高有机硫煤抽提物中含硫化合物的组成与热演化特征

高有机硫煤是一种十分特殊的煤种,其特点之一是抽提物芳烃馏分中含丰富的含硫化合物。在我国西南地区晚二叠世碳酸盐台地潮坪成因、具不同煤化程度的四种高有机硫煤中均检测出了四种系列的含硫化合物,它们分别为二苯并噻吩系列、苯并萘并噻吩系列、菲并噻吩系列和苯并二苯半噻吩系列。含硫化合物的类型组成虽然相似,但它们的相互比例关系与煤化程度和具体的沉积环境密切相关。分析发现,随煤化程度增加:（1）具三环结构的二苯并噻吩相对于四、五环结构的化合物数量减少;（2）具稳定甲基取代位的含硫化合物数量不断增加,同时还发现含硫化合物与同环数的常规芳烃间的比值可反映碳酸盐台地受局限的程度。     

煤成烃生成及排驱加水热模拟实验

用加水热模拟实验对采于我国胜利油田附近的石炭系太原组亮褐煤（R0＝0．56%）生烃潜力进行研究。煤样富含镜质组（74．5%）,壳质组少（8．8%）,惰性组占16．7%,其中镜质组以富氢的基质镜质体为主。煤样裂隙发育,形成于滨海沼泽相沉积环境。实验设200℃、230℃、260℃、290℃、320℃和350℃六个温度点,每个温度点加热72小时。实验结果表明该煤具有较高的生烃潜力和排油效率。其液态烃大量生成和排出始于R0＝0．76%（290℃）,在R0＝1．18%（320℃）时达高峰。气态产物从R0＝1．18%大量形成,直到R0＝1．53%（350℃）继续增大。实验分析认为煤的生烃能力除了与其有机质类型、有机质丰度等有关外,还与其形成的沉积环境有关,缺氧的还原环境是煤作为烃源岩形成和保存的有利沉积环境。裂隙的发育有助于煤成油的排驱和运移。     

热模拟实验中煤岩显微组分烷烃系列化合物地球化学特征

塔里木盆地侏罗系煤岩显微组分在封闭体系热模拟产物的色质分析表明,各显微组分的正构烷烃系列化合物的碳数均呈双峰型分布。随着温度的升高,后峰相对强度逐渐降低,表明正构烷烃系列化合物在热作用下易发生降解。由于各显微组分化学组成和结构的不同,它们的生烃过程也各不相同。镜质组热降解排烃需要较高热能,以产气为主;壳质组热效应作用下可以有效排烃,为好生烃组分;惰质组虽然生烃潜力有限,但产出烃类的稳定性较好,不易受热降解效应的影响,可以作为气源岩。在整个热模拟实验中,煤岩各显微组分表现为姥鲛烷优势,随着热模拟温度生高,Pr/Ph值表现为先增加后逐渐降低的变化趋势。     

煤热解气体主产物及热解动力学分析

为了研究不同煤化程度煤的热解气相产物、热解动力参数,采用热重-红外光谱-质谱（TG-IR-MS）联用技术对4种不同热演化程度的煤进行了热解实验。实时记录了4种煤样在30~1 100℃、10/min℃升温速率、氦气气氛下热解过程中释放的各种气体成分及其释放量的变化趋势。研究结果表明,随煤热演化程度升高,煤的失重率和最大失重速率逐渐降低,与煤的干燥无灰基挥发分呈正相关关系;随着热解温度的升高,煤中逐渐释放出水、甲烷、二氧化碳、氢气和二氧化硫等小分子气体,且随着煤化程度的升高,各种气体的释放峰逐渐向高温处偏移,说明煤的热稳定性逐渐升高。不同变质程度煤的热解动力学分析结果表明,随着煤变质程度增高,其活化能逐渐降低,说明其热效应强度和发生热解反应的能力在逐渐降低。     

