Maceral evolution of lacustrine shale and its effects on the development of organic pores during low mature to high mature stage:A case study from the Qingshankou Formation in northern Songliao Basin,northeast China

Organic matter(OM)hosted pores are crucial for the storage and migration of petroleum in shale reservoirs.Thermal maturity and macerals type are important factors controlling the development of pores therein.In this study,six lacustrine shale samples with different thermal maturities from the first member of the Qingshankou Formation in the Songliao Basin,of which vitrinite reflectance(R_(o))ranging from 0.58% to 1.43%,were selected for a comparative analysis.Scanning electron microscopy(SEM)and reflected light microscopy were combined to investigate the development of organic pores in different macerals during thermal maturation.The results show that alginite and liptodetrinite are the dominant primary macerals,followed by bituminite.Only a few primary organic pores developed in the alginite at the lowest maturity(R_(o)=0.58%).As a result of petroleum generation,oil-prone macerals began to transform to initial-oil solid bitumen at the early oil window(R_(o)=0.73%)and shrinkage cracks were observed.Initial-oil solid bitumen cracked to oil,gas and post-oil bitumen by primary cracking(R_(o)=0.98%).Moreover,solid bitumen(SB)was found to be the dominant OM when R_(o)>0.98%,which indicates that SB is the product of oil-prone macerals transformation.Many secondary bubble pores were observed on SB,which formed by gas release,while devolatilization cracks developed on migrated SB.Additionally,at the late oil window(Ro?1.16%),migrated SB filled the interparticle pore spaces.With further increase in temperature,the liquid oil underwent secondary cracking into pyrobitumen and gas,and spongy pores developed on the pyrobitumen at higher levels of maturity(Ro=1.43%),which formed when pyrobitumen cracked into gas.Vitrinite and inertinite are stable without any visible pores over the range of maturities,verifying their low petroleum generation potential.In addition,it was concluded that clay minerals could have a catalytic effect on the petroleum generation,which may explain why organicclay mixtures had more abundant pores than single OM particles.However,after R_(o)>0.98%,authigenic minerals occupied the organic pore spaces on the organic-clay mixtures,resulting in fewer pores compared to those observed in samples at the early to peak oil window.

Paleo-fires and Atmospheric Oxygen Levels in the Latest Permian:Evidence from Maceral Compositions of Coals in Eastern Yunnan,Southern China

Inertinite maceral compositions of the Late Permian coals from three sections in the terrestrial and paralic settings of eastern Yunnan are analyzed in order to reveal the paleo-fire events and the atmospheric oxygen levels in the latest Permian. Although the macerals in the studied sections are generally dominated by vitrinite, the inertinite group makes up a considerable proportion. Its content increases upward from the beginning of the Late Permian to the coal seam near the Permian- Triassic boundary. Based on the microscopic features and the prevailing theory that inertinite is largely a by-product of paleo-fires, we suggest that the increasing upward trend of the inertinite abundance in the latest Permian could imply that the Late Permian peatland had suffered from frequent wildfires. Since ignition and burning depend on sufficient oxygen, a model-based calculation suggests that the 02 levels near the Wuchiapingian/Changhsingian boundary and the Permian-Triassic boundary are 27% and 28% respectively. This output adds supports to other discoveries made in the temporal marine and terrestrial sediments, and challenges the theories advocating hypoxia as a mechanism for the PermianTriassic boundary crisis.

Research on the maceral characteristics of Shenhua coal and efficient and directional direct coal liquefaction technology

In this research,molecular structure models were developed respectively for Shenhua coal vitrinite concentrates(SDV)and inertinite concentrates(SDI),on the basis of information on constitutional unit of Shenhau coal and elemental analysis results obtained from^(13)C-NMR analysis characterization,FTIR analysis characterization,X-ray diffraction XRD and XPS analysis characterization.It can be observed from characterization data and molecular structure models that the structure of SDV and SDI is dominated by aromatic hydrocarbon,with aromaticity of SDI higher than that of SDV;SDV mainly consists of small molecule basic structure unit,while SDI is largely made from macromolecular structure unit.Based on bond-level parameters of the molecular model,the research found through the autoclave experiment that vitrinite liquefaction process goes under thermodynamics control and inertinite liquefaction process under dynamics control.The research developed an efficient directional direct coal liquefaction technology based on the maceral characteristics of Shenhua coal,which can effectively improve oil yield and lower gas yield.

