煤层气及天然气中的H2S与SO2及其危害性

毒害性气体是影响煤层气和天然气质量及安全生产的一个重要因素,但目前缺乏对煤层气中H2S与SO2及其毒害性的系统性研究。本文在介绍H2S和SO2的毒害性及其机理的基础上,研究并讨论了煤层气及天然气中H2S和SO2的含量分布及其存在的主要问题、天然气和煤层气勘探开发中H2S和SO2的腐蚀性与毒性, 提出在优选勘探开发煤层气区时,需考虑H2S和SO2的含量问题。气体中H2S的安全临界含量近似值为0.0013%, SO2的安全临界含量可选取为0.036%(尚需进一步研究)。另外,在煤层气勘探开发选区时,成煤期的沉积古地理环境可作为一个考虑因素。     

Radioactive Genesis of Hydrogen Gas under Geological Conditions: an Experimental Study

The coexistence of hydrogen-containing materials and radioactive substances in source rocks is universal. Few documents have researched whether the latter can radiate the former to generate hydrogen gas (H2) as well as the factors controlling this process. This work conducted a series of radiation experiments to address this issue. Samples were placed in sealed Pyrex glass containers and subject to cobalt (60Co) γ irradiation and components and contents of resultant gases were analyzed using gas-chromatography. The results show that all the samples released variable amounts of H2 after irradiation and that the yield (H2) of decane is lower than that of 3-tetradecylthiophene but higher than that of distilled water, which implies that a weaker H-X bond energy (X indicates O, C or other element) in homogeneous materials corresponds with increased yield (H2). The yields (H2) of samples decreased with the decreasing solutions concentrations in sequence from mixed salts solution, KCl solution, Yellow Sea water, oil field water, gypsum solution to distilled water. The experimental results also show that the yield (H2) of distilled water with montmorillonite is higher than that of distilled water with kaolinite, because due to the larger specific surface area, ion exchange capacity and more effective energy transfer effect of montmorillonite. Meanwhile, the irradiation of oxygen- and carbon-containing materials also releases O2 and CH4. The production of H2 via the irradiation of hydrogen-containing materials makes the involvement of exogenous H2 into hydrocarbon generation possible, which can enhance the hydrocarbon volume and optimize crude oil.     

煤矿瓦斯中H_2S气体的吸附特性及其对治理的影响

基于新疆和山西气煤及瘦煤对H_2S、CH_4和N_2的平衡水条件下的等温吸附实验及Langmuir模型和D-A模型对实验数据的模拟结果,来研究煤矿瓦斯中H_2S气体的吸附特性及其影响因素,并探讨其与H_2S异常矿井的治理关系。结果显示:不同于CH_4和N_2在煤中主要以微孔吸附为主(90%以上),煤中H_2S气体的微孔吸附量仅占Langmuir最大吸附量的36.26%~57.21%,平均为45.99%;气体分子本身的性质是影响煤中H_2S吸附的主要因素,尤其分子直径是影响H_2S气体V_0/V_L远小于CH_4和N2的这种现象的主要原因,也是造成微孔中H_2S气体难以解吸的主要原因;基于H_2S气体在煤中吸附解吸特征,提出应从H_2S气体分子本身入手,结合矿井煤层地质条件来治理煤矿中的硫化氢。     

四川盆地东北部三叠系飞仙关组高含硫气藏H2S成因研究

四川盆地东北部宣汉－开县地区的下三叠统飞仙关组气藏埋深3000－4500m,地温在100℃左右,天然气中H2S含量为12％－17％。这些H2S为飞仙关组气藏附近的硬石膏经硫酸盐热化学还原作用（TSR）而成。与TSR有关的硬石膏,H2S,S^0和FeS2的δ^24S分别为＋30.4‰, 12.9‰, 19.1‰和＋19.4‰,交代硬石膏的方解石的δ^13C为－7.26‰,δ^18O为－6.41‰,其内所含两相流体包裹体的均一温度为109－151℃。这些高含硫气藏的天然气和储层沥青的热演化程度比其他地区飞仙关组气藏的更高。该区飞仙关组最大埋藏温度超过180℃,但由于后期构造抬升,大于104℃地温的埋藏时间小于20Ma,故气藏H2S含量低于20％。     

