Carbon and hydrogen isotopic compositions and their evolutions of gases generated by herbaceous swamp peat at different thermal maturity stages

Coalbed methane (CBM) accumulation models include continuous gas accumulation and staged gas accumulation.However,studied on the geochemical characteristics and indices to evaluate staged accumulation CBM are lacking.This study for the first time obtained the carbon and hydrogen isotopic compositions of methane and ethane generated at different evolution stages using thermal simulation of samples prepared by treating an herbaceous swamp peat at different temperatures.The results showed that the carbon isotopic compositions of methane and ethane were obviously affected by the thermal evolution level of the starting sample,while the hydrogen isotopic compositions were closely related to the maturity of gases.The carbon and hydrogen isotopic compositions of gases generated by coal-forming organic matter with Ro values from 1.2%,1.7%,2.4%,3.2% and 3.7% to 5.2% were determinated.The relationship between Ro values and the carbon and hydrogen isotopic compositions of gases generated by coal-forming organic matter at different evolution stages as well as the carbon or hydrogen isotopic relationships between methane and ethane were established.The results provide a scientific basis for studying the genesis of CBM generated at different maturity intervals and understanding the geochemical characteristics of staged accumulation CBM.These results were applied to a case study on CBM from the southern Qinshui basin,and it was found that the CBM accumulated after the Middle Jurassic and was characteristic of staged gas accumulation.This is consistent with the result of geological studies,and further showed that the results of thermal simulation experiments are very important for evaluating the genesis of natural CBM.     

Oil cracking： An important way for highly efficient generation of gas from marine source rock kitchen

The potentials of gas generation by kerogen in the late period and by crude oil cracking are closely related to the origin of natural gas in the high- to over mature marine area and their exploration perspectives. The carbon structure of kerogens, with different types and at different evolution stages, have been experimentally studied using the high magnetic field solid ^13C nuclear magnetic resonance technique in order to determine the oil and gas potential of kerogens. Results show that the contents of gas potential carbon（GPC） of types Ⅰ, Ⅱ, Ⅲ kerogens at the high- to over mature stage are very low, indicating their weak gas-generating capacity and limited gas production; however, the content of oil potential carbon（OPC） of the low mature type Ⅰ kerogen is much higher, implying that a large amount of crude oil generated during the oil-generating period will be the material for later gas generation by oil cracking. The kinetic experiment of gas generation by crude oil cracking shows that, when the temperature is about 160℃（R0=1.6%）, the crude oil will start to produce large amounts of gas; the temperature range for major gas generation of crude oil is higher than that of the kerogens, and the gas production is 2 to 4 times higher than that of kerogens. The natural gas derived from oil cracking （called oil-cracked gas） is much abundant in methyl hexamethylene, which is quite different from the natural gas produced by thermal degradation of kerogens （named kerogen degradation gas） at high- to over mature stage.     

Groundbreaking gas source rock correlation research based on the application of a new experimental approach for adsorbed gas

Many years of experimentation have led to the development and improvement of equipment and methods used to make gas source rock correlations.By crushing samples using a ball mill and directly collecting adsorbed gases in the absence of aqueous media under high vacuum conditions,most possible interference factors,such as atmospheric pollution,crushing-induced pyrolysis,and gas collection by aqueous media are eliminated.This greatly enhances the volume percentage of hydrocarbon gas in the acquired adsorbed gases,with maxima up to more than 80%.The actual measurement of carbon isotopic series can be carried out to such an extent as to be δ13C1-δ13C5.A preliminary study using newly established equipment and methods has indicated the following.(1) The carbon isotopic composition of ethane in adsorbed gases on hydrocarbon source rocks can be used to distinguish the types of source rocks.This is consistent with results obtained by using organic geochemical parameters for source rocks,and illustrates that it is highly feasible to use the carbon isotopic composition of ethane in natural gases as a parameter for distinguishing the types of source rocks.(2) The thermal evolution degree(Ro) of hydrocarbon-source rocks calculated in terms of the carbon isotopic composition of methane in adsorbed gases on hydrocarbon source rocks agrees well with the vitrinite reflectance actually measured in the source rocks.This confirms the reliability of the relationship between the carbon isotopic composition of methane in natural gases and the thermal evolution degree determined using statistics.(3) Finally,a direct gas source correlation method for natural gases has been established,and the expression of log Ro vs.δ13C1 established in terms of actually measured δ13C1 values of methane in absorbed gases.Ro values of hydrocarbon source rocks have been established as well,thus creating favorable conditions for precise oil-and-gas source correlations in exploration areas.     

