Discovery of nano organo-clay complex pore-fractures in shale and its scientific significance:A case study of Cretaceous Qingshankou Formation shale,Songliao Basin,NE China

A new pore type,nano-scale organo-clay complex pore-fracture was first discovered based on argon ion polishing-field emission scanning electron microscopy,energy dispersive spectroscopy and three-dimensional reconstruction by focused ion-scanning electron in combination with analysis of TOC,R_(o)values,X-ray diffraction etc.in the Cretaceous Qingshankou Formation shale in the Songliao Basin,NE China.Such pore characteristics and evolution study show that:(1)Organo-clay complex pore-fractures are developed in the shale matrix and in the form of spongy and reticular aggregates.Different from circular or oval organic pores discovered in other shales,a single organo-clay complex pore is square,rectangular,rhombic or slaty,with the pore diameter generally less than 200 nm.(2)With thermal maturity increasing,the elements(C,Si,Al,O,Mg,Fe,etc.)in organo-clay complex change accordingly,showing that organic matter shrinkage due to hydrocarbon generation and clay mineral transformation both affect organo-clay complex pore-fracture formation.(3)At high thermal maturity,the Qingshankou Formation shale is dominated by nano-scale organo-clay complex pore-fractures with the percentage reaching more than 70%of total pore space.The spatial connectivity of organo-clay complex pore-fractures is significantly better than that of organic pores.It is suggested that organo-complex pore-fractures are the main pore space of laminar shale at high thermal maturity and are the main oil and gas accumulation space in the core area of continental shale oil.The discovery of nano-scale organo-clay complex pore-fractures changes the conventional view that inorganic pores are the main reservoir space and has scientific significance for the study of shale oil formation and accumulation laws.

Diversified roles of mineral transformation in controlling hydrocarbon generation process,mechanism,and pattern

Organic matter(OM)is intimately associated with minerals in clay-rich mudstones,leading to widespread organic-mineral interaction during hydrocarbon generation in argillaceous source rocks.What we are concerned is the effects of the different mineral properties on hydrocarbon generation process and mechanism during mineral transformation.In this way,pyrolysis experiments with smectite-octadecanoic acid complexes(Sm-OA and Ex-Sm-OA)were conducted to analyze correlation of mineralogy and pyrolysis behaviors.Based on organicmineral interaction,hydrocarbon generation process was divided into three phases.At 200–300℃,collapse of smectite led to desorption of OM,resulting in high yield of resin and slight increase in saturates.Subsequently,enhanced smectite illitization at 350–450℃was accompanied with large amounts of saturates and a mere gaseous hydrocarbon.Featured by neoformed plagioclase,ankerite,and illite,500C saw plenty of asphaltene and methane-rich gaseous hydrocarbons,revealing cracking reactions of OM.Noteworthy is that saturated and gaseous hydrocarbons in Ex-Sm-OA were considerably more than that in Sm-OA during second and third phases.Quantitative calculation of hydrogen revealed organic hydrogen provided by cross-linking of OM could not balance hydrogen consumed by cracking reactions,but supply of inorganic hydrogen ensured cracking could readily occur and consequently greatly promoted hydrocarbon generation.Further investigating characteristics of mineralogy and pyrolytic products,as well as effects of solid acidity on hydrocarbon generation,we concluded desorption of OM and decarboxylation promoted by Lewis acid were dominated at 200–300C,resulting in lowdegree hydrocarbon generation.While high yield of saturated and gaseous hydrocarbons in second and third phases,together with occurrence of ankerite,indicated predominance of decarboxylation and hydrogenation promoted by Lewis and Brønsted acid,respectively.Variations in organic-mineral interactions indicated(1)the controls of mineral transformation on hydrocarbon generation process and mechanism include desorption,decarboxylation,and hydrogenation reactions;(2)clay minerals acted as reactants evolving together with OM rather than catalysts.These findings are profoundly significant for understanding the hydrocarbon generation mechanisms,organic-inorganic interactions,and carbon cycle.