温泉水中H2S对游离C02检测的影响

在实验室条件下模拟温泉水中H2S和游离C02来研究温泉水中H2S对游离C02现场检测的影响,以及现场检测时如何消除H2s的影响。实验结果证明：温泉水中H2S对游离C02的测定存在影响,其影响结果随H2S含量的不同而不同;采用扣除法可以很好的消除温泉水中H2S对游离CO2测定的影响。     

乌鲁木齐西山井田原位煤层瓦斯中H_2S含量的影响因素及成因分析

H2S是一种剧毒、有害性气体,乌鲁木齐西山井田是我国最早发现煤层瓦斯中H2S异常的井田之一。为了新建矿井煤炭资源开采安全,基于煤田地质勘查和矿井开拓成果,分析了影响原位煤层中H2S含量的因素,探讨了H2S异常的成因。研究结果表明:1)在煤田勘探范围内(埋深浅于600m),实测H2S含量与煤层埋深、煤层瓦斯总含量、CH4、CO2、N2含量、水分含量(Mad)、灰分产率(Ad)呈负相关趋势,与全硫含量(St,d)、挥发分产率(Vdaf)呈正相关趋势;2)H2S异常的主要成因为煤层自燃、BSR、TDS、TSR混合成因及地下水的迁移。     

潘北矿–580m水平出水点H_2S成因分析及处理试验

安微淮南潘北煤矿–580 m水平探4孔与ES1C3上3-1孔在疏放太原组灰岩水时带有臭鸡蛋气味,且水流过程中伴有白色絮状漂浮物。通过采集水样,测试了出水孔水质及气体,分析了其形成原因。结果表明:气体为H2S,两出水孔的水质均具有低SO2–4、高HCO–3、弱碱性特征,白色絮状物为有机质和钙、镁物质的结合,该异常现象是脱硫酸与脱碳酸共同作用的结果。为及时处理异味对井下作业环境的影响,采用纳米二氧化钛–紫外光催化氧化法在室内对水进行硫化氢去除试验,其去除率为80%~90%,效果显著。     

Origin of the Dachang gold deposit,NW China: constraints from H,O, S,and Pb isotope data

The Dachang gold deposit is located in the Late Triassic Songpan-Ganzi Fold Belt, NE Tibetan Plateau. Gold ore is concentrated as veins along secondary faults and fracture zones in the Bayan Har Group metaturbidites. No exposed felsic plutons are present in the vicinity of the deposit. The auriferous veins contain <15% sulphide minerals, mainly arsenopyrite, pyrite, and stibnite. Gold is commonly enclosed within arsenopyrite and pyrite. Typical alteration around the ore bodies includes silicification, sericitization, and weak carbonatization.

Gold-bearing quartz samples have δ¹⁸O values of 16.9–21.2‰ (V-SMOW) from which δ¹⁸O_H2O values of 6.2–9.6‰ can be calculated from the fluid inclusion temperatures (or 10.0 to 12.7‰ if we used the average arsenopyrite geothermometer temperature of 301°C). The δD values of fluid inclusions in quartz range from –90‰ to –72‰. δ³⁴S values of gold-bearing sulphides mainly range from –5.9‰ to –2.8‰ (V-CDT). Pyrite and arsenopyrite in ores have ²⁰⁶Pb/²⁰⁴Pb ratios of 18.2888 to 18.4702, ²⁰⁷Pb/²⁰⁴Pb ratios of 15.5763 to 15.6712, and ²⁰⁸Pb/²⁰⁴Pb ratios of 38.2298 to 38.8212. These isotopic compositions indicate that the ore-forming fluids were of metamorphic origin, and the S and Pb may have been derived from the host metaturbidites of the Bayan Har Group. The Dachang Au deposit has geological and geochemical features similar to orogenic gold deposits. We propose that the ores formed when the Songpan-Ganzi Fold Belt was intensely deformed by Late Triassic folding and thrusting. Large-scale thrusting resulted in regional allochthons of different scales, followed by secondary faults or fracture zones that controlled the ore bodies.     