TOF-SIMS Study of the Hydrocarbon-generating Potential of Mineral-Bituminous Groundmass

: The TOF-SIMS fragment peak ascription of organic and inorganic ions of mineral-bituminous groundmass of Jurassic source rocks in the Turpan-Hami and Junggar basins was studied by using the high-resolution Time of Flight Secondary Ion Mass Spectrometer (TOF-SIMS). The characteristics of spectrum distribution and constitution of fragment ions of the mineral-bituminous groundmass are discussed; then the methods of evaluating its hydrocarbon-generating potential are developed. In addition, the typical parameters, XAL, Yox and ZAR, for indicating the hydrocarbon-generating potential of mineral-bituminous and other organic matter in source rocks are put forward to reflect the aliphatic, oxygenous, and aromatic structures. It is confirmed by Rock-Eval that these parameters are significant in evaluating hydrocarbon generation. Moreover, the detection of the nitrogenous and oxygenous fragment ion, CH5NO3+, in the mudstone formed in semi-deep lakes and in the carbargilite formed in the arms of lakes reflects the fact that microbes take an active part in biologic degradation.

Study on the pyrolysis behavior of Shendong Shangwan coal and its macerals concentrate

The pyrolysis characteristics of Shendong Shangwan coal and its macerals concentrate were investigated using thermogravimetry （TG） coupled with mass spectrometry （MS）. The evolved gases were analyzed online by MS spectroscopy. The results of TG/DTG （derivative thermogravimetry） show ths vitrinite concentrate has greater weight loss rate and higher volatile yield than the other two samples. More light hydrocarbons C1-C5 are released from the vitfinite concentrate than from the Shendong Shangwan coal and inertinite concentrated in the process of pyrolysis. Three samples have similar shape curves of evolved gases of C2~C5 with different intensities. When the pyrolysis temperature was lower than 418℃, the amount of C6H6 evolved in the process of pyrolysis of inertinite concentrated was higher than that of raw coal and vitrinite concentrate. As the temperature rising, the production rate of C6H6 increased. Below 672℃, C6H6 evolution rate of vitrinite concentrate was far greater than the other two samples; the main evolution temperature range of C7H8 was 400℃ to 700℃ for the three samples. The amount of HE and H20 released first increased and then decreased with the temperature increase while more H2 released for pyrolysis of inertinite concentrated and more H20 released for the pyrolysis of vitrinite concentrate.

Influence of microwave treatment under a hydrogen or methane atmosphere on the flotability of the macerals in Shenfu coals

The modification of Shenfu coals by a microwave treatment carried out under a hydrogen or a methane atmosphere, and the subsequent maceral separation by flotation, are described in this paper. The surface contact angle and the Zeta potential of the coal macerals were measured both with and without the treat- ment. The results show that the surface wettability of SFF (Shenfu Fusain) and SFV (Shenfu Vitrain) can be changed by the microwave treatment. An increase in the difference in surface wettability of SFF and SFV causes in a subsequent increase in the enrichment of inertinite and vitrinite. The results of the Zeta potential measurements show that the surface potentials of SFF and SFV are also changed by the treatment.