高演化烃源岩岩石热解和总有机碳标准物质研制

南方下古生界海相页岩是我国页岩气勘探开发的重点地层,普遍具有时代老,热演化程度高的地质特征。已有基于常规测试条件制备的岩石热解及总有机碳分析标准物质无法满足此类高演化样品分析的需求,一定程度上制约了页岩气勘探开发进度。研究采集贵州织金龙潭组的泥岩及煤样,按照国家一级标准物质研制标准和规范,研制2件高演化烃源岩标准物质(编号为GBW07499和GBW07500),定值指标S₂、T_max和TOC。经均匀性检验,三个指标的F值均小于临界值F_0.05(v₁, v₂),样品单元间均无显著性差异,均匀性良好。经两年时间考察室温条件下特性量值S₂、T_max和TOC的变化趋势,结果表明拟合直线斜率■,稳定性良好。经多家权威实验室联合定值,全部定值分析数据符合正态和近似正态分布,且等精度,给出认定值和不确定度分别为:S₂为1.09±0.10mg/g,T_max为633±3℃,TOC为26.8%±1.3%;S     

热模拟实验中煤岩及壳质组饱和烃萜类系列化合物地球化学特征

通过对塔里木盆地煤岩与壳质组热模拟实验可溶有机物的色—质分析,煤岩和壳质组三环二萜烷具有低丰度、窄碳数（C19～C26）特征,且三环二萜烷主要来源于煤岩结构中具有三环萜骨架前身物的断裂释放。藿烷C31和C32-αβ22S/22（S+R）随着热模拟温度升高呈增加趋势,表明该地球化学参数是较好的热成熟度指标;αββ藿烷可以用来反映煤岩的热演化程度,且ββ构型向βα构型转化时需要一定能量;煤岩在未熟到成熟热演化过程中,藿烷具有ββ<βα<αβ的热稳定性。壳质组萜烷系列化合物的地球化学参数（以17β（H）三降藿烷、C29βα-藿烷、C31αβ22S/22（S+R））表明壳质组热演化史比煤岩有迟豫效应。      

中低煤阶高有机硫煤含硫结构演化特征

采用计算机曲线拟合方法对实验数据进行分峰处理,定量分析了9个中低煤阶高有机硫煤样的红外光谱(FT-IR)数据特征。研究表明,二硫醚与碳碳双键吸收峰面积比值(X₁)、硫醇与碳碳双键吸收峰面积比值(X₂)分别与R_max以及有机硫含量(S_o,d)呈显著的正相关性。煤质参数相近,有机硫含量及其占全硫比例受微环境的影响。同一煤样中,二硫醚、硫醇、二硫化铁三种含硫结构红外参数均依次递减。低煤阶及低-中阶烟煤阶段,以二硫醚、硫醇为代表的有机硫与含氧官能团的红外参数呈现此消彼长关系,且在第二次煤化跃变点附近,参数急剧增大。高有机硫煤样随煤阶升高,脂肪链支链化程度下降,芳构化程度加大,与一般低硫煤结构演化特征相符。     

煤系热解参数及其与有机碳的相关性

通过对煤系热解参数之间及其与有机碳含量的研究,分析了煤系热解参数与有机碳的关系,认为煤系热解参数及有机碳含量变化范围均较宽,不同热解参数之间具有一定的相关性。Ｓ１、Ｓ２和Ｓ１＋Ｓ２与有机碳具正相关关系,基本可以用于评价有机质丰度。热解类型指数Ｓ２／Ｓ３、氢指数、氧指数和Ｓ３明显地受有机碳的影响,尤其Ｓ２／Ｓ３受到的影响更为明显,这样就影响有机质类型的评价。给出了各参数间的相关关系式,这对于煤系烃源     

Release of sulfur- and oxygen-bound components from a sulfur-rich kerogen during simulated maturation by hydrous pyrolysis