The comparison of biomarkers released by hydropyrolysis and Soxhlet extraction from source rocks of different maturities

The Permian Dalong Formation(P2d) source rocks from the mature Guangyuan outcrop section and the overmature Wangcang outcrop section in Sichuan Basin were selected.The Soxhlet extraction and kerogen catalytic HyPy were conducted on the P2d source rocks.The biomarkers obtained by both methods were compared to discuss their difference and the influence extent of thermal maturation on covalently bound biomarkers.The results show that covalently bound biomarkers can hardly be correlated to the corresponding free biomarkers due to severe thermal alterations and/or interference of migrated hydrocarbons in both outcrop sections and thermal maturation have much lower influence on covalently bound biomarkers in kerogens than on free biomarkers in Soxhlet extracts.The application of HyPy in study of biomarker geochemistry can reduce the thermal maturation effect on biomarkers(Ro≤2.4%) to a greater extent and the interference of migrated hydrocarbons between interbedded layers.The covalently bound biomarkers released by HyPy are useful in the study of biomarker geochemistry and oil-source correlation on high-overmature source rocks.     

微藻生物质暗发酵产氢气和甲烷的研究

微藻生物质厌氧消化生产氢气和甲烷效率低下,本研究报道了一种新型微藻处理工艺即两段式暗发酵提高氢气和甲烷产量。结果表明微藻生物质的最佳有机负荷为10 g/L,相应的氢气产量为18.6 mL/g (每克挥发性有机质产气量)。进一步研究表明蛋白酶预处理能进一步提高水解酸化相中氢气的产量至35.5 mL/g,反应pH最低为6.0。同时,蛋白酶预处理能够提高产甲烷相中甲烷产量,并且最大产量为251 mL/g,显著高于空白对照组。机理研究表明两段式消化分别为水解酸化相和产甲烷相提供最佳环境。     

Simulation experiments for evolution of fatty acids in immature source rocks

The anhydrous, hydrous and bitumen-extrac- ted simulations were carried out for the immature source rocks from the Liaohe sag. It has been shown from the result that with increasing temperature in simulation experiments, the fatty acids content decreased at first and then increased. The decrease of fatty acids in immature rocks is presumably related to alkanes generation in immature oils, whilst the increase may be related to the fact that some additional fatty acids are generated from kerogen and the tightly bound fatty acids in kerogen are released as bound fatty acids in kerogen and unbound fatty acids in bitumen. The fact that the bitumen generated from kerogen contains fatty acids has demonstrated that some bound and tightly bound fatty acids in kerogen can be transferred into bitumen. The preferential fatty acids in the immature source rocks are found to be mono-carboxylic acids with longer chains, whilst krogen contains relatively more di-carboxylic acids. It has been found that the fatty acids in immature source rocks can be changed from that with more longer chains to that with more shorter chains when evolution extent has been increased. Based on simulation results and the fact that the majority of fatty acids in immature oils are those with longer chains, it is inferred that the contribution of fatty acids to forming alkanes in immature oils mainly takes place at the evolution stage with R₀ <0.6%. The simulation experiments have also demonstrated that H₂O could promote the generation of fatty acids with more di-carboxylic acids and delay alkanes formation from fatty acids.     