Preparation and coking properties of coal maceral concentrates

The concentrates with different maceral contents were obtained from Kailuan coking coals with different coal ranks(Ro;ranvarying from 0.88%to 1.73%)by float–sink separation in lab.Then these concentrates were characterized by proximate analysis,ultimate analysis,petrography analysis and coking index determination.The results show that the vitrinite is characterized as nature of lower carbon content,higher hydrogen content,higher volatile matter and stronger caking property compared to inertinite.The relationships between variation rate of volatile matter and maximum volatile matter and coal ranks are identified,and a linear model is developed for fast determination of the maceral contents.Compared to inertinite-rich concentrate,the blending ratio of vitrinite-rich concentrate is increased by 13%,which is considered to be a potential technique based on maceral separation for expanding the coking coal resources.

Explanation for peat-forming environments of coal seam 2 and 9^(-2)based on the maceral composition and aromatic compounds in the Xingtai coalfield,China

Maceral composition and aromatic compounds were determined on columnsamples to study the peat-forming environments of Permian coal seam 2 and Carboniferouscoal seam 9^(-2) from the Xingtai coalfield,China.The macerals were dominated by inertinitein seam 2 and by vitrinite in seam 9^(-2).Three maceral groups were selected as indicatorsof peat-forming environments.Two triangle diagrams were drawn based on the indicatorsto explicate the peat-forming environments of permian seam 2 and Carboniferousseam 9^(-2).The results indicate that the peat of carboniferous seam 9^(-2) formed dominantlyin wet swamps,whereas the peat of Permian seam 2 formed dominantly in dry swampsand open moor environments.

Flotation characteristics of Shenfu coal macerals

The flotation characteristics of Shenfu coal macerals was researched. Taking flotation recovery and enrichment of macerals as the evaluation objects, the influence of the agent dosage, pulp concentration, impeller speed and aeration rate on the separating effect was investigated. And the optimum process conditions of flotation were confirmed. The results show that the agent dosage, pulp concentration, impeller speed and aeration rate have a significant impact on flotation recovery and en- richment of macerals. The float recovery was 73.28% and enrichment ratio of vitrinite was 83.89% when CTAB dosage of 1.0 kg/t, pulp concentration of 100 g/L, impeller speed of 1 700 r/min and aeration rate of 0.25 m3/（m2·min） were used. The tailings yield was 60.30% and enrichment ratio of inertinite was 61.44% when CTAB dosage of 0.5 kg/t, pulp concentration of 100 g/L, impeller speed of I 700 r/min and aeration rate of 0.20 m3/（m2·min） were used.

Compositional and Structural Study of Macerals in Coals and Source Rocks Using SIMS

The authors applied the Secondary Ion Mass Spectrometry (SIMS) technique to the analysis of compositions and structures of vitrinites fusinites, fusinites bitumens and graptolites in the hydrocarbon source rocks with different maturities dscribed their SIMS spectral characteristics and found that different macerals have differnt spectra which, reflected the compositional and structural differences of macerals. Moreover, the change bod of parameter CH2+/CH3+ can be used for the evaluation of thermal evolution regularity of macerals in the hydrocarbon source rocks The study results show that the SIMS technique is a powerful means for microara analysis of macerals in coals and source rocks. It is certain that the study level of macerals can be raised by detailed study of SIMS results of SIMS results of macerals.

Modeling of the whole hydrocarbon-generating process of sapropelic source rock

Based on experimental data from hydrocarbon generation with a semi-open system, hydrocarbon generation kinetics modeling in gold tube of closed system, high temperature pyrolysis chromatography mass spectrometry experiment with open system and geological data, the characteristics of whole hydrocarbon-generating process, hydrocarbon expulsion efficiency and retained hydrocarbon quantity, origins of natural gas generated in high-over mature stage and cracking temperature of methane homologs were investigated in this study. The sapropelic source rock has a hydrocarbon expulsion efficiency of 30%-60% and 60%-80% in the major oil generation window(with Ro of 0.8%-1.3%) and high maturity stage(with Ro of 1.3%-2.0%) respectively; and the contribution ratio of kerogen degradation gas to oil cracking gas in total generated gas in high maturity stage is about 1:4. The degradation gas of kerogen accounts for 20%, the retained liquid hydrocarbon cracking gas accounts for 13.5%, and the amount of out-reservoir oil cracking gas(including aggregation type and dispersed oil cracking gas) accounts for 66.5%. The lower limit of gas cracking is determined preliminarily. Based on the new understandings, a model of the whole hydrocarbon-generating process of source rock is built.