An immature sulfur-rich marl from the Gessosso-solfifera Formation of the Vena del Gesso Basin (Messinian, Italy) has been subjected to hydrous pyrolysis (160 to 330°C) to simulate maturation under natural conditions. The kerogen of the unheated and heated samples was isolated and the hydrocarbons released by selective chemical degradation (Li/EtNH₂ and HI/LiAlH₄) were analysed to allow a study of the fate of sulfur- and oxygen-bound species with increasing temperature. The residues from the chemical treatments were also subjected to pyrolysis–GC to follow structural changes in the kerogens. In general, with increasing hydrous pyrolysis temperature, the amounts of sulfide- and ether-bound components in the kerogen decreased significantly. At the temperature at which the generation of expelled oil began (260°C), almost all of the bound components initially present in the unheated sample were released from the kerogen. Comparison with an earlier study of the extractable organic matter using a similar approach and the same samples provides molecular evidence that, with increasing maturation, solvent-soluble macromolecular material was initially released from the kerogen, notably as a result of thermal cleavage of weak carbon–heteroatom bonds (sulfide, ester, ether) even at temperatures as low as 220°C. This solvent-soluble macromolecular material then underwent thermal cleavage to generate hydrocarbons at higher temperatures. This early generation of bitumen may explain the presence of unusually high amounts of extractable organic matter of macromolecular nature in very immature S-rich sediments.     

泥岩有水热解产生低分子量有机酸实验研究

直接采用泥岩岩屑进行有水热解,测定实验后水溶液中几种常见低分子量有机酸.结果表明,在实验的水溶液中检测到了丰富的低分子量有机酸,组成上主要为一元羧酸,其中又以乙酸占优势.讨论了不同热解条件对有机酸产率以及组成的影响.实验结果表明,有机酸总量随加热温度和时间增加而增加,并且溶液中不同有机酸相对组成也发生变化.当温度高于1...     

Effect of artificial maturation on carbazole distributions, as revealed by the hydrous pyrolysis of an organic-sulphur-rich source rock (Ghareb Formation, Jordan)

Hydrous pyrolysis experiments were performed on the Ghareb Formation (Upper Cretaceous, Jordan), a carbonate- and organic-rich (TOC 19.6%) source rock, using a temperature range of 200 to 360°C (72 h). The original sediment contains only low amounts of carbazoles, (maximum 2.2 μg/g bitumen for 1-methylcarbazole). With increasing thermal maturation, intense generation begins at temperatures only in excess of 300°C, reaching a maximum at 360°C. Likewise, during natural maturation, generation occurs at later stages of maturity (e.g. for Tithonian source rocks at >0.81% R_r and for Posidonia Shale at >0.88% R_r). Some isomeric changes during hydrous pyrolysis do not resemble those in nature whereas others do. The relative abundances of selected C₁- and C₂-alkylcarbazoles on ternary diagrams reveal differences, whereas the benzo[a]carbazole/benzo[a]carbazole+benzo[c]carbazole ratio is closely similar. The latter result supports the contention that maturation plays a key role in controlling carbazole distributions in source rocks. However, the results for alkylcarbazoles, especially the C₂-carbazoles, are not easy to interpret.     

Patterns of organic and inorganic sulfur transformations in sediments

Two new methods for analysis of sedimentary sulfur employing sensitive flame photometric detection have been developed and applied to a study of marine, estuarine and freshwater sediments. Volatile organosulfur compounds generated from freeze-dried sediments upon heating in a H₂ atmosphere reflect the distribution and extent of degradation of detrital organic matter. Regions of biogeochemical sulfur transformations, as characterized by the presence of SO₂ progenitors, sulfite and thiosulfate, are also depicted. Scrubbing of sediment slurries treated with the reducing agent, acidic Cr(II) solution, releases H₂S and CH₂SH from their metal-complexed forms. CH₃SH is a common constituent of marine and estuarine sediments at sub-ppm concentrations.     

中国煤中有机硫的分布及其成因

对来自全国26个省、市、自治区的290个煤样中有机硫的质量分数测试及研究,发现煤中有机硫质量分数基本分布在0%¹.0%范围内。在低硫煤中硫分以有机硫为主,在高硫煤中以无机硫为主。中、高硫煤中,广西、湖南等地区很大一部分煤中硫分以有机硫为主。在所采集的样品中,高有机硫煤(有机硫>1%)均分布在华南、华北两大聚煤区,属于石炭、二叠纪煤。高有机硫煤中有机硫质量分数的变化与变质程度无明显关系。煤炭形成过程中海水作用的影响,是导致煤中有机硫含量偏高的最主要原因。     

Oxidant-elemental sulfur as an effective promoter for transformation of organic matter to hydrocarbons at moderate-low temperatures

