and distribution prediction of H_2S formation in marine carbonate gas reservoir,China

Generally, there are some anhydrites in carbonate reservoir, as H2S is also familiar in carbonate oil and gas reservoirs. Nowadays, natural gas with high H2S concentration is usually considered as TSR origin, so there is close relationship between H2S and anhydrite. On the contrary, some carbonate rocks with anhydrite do not contain H2S. Recently, researches show that H2S is only a necessary condition of H2S formation. The reservoir porosity, sulfate ion content within formation water, reservoir temperature, oil/gas and water interface, hydrocarbon and some elements of reservoir rock have great controlling effects on the TSR occurrence. TSR deoxidizes hydrocarbon into the acidic gas such as H2S and CO2, and the H2S formation is controlled by TSR occurrence, so the relationship among reaction room, the contact chance of sulfate ion and hydrocarbon, the reservoir temperature has great influence on the TSR reaction. H2S has relatively active chemical quality, so it is still controlled by the content of heavy metal ion. Good conditions of TSR reaction and H2S preservation are the prerequisite of H2S distribution prediction. This paper builds a predictive model based on the characteristic of natural gas reservoir with high H2S-bearing. In the porosity reservoir with anhydrite, the formation water is rich in sulfate and poor in heavy metal ion. Oil and gas fill and accumulate in the gas reservoir with good preservation conditions, and they suffered high temperature later, which indicates the profitable area of natural gas with high H2S-bearing.     

川东南二三叠系气藏硫化氢成因探讨

通过天然气组分、碳氢同位素组成与薄片、包裹体等资料分析,研究了川东南二-三叠系的长兴组、飞仙关组与茅口组气藏H₂S成因。结果表明,天然气组分以烷烃气为主,非烃含量平均24.68%。其中,烷烃气均偏干,部分样乙烷低于检测下限,可测样乙烷含量0.03%~0.39%,均值0.15%;δ¹³C₁值均偏重,为–28.3‰~–35.2‰,平均–31.1‰,部分样出现δ¹³C₁ > δ¹³C₂倒转。非烃以CO₂和H₂S为主,H₂S含量1.0%~21.7%,平均5.3%。储层中代表原油充注与古油藏裂解的各类沥青较少见,方解石脉中烃类包裹体以含气态烃包裹体为主,含油包裹体少见。结合前人研究成果认为,川东南茅口组几乎不含H₂S的岩溶缝洞型气藏（分布于涪陵北部与綦江地区）未见遭TSR改造迹象;飞仙关组气藏（分布于涪陵北部）、长兴组气藏（主要分布于涪陵北部与中部）与茅口组热液白云岩气藏（分布于涪陵中南部）的H₂S均为TSR成因,部分遭受TSR改造气藏现今H₂S含量较低或为后期被消耗所致;其中,飞仙关组参与TSR反应的烃类以液态烃为主,而其他层位气藏以气态烃（甲烷）为主,这可能与TSR发生时储层中是否存在一定量液态烃有关。TSR反应于各层内独立发生,并非飞仙关组发生后向下“倒灌”。长兴组TSR反应所需硫源或来自飞仙关沉积期卤水的侧向排泄,茅口组硫源或来自相邻层位富含SO₄^2-流体。     

列车餐车油烟雾的采集及化学成分分析

本文采用气相色谱质谱联用仪(GC/MS)对采集于列车餐车的食用油烟雾样品进行全谱分析,发现样品有66种化合物,包括烃类、卤代烃类、醇酚醚类、醛酮类、羧酸及衍生物类、芳稠环杂环类和胺类等七类,其中一些化合物如芳杂环化合物、卤代烃和胺类等具有毒性作用     