Optimization of Baosteel's digital automatic analysis technique for maceral specification

Baosteel developed a digital automatic analysis technique for maceral specification in 2002. This analysis system combines digital image processing, graphics, databases, expert systems, artificial intelligence and other advanced technologies. After 6 years of application in coke production, the system proved itself successful in coal quality testing and coal blending guidance on maceral. However,during this long process, some inadequacies were found that impacted the precision and accuracy of the analysis. So ,in 2008 Baosteel began to work on improving the coal maceral analysis system. The improvements included the following：further upgrading and enhancing the analysis performance of microscopic images ;extending the gray levels to increase the reflectance measurement accuracy 64 times;changing the focus method and effectively eliminating the interference of halo. In addition, an improved image recognition method was adopted to make the extraction of vitrinite more accurate and a new model of coal constituent algorithm was added which can accurately determine the composition of maceral （exinite, vitrinite,inertinite）. Since these improvements were completed, the system has achieved higher automation, speed and accuracy, collected more information and performed more accurate maceral analysis for coke production. Meanwhile, the improved system has provided a reliable analytical basis for the further study on the relationship between coke quality and coal blending.

Organic Petrologic Characteristicsand Hydrocarbon-Generating Significance of Epiphyton

The Epiphyton occurred in the carbonate rock of lower Paleozoic in North China was analyzed by using the optical and some micro-area methods such as Micro-FT-IR and TOF-SIMS. The result shows that tbe Epiphyton belonging to the calcic algae has a certain hydrocarbon-generating potential and the hydrocarbou-generating action may continue to the high mature stage.

Geochemical characteristics of different maceral groups in the Huangxian Coal,China

In order to research how lignite is utilized, two coal samples of seams 2 and 4 were taken from the Huangxian Basin, China. The samples were separated into vitrinite, sporinite, and resinite. Geo-chemical and pyrolysis methods were used to analyse three maceral groups and two seam samples. The results indicate that the resinite and sporinite groups have higher extract yields, S1, S2, HI values, and pyrolysis compounds. These differences may shed light on the usage of the Huangxian lignite. Seam 2 pro- duces more gas and oil than seam 4 does because seam 2 contains more resinite and sporinite macerals.

Carbon monoxide adsorptive capability of low rank coal's maceral

The centrifugal separation with gravity experiment was made for getting every pure macerals like inertinite and vitrinite,and the isothermal adsorption tests of pure mac- eral are carried out at 30,40,50,55,60,65℃,respectively,after analyzing the proximate element and maceral of coal samples,which was aimed to study the CO adsorptive capa- bility of every maceral of low rank coal at difference temperature and pressure.The results show that the adsorption isotherm of CO can be described by Langmuir equation because it belongs to the Type I adsorption isotherm at low temperature(T≤50℃),and the tem- perature effect on coal adsorption is greater than of pressure in lower temperature and pressure area;what's more,the relationship is linear between the coal adsorption quantity of CO and the pressure at high temperature(T>50℃),it can be described by Henry equation(Q=KP),which increases with pressure.Both temperature and pressure has great influence on CO adsorptive capability of low rank coals,especially the temperature's effect is so very complex that the mechanism need to study further.At the same time,the volatile matter,inertinite,oxygen-function groups and negative functional groups are high popu- larly in low rank coal samples,especially,the content of hydroxide(-OH) has great influ- ence on CO adsorption in that the inertinite has stronger effect than vitrinite on adsorptive capability of low rank coal samples,the result is same to the research on CH4 adsorption.