Effects of various pretreatments on biohydrogen production from sewage sludge

The sewage sludge of wastewater treatment plant is a kind of biomass which contains many organics, mainly carbohydrates and proteins. Four pretreatments, acid pretreatment, alkaline pretreatment, thermal pretreatment and ultrasonic pretreatment, were used to enhance biohydrogen production from sewage sludge. The experimental results showed that the four pretreatments could all increase the soluble chemical oxygen demand （SCOD） of sludge and decrease the dry solid （DS） and volatile solid （VS） because the pretreatments could disrupt the floc structure and even the microbial cells of sludge. The results of batch anaerobic fermentation experiments demonstrated that all of the four pretreat- ments could select hydrogen-producing microorganisms from the microflora of sludge and enhance the hydrogen production. The hydrogen yield of the alkaline pretreated sludge at initial pH of 11.5 was the maximal （11.68 mL H2/g VS） and that of the thermal pretreated sludge was the next （8.62 mL H2/g VS）. The result showed that the hydrogen yield of pretreated sludge was correlative with its SCOD. The hydrogen yields of acid pretreated sludge and alkaline pretreated sludge were also influenced by their initial pH. No methane could be detected in the anaerobic fermentation of alkaline pretreated sludge and thermal pretreated sludge, which suggested that these pretreatments could fully inhibit the activity of methanogens. The volatile fatty acids （VFA） production in anaerobic fermentation of alkaline pretreated sludge was the maximum and the next is that of thermal pretreated sludge.     

多粘类芽孢杆菌同步糖化发酵玉米粉生产(R,R)-2,3-丁二醇

【目的】对多粘类芽孢杆菌Paenibacillus polymyxa的玉米粉同步糖化发酵工艺进行优化,以获得低成本、高效的(R,R)-2,3-丁二醇生产技术。【方法】研究玉米粉浓度、氮源种类和氮源浓度对菌体生长、耗糖能力以及(R,R)-2,3-丁二醇产量、产率、得率和转化率的影响,并在此基础上进一步考察培养基中其它成分对(R,R)-2,3-丁二醇发酵的影响。【结果】优化后的培养基组分为玉米干粉140g/L,酵母粉30g/L,Na_2HPO_4 3g/L,KH_2PO_43g/L,(NH_4)2SO_42g/L,MgSO_40.8g/L,微量元素溶液2mL/L。使用优化后的培养基进行同步糖化发酵,发酵50h后(R,R)-2,3-丁二醇产量达到56.28g/L(光学纯度为98.3%),对葡萄糖的得率为0.44g/g,产率为1.13g/(L·h)。【结论】(R,R)-2,3-丁二醇生产技术低价高效,可为其工业化生产提供参考。     

鄂尔多斯盆地宜川地区上古生界烃源岩评价

依据氢指数（HI）、降解率（PC/TOC）等两个方面的地球化学指标,按照煤系地层烃源岩有机质类型划分标准,对研究区的山西-太原组烃源层的有机质类型作剖析,进行上古生界烃源岩系统评价。研究认为,本溪组烃源岩主要是泥岩,有机质丰度平均2.51%,泥岩干酪根母质类型主体属腐殖型干酪根,即Ⅲ型干酪根;太原组暗色泥岩有机质丰度平均2.26%,煤层比较发育,有机质丰度平均81.66%;山西组的泥岩比较发育,泥岩有机质丰度平均2.26%,煤层有机质丰度平均72.66%。本区上古生界干酪根显微组分都以镜质组为主,显示干酪根母质为腐殖型,即Ⅲ型干酪根,热成熟度演化较高,Ro都大于2.5%,Tmax为490℃以上,表明泥岩已达到过成熟阶段,本区暗色泥岩及煤层属中等—好气源岩,此次烃源岩的认识对该区下一步的勘探提供重要的依据。     

Photoelectrochemical synergetic degradation of Acid Orange II with TiO2 modified β-PbO2 electrode

Electrochemically assisted photocatalysis is an effective approach to improve photocatalytic efficiency. In this paper, modified β-PbO2 electrode was prepared by TiO2 co-deposition and characterized by SEM and XRD. Then 2.0g TiO2 modified β-PbO2 electrode (2.0 g TiO2 involved in the 200 mL co-deposition solution) was used in electrochemically assisted photocatalytic degradation of Acid Orange II and the influence of initial pH values was investigated when the potential applied across the electrodes was 1.5 V. When the potential applied was 2.5 V, the difference of the degradation process and the final products were studied. The results indicated that 2.0 g TiO2 modified β-PbO2 electrode was different from the unmodified one in that the β-PbO2 crystals became finer and the electrode became more compact and more uniform. The synergetic effect in electrochemically assisted photocatalytic degradation of Acid Orange Ⅱ was observed and degradation efficiency and TOC removal were the highest at initial solution pH 2.0. By UV-visible spectral analysis, it was proved that photoelectrochemical synergetic degradation of Acid Orange Ⅱ went through the step of producing main product maleic acid for the solution at the initial pH 2.0 within 2 h, but the degradation was slow for the solution at the initial pH 12.0.     