碳酸盐倒退溶解模式的化学热力学基础——与H_2S有关的溶解介质及其与CO_2的对比

以化学热力学中的吉布斯自由能增量为基础,计算了与H2S(g)/ H2S(aq) /HS-/ H+/S2-系统有关反应在不同温度下的平衡常数,同时根据方解石和白云石在酸性条件下的溶解过程,获得了这两种碳酸盐矿物溶解过程中地层中流体pH值与PCO2、地层压力和埋藏深度的关系。在此基础上,对比了从地表到深埋藏的温度和压力条件下,与CO2和H2S有关的酸性介质对流体\[H+\]贡献的差异性,以及对于碳酸盐溶解作用的差异性。计算结果表明:1）无论以CO2还是以H2S作为溶解介质,温度增加和（或）PCO2增加,都会造成方解石和白云石溶解所需要的\[H+\]增加,在深埋藏相对高温和高压条件下,高PCO2条件会使得碳酸盐矿物的溶解更加困难,如果\[H+\]受到缓冲,CO2的增加不仅不能造成碳酸盐矿物的溶解,反而会造成碳酸盐矿物的沉淀;2）无论在何种酸性介质中,碳酸盐矿物的倒退溶解模式在化学上都是成立的,低温的成岩环境,深部地层中高温流体的向上运移、构造抬升所造成的温度降低（-ΔT）都会提高H2S和（或）CO2流体（也包括其它酸性介质）对碳酸盐矿物溶解能力;3）在地表和近地表条件下（几百米深度范围内）,在同时存在CO2和H2S的环境中,CO2对应酸的电离提供的\[H+\]略多于H2S对应酸的电离,与CO2有关的酸性流体对碳酸盐矿物溶解相对重要,而在深埋藏条件下、尤其是深度大于4 000 m的深埋藏地层中,H2S对应酸的电离提供的\[H+\]显著大于CO2,其对碳酸盐矿物的溶解更为重要,在存在硫酸盐还原作用的深埋藏地层中,碳酸盐的深部溶解作用会更为发育,这可能是川东北地区深埋藏条件下次生孔隙发育的重要原因之一。     

四川盆地高含H2S天然气的分布与TSR成因证据

四川盆地是中国高含硫化氢天然气分布最集中的地区,目前已在震旦系(威远气田)、下三叠统飞仙关组(罗家寨、普光、渡口河、铁山坡、七里北)、嘉陵江组(卧龙河)和中三叠统雷口坡组(磨溪、中坝)发现了近10个高含硫化氢的大中型气田(藏),探明储量5000×108 m3.这些高含硫化氢气藏普遍经历过较大的埋深过程(储层经历过较高温度),储层上下或储层中间均发育有膏质岩类,且气源充足,具备硫酸盐热化学还原反应(Thermochemical Sulfate Reduction,TSR)发生的物质基础和热动力条件.从气藏地质特征以及天然气组成和碳、硫同位素等方面的证据表明,四川盆地中、下三叠统和震旦系气藏的硫化氢属于TSR成因.而且TSR对烃类的大量选择性消耗一方面导致天然气干燥系数增大,另一方面导致气藏充满度降低,气藏压力系数变小.     

Dissolution of Quartz, Albite, and Orthoclase in H2O-Saturated Haplogranitic Melt at 800{degrees}C and 200 MPa: Diffusive Transport Properties of Granitic Melts at Crustal Anatectic Conditions