Characteristics of Hydrocarbon Generation from Organic Macerals in Jurassic Coal Measures, Xinjiang, China

The Jurassic coals of the Junggar and Turpan\|Hami basins, Xinjiang, China, are characterized by abundant vitrinite. Microscopic analysis of Junggar coal samples indicates that they contain desmocollinite and hydrogen\|rich vitrinite with a low reflectivity. The hydrocarbon\|generating potential of various macerals follows the decreasing order of exinite>vitrinite>inertinite. However, desmocollinite is a principal maceral for hydrocarbon generation in this area because the content of vitrinite is higher than that of exinite. Data from simulating experiments and infrared spectra show that the hydrocarbon\|generating process occurred primarily at the lower\|mature stage in the Middle\|Lower Jurassic coal measures. Generally, crude oil from the Qigu oilfield has a close similarity in hopanoid distribution to the vitrinite and exinite from the Jurassic strata with C 23 \|C 32 pentacyclic triterpanes and γ \|lupane being present. The distribution of steranes is also similar. C 29 \|sitostane is dominant and C 27 ergostane is subordinate. Only a trace amount of cholestane is present. All this suggests that the crude oil from the Qigu oilfield was derived from Jurassic coal measures.

Improved maceration techniques to study the fruit vascular anatomy of grape

The visualization and evaluation of fruit vascular bundles in grape are indispensable for understanding the development and growth of the fruit. The vascular bundles in grape are as thin as human hair, and strongly adhere to flesh cells, making it difficult to isolate individual intact vessel elements. Currently there is little information about methods to characterize grape vascular tissue. In this study, we describe an easy and effective technique to visualize the xylem cell structure of the ‘Red Globe' grape(Vitis L.). The intact vascular bundles of the grape were isolated through enzymatic degradation of flesh cells by hydrolases which were effective in removing flesh cells from vascular bundles. This enabled the illustration of the fine surface structure of vessel elements and their arrangement in the vascular bundles of the grape. This modified method to separate the vascular bundles into individual vessel elements was more effective than former methods of manually shaking to isolate individual vessels. Clear images of xylem vessel arrangement and structural characteristics of individual vessel element were acquired by light microscopy(BX51, Olympus, Tokyo, Japan), transmission electron microscopy(Tecnai 12, Philips, Netherlands) and scanning electron microscopy(GeminiSEM 300, Carl Zeiss, Germany). In addition, the 3D structure of vessel elements was observed using confocal laser scanning microscopy(Zeiss: model: LSM-880, Oberkochen, Germany). The imaging techniques for visualizing and analyzing the structure of xylem vessels in grape described in this study are an improvement of past methods. An effective method to isolate grape vascular bundles from flesh cells was also developed, which enables the imaging of the fine surface structure of vessel elements and their arrangement in grape vascular bundles. By adjusting the process of maceration of vascular bundles, an easy and effective method was developed to gently disrupt the plant tissue and isolate individual vessel elements. These improved techniques are suitable to observe the intact morphology of vascular bundles in the grape, improve experimental efficiency and accelerate new discoveries on the anatomical structure of the grape.

神府烟煤及其煤岩组分制备氧化石墨烯的组成、结构演变

以煤为原料制备石墨烯是一种非常有前景的煤炭材料化、高值化利用途径。针对煤岩组分的组成、结构差异,探明煤岩组分在制备氧化石墨烯过程中的演变规律,是开发煤基石墨烯制备技术的理论基础。利用重选法富集低变质神府煤中镜质组和惰质组,并将富集煤岩组分通过高温石墨化得到石墨化碳,以石墨化碳为前驱体通过改良的Hummers氧化法制备煤基氧化石墨烯。利用元素分析、红外光谱、X射线衍射、拉曼光谱、扫描电镜、透射电镜以及原子力显微镜等研究煤及其煤岩组分在制备氧化石墨烯过程中的组成和结构演变规律。结果表明炭化处理使煤有机大分子结构向无定形碳结构转变,高温石墨化使煤有机大分子结构向石墨碳结构转变;惰质组呈片状结构且分子结构中芳香结构单元较多导致石墨化碳微晶尺寸较大,高温石墨化处理后其拉曼光谱的(A_(D1)/A_(G))值为0.382,镜质组高温石墨化处理后的(A_(D1)/A_(G))值为0.686,原煤高温石墨化处理后的(A_(D1)/A_(G))值为0.864;利用富惰质组得到的石墨化碳制备氧化石墨烯厚度尺寸约5 nm;而镜质组的石墨化碳中石墨微晶结构较小,得到的氧化石墨烯尺寸较小,且氧化石墨烯平均厚度超过10 nm;原煤中由于石墨化过程形成棒状结构,较难形成有序片层结构,氧化剥离也难以得到氧化石墨烯。