Characterization and origin types of immature and low-mature amorphous kerogen in terrestrial source rocks

The microfluorescent technique was applied to investigate the fluorescence alteration patterns of amorphous kerogen of the terrestrial source rocks of China. Two fluorescence parameters, I ₅₄₆ ²⁰ andR were suggested, which can be taken to divide the amorphous kerogen into five types: algae amorphinite, biodegraded amorphinite A, B, C, and humic amorphous. On the basis of this, the Rock-Eval analysis results of source rocks were used to investigate the hydrocarbon generating potential of these amorphinite.     

Kinetic study of the hydrocarbon generation from marine carbonate source rocks characterization of products of gas and liquid hydrocarbon

The kinetic parameters of hydrocarbon generation from the marine carbonate source rocks were determined and calibrated through kinetic simulating experiment. The kinetic parameters of hydrocarbon generation then were extrapolated to geological condition by using the relative software. The result shows that gaseous hydrocarbons (C_1, C_2, C_3, C_(4-5)) were generated in condition of 150℃相似文献   

长岭断陷南部地区断陷层油气成藏机制及勘探潜力

利用天然气组成、轻烃指纹、碳同位素和生物标志化合物以及储层流体包裹体等地球化学特征,结合地质条件以及生烃史-热史模拟研究长岭断陷南部的龙凤山地区油气成因及成藏过程,揭示其油气成藏机制。结果表明:龙凤山地区断陷层天然气属于腐殖型和腐泥型的混合气,且为裂解气和干酪根热降解气组成的混合气,油气源主要为本地的沙河子组烃源岩,原油成熟度低于天然气,为同一油源不同热演化阶段的产物,属于次生凝析气藏,成藏表现为"近源多向供烃,复合输导,早期干酪根热降解成气与晚期原油裂解成气"的多期成藏模式;长岭南部地区发育优质烃源岩、营城组末期形成的反转构造提供了圈闭条件,具备较好油气输导条件、存在多期油气充注,油气勘探潜力大。     

Pyrolysis of oil at high temperatures: Gas potentials, chemical and carbon isotopic signatures

Although the gas cracked from oil has been believed to be one of the important sources in highly ma-tured marine basins, there are still some debates on its resource potentials and chemical and isotopic compositions. In this study a Cambrian-sourced marine oil sample from the Silurian reservoir of well TZ62 in the central Tarim basin was pyrolyzed using sealed gold tubes with two different pyrolysis schemes: continuous pyrolysis in a closed system and stepwise semi-open pyrolysis. The results show that the maximum weight yield of C_1–5 gases occurs at EasyRo=2.3% and the residual gas poten-tial after this maturity is only 43.4 mL/g, about 12% of the yield of 361 mL/g at EasyRo=2.3%. Combined with the results of kinetic modeling, the main stage of gas generation from oil cracking is believed within the EasyRo=1.6%―2.3%. The increase in the volume yield of C_1–5 gases at EasyRo>2.3% in a closed system is mainly related to the re-cracking of previously formed C_2–5 wet gases, not the direct cracking of oil. The stepwise pyrolysis experiments show that the gas from the cracking of residual oil at EasyRo>2.3% is characterized by very high dryness index (higher than 92%) and heavy methane carbon isotopes ranging from -28.7‰ to -26.7‰, which is quite different from the gases from the con-tinuous pyrolysis in a closed system. The kinetic modeling of methane carbon isotope fractionation shows that the carbon isotopes of methane within the main stage of gas generation (EasyRo<2.3%) are far lighter than the carbon isotopes of the precursor oils under a geological heating rate of 2 ℃/Ma. The above observations and results provide some new clues to the accurate recognition and objective re-source evaluation of oil cracking gas in highly mature marine basins.     