Simulation experiments on the reaction system of CH4-MgSO4-H2O

H2S-rich gas in carbonate reservoirs is usually attributed to thermochemical sulfate reduction （TSR）. In this paper, thermal simulation experiments on the reaction system of CH4-MgSO4-H2O were carried out using autoclave at 425℃--525℃. The threshold temperature for initiating TSR is much lower than our previous studies （550℃）. Properties of the reaction products were analyzed by microcoulometry, gas-chromatography （GC）, Fourier transform-infrared spectrometry （FT-IR） and X-ray diffraction （XRD） methods. Thermodynamics and reaction kinetics of TSR processes were investigated on the basis of the experimental data. The results show that thermochemical reduction of magnesium sulfate with methane can proceed spontaneously to produce magnesium oxide, hydrogen sulfur, and carbon dioxide as the main products, and high temperature is thermodynamically favorable to the reaction. Ac- cording to the reaction model, the calculated activation energy of TSR is 101.894 kJ/mol, which is lower than that by most previous studies. Mg^2＋ may have played a role of catalytic action in the process of TSR. The elementary steps of TSR and reaction mechanism were discussed tentatively. The study can provide important information on the explanation of geochemical depth limit for natural gas and on the generation of high H2S gas in deep carbonates reservoirs.     

药用皖鄂鼠尾草精油成分的初步分析

以同时蒸馏萃取法提取了药用皖鄂鼠用草精油，用毛细管ＧＣ／ＭＳ／ＤＳ联用仪分离并初步鉴定了其中的３５种化合物，占总峰面积的８７％的再用气相色谱－傅里叶红外光谱联用技术、双柱程序升温保留指数和标样核对等方法鉴定了１９种化合物，占总峰面积２５％。     

紫花地丁挥发性化学成分的分析

用同时蒸馏-萃取装置提取紫花地丁挥发性物质,测得紫花地丁挥发油的含量为1．65％,用GC／MS法从紫花地丁挥发油中分离并确定出36种化学成分,占挥发油总量的83．92％。用峰面积归一化法通过化学工作站数据处理系统得出各化学成分在挥发油中的相对百分含量。     

稠油硫酸盐热化学还原生成H2S实验研究

为了研究稠油注汽热采过程中生成H₂S机理，以Na₂SO₄，CaSO₄，MgSO₄，Fe₂（SO₄）₃，Al₂（SO₄）₃与稠油硫酸盐热化学还原（TSR）实验为基础，探究稠油TSR生成H₂S机理。实验表明，不同硫酸盐与稠油反应生成H₂S不尽相同，硫酸盐的阳离子所带电荷数决定TSR反应程度的难易，电荷数越多越容易进行反应，且H₂S生成量顺序为Al₂（SO₄）₃>Fe₂（SO₄）₃ > MgSO₄ > CaSO₄ > Na₂SO₄，但生成的烃量顺序为Fe₂（SO₄）₃ > Al₂（SO₄）₃ > MgSO₄ > CaSO₄ > Na₂SO₄。与其他硫酸盐不同的是，由于Fe₂（SO₄）₃的氧化性，Fe³⁺可能与生成的H₂S进一步反应。通过傅里叶红外变换光谱（FT-IR）对固相检测发现，不仅存在金属氧化物（CaO，MgO，Fe₂O₃，Al₂O₃）还存在FeS₂。最后，通过对MgSO₄油相硫含量的检测发现，反应后硫含量高于原油硫含量，证明了无机硫向有机硫的转化。     

钾盐在烟草燃烧过程中的作用

采用等体积浸渍法分别在烟草中加入硝酸钾KNO3、柠檬酸钾K3C6H5O7、草酸钾K2C2O4及酒石酸钾K2C4H4O6，并用差热分析（differential thermal analysis,DTA)、程序升温反应在线质谱分析（temperature-programmed reaction mass spectrometry on-line analysis,TPR-MS)方法对烟草进行了表征，用气相色谱法考察了主流烟气中CO含量的变化。结果表明，加入钾盐后，CO含量都有不同程度的降低。在钾盐含量为0．2475mmol/g的上述四种烟草样品上，烟气中CO含量按空白烟草T＞KNO3／T＞K2C2O4／T＞K3C6H5O7／T＞K2C4H4O6／T顺序排列。DTA给出的低温峰减弱、高温峰增强的结果表明，K^ 的加入改变了烟草燃烧过程中物质的转化历程，从而降低了卷烟的燃烧温度。通过对TPR－MS和DTA结果的联合分析，得出由于钾与烟草中的有机组分作用，含不同钾盐的烟草燃烧时产生了类似的含钾中间物质。证实了K^ 对烟草燃烧的作用机理，说明了钾盐降低烟草燃烧温度的原因。最后，还分析了主流烟气中CO含量的变化与DTA结果间的联系。     