We have conducted experiments on dissolution of quartz, albite,orthoclase, and corundum into H₂O-saturated haplogranite meltat 800°C and 200 MPa over a duration of 120–1488 hwith the aim of ascertaining the diffusive transport propertiesof granitic melts at crustal anatectic temperatures. Cylindersof anhydrous starting glass and a single mineral phase (quartzor feldspar) were juxtaposed along flat and polished surfacesinside gold or platinum capsules with 10 wt % added H₂O. Concentrationprofiles in glass (quenched melt) perpendicular to the mineral–glassinterfaces and comparison with relevant phase diagrams suggestthat melts at the interface are saturated in the dissolvingphases after 384 h, and with longer durations the concentrationprofiles are controlled only by diffusion of components in themelt. The evolution of the concentration profiles with timeindicates that uncoupled diffusion in the melt takes place alongthe following four linearly independent directions in oxidecomposition space: SiO₂, Na₂O, and K₂O axes (Si-, Na-, and K-eigenvectors,respectively), and a direction between the Al₂O₃, Na₂O, andK₂O axes (Al-eigenvector), such that the Al/Na molar ratio isequal to that of the bulk melt and the Al/(Na + K) molar ratiois equal to the equilibrium ASI (= mol. Al₂O₃/[Na₂O + K₂O])of the melt. Experiments in which a glass cylinder was sandwichedbetween two mineral cylinders—quartz and albite, quartzand K-feldspar, or albite and corundum—tested the validityof the inferred directions of uncoupled diffusion and exploredlong-range chemical communication in the melt via chemical potentialgradients. The application of available solutions to the diffusionequations for the experimental quartz and feldspar dissolutiondata provides diffusivities along the directions of the Si-eigenvectorand Al-eigenvector of (2·0–2·8) x 10^–15m²/s and (0·6–2·4) x 10^–14 m²/s, respectively.Minimum diffusivities of alkalis [(3–9) x 10^–11m²/s] are orders of magnitude greater than the tetrahedral componentsof the melt. The information provided here determines the rateat which crustal anatexis can occur when sufficient heat issupplied and diffusion is the only mass transport (mixing) processin the melt. The calculated diffusivities imply that a quartzo-feldspathicsource rock with initial grain size of 2–3 mm undergoinghydrostatic, H₂O-saturated melting at 800°C (infinite heatsupply) could produce 20–30 vol. % of homogeneous meltin less than 1–10 years. Slower diffusion in H₂O-undersaturatedmelts will increase this time frame. KEY WORDS: chemical diffusion; haplogranite; mineral dissolution experiments; crustal anatexis     

Phase Relations and Stability of Magnetoplumbite- and Crichtonite-Series Phases under Upper-Mantle P-T Conditions: an Experimental Study to 15 GPa with Implications for LILE Metasomatism in the Lithospheric Mantle

High-pressure–high-temperature experiments were performedin the range 7–15 GPa and 1300–1600°C to investigatethe stability and phase relations of the K- and Ba-dominantmembers of the crichtonite and magnetoplumbite series of phasesin simplified bulk compositions in the systems TiO₂–ZrO₂–Cr₂O₃–Fe₂O₃–BaO–K₂Oand TiO₂–Cr₂O₃–Fe₂O₃–BaO–K₂O. Both seriesof phases occur as inclusions in diamond and/or as constituentsof metasomatized peridotite mantle xenoliths sampled by kimberlitesor alkaline lamprophyres. They can accommodate large ion lithophileelements (LILE) and high field strength elements (HFSE) on awt % level and, hence, can critically influence the LILE andHFSE budget of a metasomatized peridotite even if present onlyin trace amounts. The Ba and K end-members of the crichtoniteseries, lindsleyite and mathiasite, are stable to 11 GPa and1500–1600°C. Between 11 and 12 GPa, lindsleyite breaksdown to form two Ba–Cr-titanates of unknown structurethat persist to at least 13 GPa. The high-pressure breakdownproduct of mathiasite is a K–Cr-titanate with an idealizedformula KM₇O₁₂, where M = Ti, Cr, Mg, Fe. This phase possessesspace group P6₃/m with a = 9·175(2) Å, c = 2·879(1)Å, V = 209·9(1) ų. Towards high temperatures,lindsleyite persists to 1600°C, whereas mathiasite breaksdown between 1500 and 1600°C to form a number of complexTi–Cr-oxides. Ba and K end-members of the magnetoplumbiteseries, hawthorneite and yimengite, are stable in runs at 7,10 and 15 GPa between 1300 and 1400°C coexisting with anumber of Ti–Cr-oxides. Molar mixtures (1:1) of lindsleyite–mathiasiteand hawthorneite–yimengite were studied at 7–10GPa and 1300–1400°C, and 9–15 GPa and 1150–1400°C,respectively. In the system lindsleyite–mathiasite, onehomogeneous Ba–K phase is stable, which shows a systematicincrease in the K/(K + Ba) ratio with increasing pressure. Inthe system hawthorneite–yimengite, two coexisting Ba–Kphases appear, which are Ba rich and Ba poor, respectively.The data obtained from this study suggest that Ba- and K-dominantmembers of the crichtonite and magnetoplumbite series of phasesare potentially stable not only throughout the entire subcontinentallithosphere but also under conditions of an average present-daymantle adiabat in the underlying asthenosphere to a depth ofup to 450 km. At still higher pressures, both K and Ba may remainstored in alkali titanates that would also be eminently suitablefor the transport of other ions with large ionic radii. KEY WORDS: crichtonite; magnetoplumbite; high-P–T experiments; phase relations; upper mantle     