煤层微观孔隙特征及沉积环境对孔隙结构的控制作用-以鄂尔多斯盆地8号煤层为例

寻找深部煤层气资源分布,亟待查明深部煤储层沉积环境和孔隙分布特征。为此,在开展鄂尔多斯盆地煤岩显微组分、核磁共振孔隙和电镜分析的基础上,查明了煤岩显微组分和孔隙分布特征,评价了鄂尔多斯盆地8号煤的煤沉积环境和孔隙结构特征之间的关系。结果表明:①研究区8煤层煤岩有机显微组分以镜质组为主,成煤早期植物类型应主要为木本植物,后期随着覆水程度增大而逐渐转变为木本+草本混生植物为主;②本溪期8号煤由早期为湿地森林沼泽逐步演化为后期开阔水域沼泽,沼泽水体相对滞留,沼泽环境稳定,利于有机质富集和煤层结构稳定;③研究区8煤大孔占比与结构保存指数(TPI)两者呈正相关,而与凝胶化指数(GI)呈负相关;④基质镜质体发育密集气孔群或稀疏带状气孔群,团块镜质体中发育少量气孔,结构镜质体中发育原始组织孔,多为矿物充填,均质镜质体气孔不发育。研究认为榆林地区煤层孔隙分布受到煤沉积环境和显微组分控制,开阔水域沼泽相的煤层孔隙结构呈现三峰,其中微孔和大孔发育最好,湿地森林沼泽相煤层孔隙结构呈现双峰,微孔发育好,大孔发育较差。

煤岩显微组分电浮选分离与制氢过程中氢/氧气泡的影响机制

电浮选技术是实现煤岩显微组分高效分离的有效途径,也是一种有显著优势的制氢技术。电浮选中电解气泡既是浮选分离的载体,又是有效的氢气/氧气产物。本文探讨了高惰质组煤电浮选过程中电解气泡对煤岩显微组分分离效果的影响机制,利用诱导时间测定仪、红外光谱、接触角测量仪及气相色谱等考察了氢气泡和氧气泡对煤岩显微组分的选择性以及电化学反应对煤结构和可浮性的影响规律和气体产物组成等。结果表明,电解氢气泡浮选所得的浮物收率及浮物镜质组含量较氧气泡高,相应的镜质组回收率也高于氧气泡;电浮选过程中的电解作用会改善煤岩显微组分的表面结构,引起润湿性的变化,电浮选阴极区对煤具有电化学还原作用,可减少煤中—OH、—COOH与C==O等亲水性官能团,从而增加煤样的接触角,减小氢气泡对煤的诱导时间,从而增加煤的可浮性,而阳极区的作用相反;煤浆电浮选过程中可获得纯度>94%的氢气和>96%的氧气,且镜质组为电解质时的气体产物纯度高于惰质组,但惰质组可获得更高的产气速率;采用两级串联流程进行煤岩显微组分的电浮选分离时,浮选分离的综合效率最高可达到83.7%,此时浮物的镜质组回收率为86.7%,两个沉物产品的回收率分别为41.6%和54.9%,氢气的产率可达到6.49mL/(min∙cm^(2))。