Discussion of gas enrichment mechanism and natural gas origin in marine sedimentary basin,China

There are abundant natural gas resources in Chinese marine sedimentary basin. The exploration hot shots of natural gas are the Palaeozoic marine strata here in recent years, and several large scale gas fields have been discovered. Chinese Palaeozoic high-post matured and coal measure hydrocarbon source rocks are mainly prone to gas generation in the present. This research considered that gas source rocks and TSR are the key cause of gas enrichment of marine strata. High-quality argillaceous and coal measure hydrocarbon rocks are distributed widely in the Palaeozoic marine strata, which have been in highly matured phase in the present. The argillaceous source rock generally contains various sulfates that could accelerate crude oil cracking to gas for TSR occurrence, and coal measure source rock mainly generates gas, so Chinese marine basin gives priority to accumulating gas. Marine strata have not founded oil reservoirs in the Sichuan Basin and Ordos Basin, and they consist mainly of dry gas. Marine natural gases are the mixed gases of oil cracking gas and coal-formed gas in a general way, oil cracking gases contain usually some H2S and CO2. Hydrocarbon carbon isotopes are very complicated, and methane and ethane isotopic values bear apparent reversal caused by thermal evolution and mixing among different genetic types of natural gas. Coal-formed gases are the main component of Chinese marine natural gas. The Upper Permian of the Sichuan Basin and the Carboniferous-Permian of the Ordos Basin coal measure hydrocarbon source rock present large hydrocarbon generation potential, which are the prospecting highlight of marine natural gas hereafter. Oil cracking gas exploration will be paid much attention to in the Tarim Basin because of the lack of coal measure hydrocarbon source rock.     

某型航空发动机润滑油热衰变结构组成分析

利用高温反应釜与傅立叶红外光谱(FTIR)、气相色谱/质谱联用(GC/MS)技术,从分子水平分析添加有抗氧剂N-苯基-α-萘胺(T531)的聚α-烯烃(PAO)航空润滑基础油高温衰变,考察该润滑油的热安定性能.结果显示:低于200℃时,T531具有优良的抗氧化作用,能够较好地延缓基础油的高温衰变,但温度超过270℃后,T531的抗氧化性能降低,无法有效保护基础油.300℃高温产物经GC/MS分析,共检测到63种化合物,包括36种烷烃类化合物、25种烯烃类化合物、1种酮类化合物和抗氧剂T531,短链烷烃和烯烃的相对含量分别为5.835%和2.32%,是200℃高温时的20多倍,直接导致润滑油黏度的降低.在200℃高温反应油样中的T531相对含量仅为0.734%,远低于170℃和300℃反应后的2.019%和1.587%.可见,T531在200℃环境中消耗剧烈,对润滑基础油分子的抗氧化保护作用十分显著.     

黔产香根油的研究

以贵州罗甸引种的香根草为原料，用常规方法提取香根油，得率０．８％左右，用气相色谱仪和色谱－质谱联用仪，对香根油的化学成分作初步分析，共分离出６０多个组分，得质谱图３３张，鉴定出２６个成分，查明黔产香根油总醇含量达５０％左右，具有开发价值。     

油页岩CS_2-NMP萃取物中含氧化合物的分离与分析

为实现依兰油页岩萃取物中含氧化合物的分离与分析,采用索氏萃取法,在60℃条件下以CS2-NMP为萃取剂萃取依兰油页岩。用TiCl4/CuCl2两步络合法和硅胶柱色谱法对依兰页岩油中的含氧化合物进行富集,并对含氧洗脱组分进行了气相色谱-质谱串联(GC/MS)分析。结果表明:TiCl4/CuCl2两步络合法可以实现油页岩中含氮化合物的分离,脱氮率为82%,硅胶柱色谱可以实现对页岩油中含氧化合物的富集,富集组分中,氧元素的质量分数为10.69%;柱色谱富集组分中鉴定出32种含氧化合物,其组成以酚、酮、醚、酯以及有机硅氧化合物为主;在这些含氧化合物中发现了甾醇类、萜类化合物的衍生物以及酰胺基团,说明依兰油页岩中的氧可能来源于成矿的高等植物和蓝绿藻。该结果可以为依兰油页岩资源的合理利用、油页岩的成因和油母结构研究提供参考。     