Elemental sulfur is widely dispersed in the hydrocarbon source rocks and its depositional environment is usually thought as a reducing environment. The presence or absence of free oxygen is a key to identify oxidizing or reducing environment. But elemental sulfur is often present as an oxidant in this environment. When elemental sulfur meets with organic matter, redox reaction will occur. In our simulation experiments at 200 -400℃ , the existence of elemental sulfur can sharply increase the amounts of hydrocarbons, hence leading to the production of immature or low-mature oils and natural gases. At the temperature of 300℃ , the addition of elemental sulfur will further enhance the relative yields of hydrocarbons,and the final yield of total extracts and gaseous hydrocarbons of similitude kerogens by more than 463% and 2760% , respectively, while those of oil shales are increased by about 71% and 2044% , respectively. But at the temperature of 450℃, elemental sulfur plays a negative role in liquid hydrocarbon formation. The presence of elemental sulfur is probably a key factor in the gypsolyte environment leading to the formation of immature or low-mature oils, as well as the coexistence of immature or low-mature oils and natural gases.     

A comparison of organosulphur compounds produced by pyrolysis of asphaltenes and those present in related crude oils and tar sands

Asphaltenes and NSO fractions from a variety of oils and tar sands have been characterized by pyrolysis-gas chromatography (Py---GC) using both flame ionization and flame photometric detectors. Organosulphur compounds were not always produced by pyrolysis of the asphaltenes isolated from the biodegraded tar sand extracts although pyrolysis of the NSO fractions produced a series of thiophenes from all of the samples examined. These observations suggest that under certain conditions, asphaltene fractions may be affected by biodegradation, leading to preferential removal of the sulphur containing compounds. In addition, it was observed that Py---GC of asphaltenes permitted oils to be differentiated on the basis of their source rock lithology. Oils derived from carbonate source rocks produced thiophene/benzothiopene ratios <1 whilst the same ratio was >1 for oils derived from shales. Thiophene/dibenzothiophene ratios could be used in a similar manner.     

Origin of low-molecular-weight alkylthiophenes in pyrolysates of sulphur-rich kerogens as revealed by micro-scale sealed vessel pyrolysis

Micro-scale sealed vessel (MSSV) pyrolysis experiments have been conducted at temperatures of 150, 200, 250, 300, 330 and 350°C for various times on a thermally immature Type II-S kerogen from the Maastrichtian Jurf ed Darawish Oil Shale (Jordan) in order to study the origin of low-molecular-weight (LMW) alkylthiophenes. These experiments indicated that the LMW alkylthiophenes usually encountered in the flash pyrolysates of sulphur-rich kerogens are also produced at much lower pyrolysis temperatures (i.e. as low as 150°C) as the major (apart from hydrogen sulfide) sulphur-containing pyrolysis products. MSSV pyrolysis of a long-chain alkylthiophene and an alkylbenzene indicated that at 300°C for 72 h no β-cleavage leading to generation of LMW alkylated thiophenes and benzene occurs. In combination with the substantial production of LMW alkylthiophenes with a linear carbon skeleton at these conditions, this indicated that these thiophenes are predominantly formed by thermal degradation of multiple (poly)sulfide-bound linear C₅–C₇ skeletons, which probably mainly originate from sulphurisation of carbohydrates during early diagenesis. LMW alkylthiophenes with linear carbon skeletons seem to be unstable at MSSV pyrolysis temperatures of ≥330°C either due to thermal degradation or to methyl transfer reactions. LMW alkylthiophenes with a branched carbon skeleton most likely derive from both multiple (poly)sulfide-bound branched C₅–C₇ skeletons and alkylthiophene units present in the kerogen.     

水资源中氯代烃污染物的去除方法

随着工业化的发展。氯代有机溶剂使用越来越广泛。并且难于去除。在20世纪90年代初期，人们就已认识到用Fe^0恢复污染的地下水的潜力。国外正在研究帮使用扔几种还原挥发性氯代烃的还原反应介质，尤其要提高的是双金属反应系统，反应速度快，而且脱Cl中国难解产物少，目前国也只停留在实验室研究阶段，个别做了地上反应器的验证实验，它的脱Cl机理、介质钝化和完全脱Cl问题还有待于进一步研究。