In-situ hydrocarbon formation and accumulation mechanisms of micro- and nano-scale pore-fracture in Gulong shale, Songliao Basin, NE China

By conducting experimental analyses, including thermal pyrolysis, micro-/nano-CT, argon-ion polishing field emission scanning electron microscopy (FE-SEM), confocal laser scanning microscopy (CLSM), and two-dimensional nuclear magnetic resonance (2D NMR), the Gulong shale oil in the Songliao Basin was investigated with respect to formation model, pore structure and accumulation mechanism. First, in the Gulong shale, there are a large number of pico-algae, nano-algae and dinoflagellates, which were formed in brackish water environment and constituted the hydrogen-rich oil source materials of shale. Second, most of the oil-generating materials of the Qingshankou Formation shale exist in the form of organo-clay complex. During organic matter thermal evolution, clay minerals had double effects of suppression and catalytic hydrogenation, which expanded shale oil window and increased light hydrocarbon yield. Third, the formation of storage space in the Gulong Shale was related to dissolution and hydrocarbon generation. With the diagenesis, micro-/nano-pores increased, pore diameter decreased and more bedding fractures appeared, which jointly gave rise to the unique reservoir with dual media (i.e. nano-scale pores and micro-scale bedding fractures) in the Gulong shale. Fourth, the micro-/nano-scale oil storage unit in the Gulong shale exhibits independent oil/gas occurrence phase, and shows that all-size pores contain oils, which occur in condensate state in micropores or in oil-gas two phase (or liquid) state in macropores/mesopores. The understanding about Gulong shale oil formation and accumulation mechanism has theoretical and practical significance for advancing continental shale oil exploration in China.

Development of Ecologically Acceptable Chlorpyrifos Formulation for Effective and Safe Application

Application of the commercial formulation of chlorpyrifos has resulted in considerable environmental contamination. This study was designed to develop environmentally acceptable chlorpyrifos formulation for safe and effective application. This involved the modification of clay surfaces from hydrophilic to hydrophobic via ion-exchange reaction with organic cations. The resulting organo-clay complexes were tested for adsorption and release of chlorpyrifos. HPLC and FTIR measurements showed considerable adsorption and strong interaction between chlorpyrifos molecules and the organo-clay complexes. Basal spacing results emphasized the formation of suitable micro-pores for chlorpyrifos molecules. HPLC and bioassay techniques confirmed the slow release of chlorpyrifos. Leaching potential showed retention of chlorpyrifos in the top soil. Therefore application of organoclay formulation of chlorpyrifos may reduce their potential environmental contamination and produce safe applications.

Research on preservation and enrichment mechanisms of organic matter in muddy sediment and mudstone

Using multidiscipline methodologies, the differences in preservation and enrichment mechanisms of organic matter (OM) in muddy sediment and mudstone are investigated. In clay fractions, concentrations of TOC and chloroform bitumen “A” are significantly higher than those in coarser fractions. This indicates that clay minerals (CM) play an important role in enriching OM. The content of chloroform bitumen “A” increases obviously in the clay fraction, which reveals that dissolvable OM is the main composition of coalesce with clay minerals. Furthermore, TG and DTA data show that OM enrichment mechanisms and preservation forms have multiplicity. Several exothermic peaks in the DTA curves demonstrate that muddy sediment and mudstone contain a number of bioclasts and amorphous OM besides dissolvable OM. Through analyzing with XRD and DTA after mudstone samples were pretreated, the conclusions can be arrived at. Firstly, CM interlayer space of XRD curves and exothermic peaks of DTA curves both change as temperature increases. Secondly, the changes of CM interlayer space and exothermic peaks are concordant and stable around 350°C. All these are the features that OM enters CM interlayers to form stable organo-clay complexes. Therefore, the combination format of OM with CM is not only surface adsorption, partial OM enters CM interlayers to form stable organo-clay complexes. Finally, through the research on OM preservation forms and enrichment mechanisms in muddy sediment and mudstone, the hydrocarbon-generation processes and the global carbon cycle and budget can be explained.

The significance and variation characteristics of interlay water in smectite of hydrocarbon source rocks

To investigate variation characteristics of interlayer water bound up with organic matter in smectite, organo-clay complexes extracted from grinded source rock samples were determined using thermo-XRD, DTA and PY-GC. The dool diffraction peak of organo-clay complexes is postponed from 250 to 550℃ before reaching 1.00 nm and accompanied by exothermal peaks on DTA and organic matter with abundant C20-C30carbon detected by PY-GC, which is different from single smectite and indicates the existence of organic matter in the interlayer of smectite. Water desorption characteristics of organo-clay complexes are in consistent with smectite at 100 and 600℃, but different from smectite at 550℃ with an additional dehydration peak and a remaining d001 diffraction peak, suggesting the vcater removed at 550℃ is interlayer adsorption water rather than constituent water of clay minerals. Comparing the dehydration order and water loss, we conclude that part of interlayer water of smectite may act as the ＂bridge＂ that binds organic matter and smectite, which results in water-expelled lag beyond 250℃ and may provide a good medium for hydrocarbon migration and oil pool formation.