高含硫化氢天然气气侵时的溢流特性

以四川某高含H2S气体的气井井身结构及钻井工况为基础,针对高含H2S气井溢流时的特点,考虑H2S在水中的溶解度,建立溢流期间环空各相流体的质量和动量守恒方程,并用有限差分法对方程进行求解。结果表明:H2S在井底的溶解度远大于CH4的,在距井口约360 m开始大量析出;H2S的含量越高,气体在上升过程中密度变化越大,气体开始剧烈膨胀的位置越接近井口;井底侵入气体量相同的情况下,H2S的含量越高,气体的膨胀倍数越大,泥浆池增量也越大,同时,刚开始气侵时H2S含量越高气相的体积分数越小,而到达井口后H2S的含量越高气相的体积分数越大,导致溢流检测的难度和井控的危险程度增加;高含H2S气井溢流时井底压力的下降值、泥浆池增量、关井套压小于纯烃类的,不能反映真实的气侵程度,而且随着时间的增加情况会更严重;高含H2S气侵时压井过程中套压值与纯烃类的相差不大,因此可以在井口施加一定的压力,抑制H2S气体的膨胀,减缓井喷事故的发生。     

The genesis of H2S in the Weiyuan Gas Field, Sichuan Basin and its evidence

The Sinian Dengying Formation gas pool in Weiyuan is the oldest large-scale sulfur-bearing gas field in China, which has a H2S content ranging from 0.8% to 1.4%. The Cambrian Xixiangchi Formation gas pool discovered recently above the Dengying Formation contains gas geochemical behaviors similar to those of Dengying Formation but different in sulfur isotopes of H2S. Investigations show that though these two Sinian and Cambrian gas pools are separate ones, they share the same Cambrian source rock. The higher dry coefficient, heavier carbon isotopes, sulfur isotopes of sulfide, lower filling of gas pools, formation water characteristics, reservoir properties and H2S distribution, indicate that H2S in both the Sinian and Cambrian gas pools originates from TSR. The sulfur isotopes of sulfates have shown that H2S was formed in respective pools, namely hydrocarbons charged into the pools reacted with the Dengying Formation and the Xixiangchi Formation gypsum （TSR）, respectively, to form H2S. Compared with sulfur isotopes of sulfates in each pool, δ^34S values of H2S are 8‰ lighter for the Dengying Formation pool and 12‰ lighter for the Xixiangchi Formation pool, respectively, which is attributed to the difference in temperatures of TSR occurrence. The reservoir temperature of the Xixiangchi Formation pool is about 40℃ lower than that of the Dengying Formation pool. Temperature plays a controlling role in both the sulfur isotopic fractionation and amounts of H2S generation during TSR.     

High density methane inclusions in Puguang Gasfield: Discovery and a T-P genetic study

Based on measurement of homogenization temperature of inclusions and Raman spectral analysis, high density methane inclusions were discovered in the Triassic reservoirs of Puguang Gasfield. The methane inclusions show a homogenization temperature Th = -117.5― -118.1℃, a corresponding density of 0.3455―0.3477 g/cm3, and a Raman scatter peak v1 shift varying between 2911―2910 cm-1, which signifies a very high density of methane inclusions. The salt water inclusions paragenetic with methane inclusions show a homogenization temperature Th=170―180℃. Based on the composition of methane inclusions as determined by Raman spectra, PVTsim software was used to simulate the trapping pressure for high density methane inclusions in geologic history, and the trapping pressure was found to be as high as 153―160 MPa. Even though Puguang Gasfield is currently a gas pool of normal pressure, and the fluid pressure for the gas pool ranges between 56―65 MPa. However, data from this study indicates that remarkable overpressure may be generated at the stage of mass production of gas cracked from oils in Cretaceous, as high density methane inclusions constitute key evidence for overpressure in gas pool in geologic history. Meanwhile, discovery of small amounts of H2S, CO2 or heavy hydrocarbon in part of the high density methane inclusions indicates that the geochemical environment for trapping of inclusions may be related to formation of H2S. Therefore, the observation results can help to explore the thermochemical sulfate reduction （TSR） conditions for oil cracking and H2S formation.     