川东北飞仙关组高含H2S气藏特征与TSR对烃类的消耗作用

四川盆地川东北地区飞仙关组近年来发现了罗家寨、渡口河、铁山坡、普光等多个大、中型气田，它们均以高含硫化氢（H2S在气体组分中占10%~17%，平均为14%）为最显著特征。深入研究后发现，虽然这些大型鲕滩气藏储量规模较大，单井产量高；但是这些气藏充满度普遍偏低（在25%~91%之间），压力系数不高（大部分小于1.2）。从成藏条件来看，该区鲕粒溶蚀孔隙发育，有效储层厚度大，二叠系龙潭组、志留系龙马溪组优质烃源岩十分发育，油气源充沛，而且由断层构成的疏导体系发育，泥岩及膏质岩类组成的盖层封盖性良好，因此气藏的低充满度现象，可能是圈闭中发生过大量烃类的损耗或消耗。由于川东北飞仙关组H2S是烃类和硫酸盐在储层中发生热化学反应（TSR）形成的，气藏中硫化氢含量与压力系数、地层水矿化度、烃类含量等都存在反相关关系，因此飞仙关组高含硫化氢气藏压力系数小、充满度低，很可能是烃类被TSR大量消耗和储集空间增容所致。     

Ammonium ion behaviour in feldspar: variable-temperature infrared and 2H NMR studies of synthetic buddingtonite, N(D,H)4AlSi3O8

The behaviour of the ammonium ion in synthetic buddingtonite, N(D,H)₄AlSi₃O₈, has been studied by infrared (IR) spectroscopy from 20 K to 298 K and by ²H NMR spectroscopy from 120 K to 298 K. IR spectra were collected from 500 to 3500 cm^–1. Static ²H NMR spectra collected at 298 K and 120 K are very similar, consisting of a single sharp isotropic resonance, indicating complete averaging of quadrupolar interactions and implying that at these temperatures the ammonium ion is in rapid (<1 s) randomised motion within the M-site cavity of the feldspar framework. NMR spectroscopy indicates that the splitting of the internal modes of the ammonium ion observed by IR spectroscopy is not due to freezing in of the ammonium ion. This observation rules out the formation of a preferred N–H...O hydrogen bond, with precession of the ion about it, as proposed by Kimball and Megaw (1978), because any N–H...O hydrogen bond must be very weak and transient in nature. Contraction of the cavity site upon cooling imposes a distortion upon the ammonium ion that affects vibrational modes. This distortion does not affect the motion of the ammonium ion as observed on the NMR time-scale.     

延边小西南岔富金斑岩铜矿床的含矿流体起源与演化--H,O,C,S,Pb同位素示踪

延边地区小西南岔富金斑岩铜矿床的H、O、C、S和Pb同位素特征如下:δ18OQ-H2O为-0.1‰～ 5.6‰、δD为-77‰～-38‰,δ18OCc-H2O为-4.3‰、δD为-62‰;石英流体包裹体的δ13CCO2为-5.6‰～-3.5‰,δ18OCc-H2O为-4.3‰～ 11.39‰、δ13CPDB为-8.8‰0～-5.3‰,δ34S集中在 2.1‰～ 4.8‰之间,206Pb/204Pb=18.103～18.388、207Pb/204Pb=15.405～15.590、208Pb/204Pb=37.888～38.184,μ值为8.52～8.79.其中:S同位素特征指示含矿流体与次大陆岛孤岩浆相似,而C、O、Pb同位素则指示初始地幔源.结合H、O同位素的地幔初生水 岩浆水 变质水和演化过程向雨水热液和海水方向进行的特征初步认为,初始含矿流体的热动力源是原始地幔,成矿物质来源于I-MORB性质地幔,含矿流体演化的浅部过程受到一定程度的雨水热液的混染作用.     