三江盆地绥滨坳陷下白垩统煤系烃源岩评价

根据烃源岩热解地球化学分析成果,应用所测岩样中有机碳(TOC)、吸附烃(S1)、干酪根热解烃(S2)含量及氢指数IH(S2/有机碳),对绥滨坳陷滨参1井和绥D1井下白垩统煤系地层中的煤系泥岩、碳质泥岩和煤岩从有机质丰度、有机质类型和成熟度三个方面进行了烃源岩分析评价。这三种岩石样品中各项生油岩指标绝大多数都达到了中-好烃源岩评价标准。绥滨坳陷下白垩统城子河组和穆棱组为两套具生烃潜力的煤系烃源岩。     

UV/O3法降解乙酸的影响因素

利用UV/O₃法对糠醛废水中的乙酸进行光氧化降解实验. 讨论了pH值、 光源、 阴阳离子等因素对乙酸降解速率的影响. 结果表明, 以高压汞灯 (400 W)为光源, 对500 mL浓度为8 mmol/L的乙酸溶液, 在温度为(35±2) ℃、 O₃含量为 0.1 mg/L, pH值为2.2的条件下, 乙酸降解效果最佳. 在此条件下, 300 min内溶液中乙酸和TOC降解率分别为86%和74%. 在所考察浓度范围内, 乙酸的降解符合零级动力学模式.     

膨润土吸附-微波催化氧化处理番茄酱生产废水的研究

采用膨润土吸附-微波催化氧化技术处理番茄酱生产废水,考察了膨润土添加量、H2O2用量、辐射时间以及微波功率对废水处理效果的影响.确定微波催化氧化的条件是:微波功率650 W、辐射时间13 min、H2O2用量0.21 mL、膨润土用量1.1 g/L.在此条件下对废水进行处理,处理时间由2 h缩短为13 min,废水的COD和TOC去除率分别为84.8 %和80.1 %.     

Oil cracking to gases： Kinetic modeling and geological significance

A Triassic oil sample from LN14 of Tarim Basin was pyrolyzed using the sealed gold tubes at 200-620℃under a constant pressure of 50 MPa. The gaseous and residual soluble hydrocarbons were analyzed. The results show that the cracking of oil to gas can be divided into two distinct stages: the primary generation of total C1-5 gases from liquid oil characterized by the dominance of C2-5 hydrocarbons and the secondary or further cracking of C2-5 gases to methane and carbon-rich matters leading to the progressive dryness of gases. Based on the experimental data, the kinetic parameters were determined for the primary generation and secondary cracking of oil cracking gases and extrapolated to geological conditions to predict the thermal stability and cracking extent of crude oil. Finally, an evolution model for the thermal destruction of crude oil was proposed and its implications to the migration and accumulation of oil cracking gases were discussed.     

The antipole evolution effect of immature-low mature organic matter ——Report from low-temperature low-pressure artificial hydropyrolysis experiment

The low-temperature and low-pressure artificial hydropyrolysis experiment proves that at the immature-low mature thermal evolution stage of source rock, the condensation reaction and the thermal degradation reaction occur continuously and simultaneously in both soluble organic matter and insoluble organic matter. This process was called "antipole evolution", which means transformation into two opposing extremes. The soluble organic matter and insoluble organic matter constitute an organic related integrity, transforming mutually in a dynamic equilibrium. Non-hydrocarbon and asphaltene are key intermediates between kerogen and hydrocarbon . Asphaltene is one of the major sources of immature hydrocarbons.     

干酪根热解聚沥青中的脂烃生物标记物

将干酪根在超临界态溶剂存在下进行热解聚,抽出物中的脂烃生物标记物的分析表明,抚顺与茂名油页岩干酪根中有相当多的陆源高等植物参与生成。甾烧萜烷的成熟度参数表明,热解聚沥青的成熟度很低。对于干酪根通过热解聚形成未熟或低熟原油的可能性作了初步探讨。