盐析辅助水蒸气蒸馏法制备红松壳挥发油研究

采用盐析辅助水蒸气蒸馏法(salt out-assisted steam distillation,SOSD)制备红松壳挥发油,探讨无机盐对蒸馏方式的影响,通过单因素试验研究了蒸馏时间、固液比、无机盐、磷酸氢二钠的质量浓度、萃取剂等因素对红松壳挥发油提取率的影响,并采用气相色谱-质谱联用技术对红松壳挥发油成分进行分析。结果表明:SOSD法最佳制备工艺条件为蒸馏时间3 h,固液比1:9(g/mL),盐析效果最好的无机盐为4×10^-3 g/mL磷酸氢二钠,在此条件下红松壳挥发油提取率为0.9%,是水蒸气蒸馏法(steam distillation,SD)制备红松壳挥发油提取率(0.64%)的1.4倍。红松壳挥发油成分分析表明:SOSD法提取红松壳挥发油共分析出17种可能成分,而SD提取红松壳挥发油共分析出16种可能成分,两种方法提取结果有9种相同可能成分,如反-α反-α,α-5-三甲基-5-乙烯基四氢化-2-呋喃甲醇、苯甲醛、左旋樟脑、2-茨醇、(1R)-(+)-诺蒎酮、2,6,6-三甲基双环[3.1.1]庚-2-烯、2-(4-甲基苯基)丙-2-醇、4,6,6-三甲基二环[3.1.1]庚-3-烯-2-酮、3-甲基-6-(1-甲基亚乙基)-2-环己烯-1-酮等,其相对百分含量差别不大。     

Discussion of gas enrichment mechanism and natural gas origin in marine sedimentary basin, China

There are abundant natural gas resources in Chinese marine sedimentary basin. The exploration hot shots of natural gas are the Palaeozoic marine strata here in recent years, and several large scale gas fields have been discovered. Chinese Palaeozoic high-post matured and coal measure hydrocarbon source rocks are mainly prone to gas generation in the present. This research considered that gas source rocks and TSR are the key cause of gas enrichment of marine strata. High-quality argillaceous and coal measure hydrocarbon rocks are distributed widely in the Palaeozoic marine strata, which have been in highly matured phase in the present. The argillaceous source rock generally contains various sulfates that could accelerate crude oil cracking to gas for TSR occurrence, and coal measure source rock mainly generates gas, so Chinese marine basin gives priority to accumulating gas. Marine strata have not founded oil reservoirs in the Sichuan Basin and Ordos Basin, and they consist mainly of dry gas. Marine natural gases are the mixed gases of oil cracking gas and coal-formed gas in a general way, oil cracking gases contain usually some H2S and CO2. Hydrocarbon carbon isotopes are very complicated, and methane and ethane isotopic values bear apparent reversal caused by thermal evolution and mixing among different genetic types of natural gas. Coal-formed gases are the main component of Chinese marine natural gas. The Upper Permian of the Sichuan Basin and the Carboniferous-Permian of the Ordos Basin coal measure hydrocarbon source rock present large hydrocarbon generation po- tential, which are the prospecting highlight of marine natural gas hereafter. Oil cracking gas exploration will be paid much attention to in the Tarim Basin because of the lack of coal measure hydrocarbon source rock.     

青海羌活挥发油化学成分的GC/MS分析

采用石油醚提取法提取青海产羌活挥发油,测得挥发油的质量分数为3.2%.以毛细管气相色谱-质谱联用技术对其进行分离、鉴定.分离出50余个峰,鉴定了41种化学成分,并用面积归一法确定其相对含量.结果表明:以单环萜烯酮、亚油酸、乙酸谷甾烯醇酯、杜松二烯醇、十六烷酸为其挥发油的主要成分.通过对羌活挥发油成分的研究,为羌活资源的进一步开发利用提供实验依据.