Subsolidus and Partial Melting Reactions in the Quartz-excess CaO+MgO+Al2O3+SiO2+H2O System under Water-excess and Water-deficient Conditions to 10 kb: Some Implications for the Origin of Peraluminous Melts from Mafic Rocks

Experimental results up to 10 kb pressure are presented on thestability of amphibole in the quartz-excess CaO+MgO+Al₂O₃ (CMASH)system under H₂O)-excess and H₂O deficient conditions. Amphiboleis stable above the solidus under H₂O-excess conditions whereasunder H₂O-deficient conditions dehydration melting of amphibole-bearingassemblages defines the solidus. The successive appearance ofamphibole, talc, and zoisite with increasing pressure considerablymodifies the plagioclase-pyroxene-garnet-kyanite reactions documentedexperimentally in the CaO+MgO+Al₂O₃+SiO₂ system for gabbro-granulite-eclogitetransitions. Although both clino pyroxene and cordierite (withanorthite+orthopyroxene+quartz) may melt eutectically at oneatmosphere to form diopside-normative and corundum-normativemelts respectively, at higher pressures under H₂O-excess conditionsthe peritectic melting of mafic rock compositions produces corundum-normativeliquids together with either clinopyroxene or amphibole. Dehydrationmelting produces melts which are not corundum-normative. Thesedata are used to discuss the origins and evolution of contrastingbasalt-andesite-dacite-rhyolite volcanic suites and graniticplutons, many of whose silicic variants are corundum-normativein character, such as the Toba luff ignimbrites, Indonesia (Beddoc-Stephenset al., 1983) and I-type granite minimum melts (White &Chappell, 1977). In contrast, it is proposed that for the Cascadesbasalt-andesite-dacite-rhyolite suite the ortho pyroxene-plagioclase-quartzthermal divide was maintained up to rhyolite compositions, therebyprohibiting the derivation of corundum-normative rocks fromdiopside-normative parent magmas. The deduced reaction relations between pyroxenes, amphibole,plagioclase, quartz, and liquid are used to explain the absenceor extreme scarcity of hydrous phases in some hydrous magmas.These phase relations can also explain the development of laterplagioclase overgrowths on resorbed plagioclase cores in graniticintrusives, and the general absence of resorption and overgrowthsin chemically equivalent extrusive rocks. A theoretical analysis of the partial melting of forsterite-bearingassemblages in the CaO+MgO+Al₂O₃+SiO₂+H₂O system shows thatunder H₂O-excess conditions partial melting may generate corundum-normative(but low SiO₂) melts from a peridotite source at shallow depths.     

四川盆地普光大型气田H2S及优质储层形成机理探讨——读马永生教授的“四川盆地普光大型气田的发现与勘探启示”有感

四川盆地普光大型气田的发现刷新了中国海相碳酸盐岩油气田的多项记录：储量规模最大、储层埋藏最深、资源丰度最高，同时也是中国原油裂解气藏规模最大、天然气最于、硫化氢储量最多的气藏；另外它还是中国目前发现的碳酸盐岩储层次生孔隙最发育的气藏。深入研究后发现，普光超大型气藏的形成具有特殊的地质地球化学条件，即充沛的烃源、储层附近发育一定的膏质岩类、储层经历过较大的埋深〈较高的温度），这些条件是硫酸盐热化学还原作用（thermochemical sulfate reduction，简称TSR，）发生所必须具备的；而正是由于TSR的发生，一方面形成了富含H2S、CO2等酸性气体的流体；同时TSR过程及其形成的硫化氢等酸性流体具有腐蚀性，对深部碳酸盐岩储层进行强烈的溶蚀改造作用，促进了次生大孔洞的发育和优质储层的形成，因此TSR的发生是普光大型气田形成的关键因素之一。