Effect of temperature on leaching behavior of copper minerals with different occurrence states in complex copper oxide ores

The effect of temperature on leaching behavior of copper minerals with different occurrence states in complex copper oxide ores was carried out by phase analysis means of XRD, optical microscopy and SEM-EDS. The results indicated that at ambient temperature, the easily leached copper oxide minerals were completely dissolved, while the bonded copper minerals were insoluble. At lukewarm temperature of 40℃, it was mainly the dissolution of copper in isomorphism state. With increasing temperature to 60℃, the copper leaching rate in the adsorbed state was significantly accelerated. In addition, when the temperature increased to 80℃, the isomorphic copper was completely leached, leaving 11.2% adsorbed copper un-leached. However, the copper in feldspar-quartz-copper-iron colloid state was not dissolved throughout the leaching process. Overall, the leaching rates of copper in different copper minerals decreased in the order: malachite, pseudo-malachite > chrysocolla > copper-bearing chlorite > copper-bearing muscovite > copper-bearing biotite > copper-bearing limonite > feldspar-quartz-copper-iron colloid.

Microscopic oil occurrence in high-maturity lacustrine shales:Qingshankou Formation,Gulong Sag,Songliao Basin

Occurrence and mobility of shale oil are prerequisites for evaluating shale oil reserves and prioritizing exploration targets,particularly for heterogeneous lacustrine shales.The Qingshankou Formation in the Gulong Sag,Songliao Basin is a classic lacustrine pure shale reservoir that contains abundant shale oil resources.The predicted geological reserves of the shale are 1.268×10^(9) t.In this study,field emission scanning electron microscope(FE-SEM),the modular automated processing system(MAPS),pyrolysisgas chromatography(Py-GC),low-pressure nitrogen gas adsorption(LPNA),Soxhlet extraction,pyrolysis,and 2-D nuclear magnetic resonance(NMR)were integrated to describe the shale oil components,microscopic occurrence,mobility,and the effective pore size distribution.Meanwhile,the related controlling factors are discussed.The shale oil in the Qingshankou Fm exists dominantly in the matrix pores of the clay minerals,with small amounts distributed in the intergranular pores of terrigenous clastic grains,intercrystalline pores of pyrite,intragranular pores of ostracod shells,and micro-fractures.Shale oil is distributed in the pore spaces of variable sizes in different lithofacies.The clay mineral-laminated shales are characterized by the broadest range of pore size and largest volume of pore spaces with shale oil distribution,while the ostracod-laminated shales have limited pore spaces retaining oil.Furthermore,the proposed integrated analysis evaluates the shale oil molecules existing in two states:movable,and adsorbed oil,respectively.The result illustrates that movable oil takes up 30.6%e79.4%of the total residual oil.TOC,mineral composition,and pore structures of the shale joint together to control the states and mobility of the shale oil.TOC values are positively correlated with the quantities of shale oil regardless of the state of oil.The mineral components significantly impact the state of shale oil.Noticeable differences in the states of oil were observed following the changing types of minerals,possibly due to their difference in adsorption capacity and wettability.Clay minerals attract more adsorbed oil than movable oil.Felsic minerals generally decrease the occurrence of total and adsorbed oil.Carbonate plays a positive role in hydrocarbon retention of all the shale oil states.As for the pore structure,the average pore size exerts a critical impact on the total,movable,and adsorbed oil content.The total pore volume and specific surface area of shales play a principal role in controlling the total yields and amounts of adsorbed oil.This research improves the understanding of the occurrence characteristics and enrichment mechanisms of shale oil in terrestrial pure shales and provides a reference for locating favorable shale oil exploration areas.

The occurrences and geochemical characteristics of thorium in iron ore in the Bayan Obo deposit, Northern China

The Bayan Obo deposit in northern China is an ultra-large Fe–REE–Nb deposit.The occurrences,and geochemical characteristics of thorium in iron ores from the Bayan Obo Main Ore Body were examined using chemical analysis,field emission scanning electron microscopy,energy dispersive spectrometer,and automatic mineral analysis software.Results identified that 91.69%of ThO2 in the combined samples was mainly distributed in rare earth minerals(bastnaesite,huanghoite,monazite;56.43%abundance in the samples),iron minerals(magnetite,hematite,pyrite;20.97%),niobium minerals(aeschynite;14.29%),and gangue minerals(aegirine,riebeckite,mica,dolomite,apatite,fluorite;4.22%).An unidentified portion(4.09%)of ThO2 may occur in other niobium minerals(niobite,ilmenorutile,pyrochlore).Only a few independent minerals of thorium occur in the iron ore samples.Thorium mainly occurs in rare earth minerals in the form of isomorphic substitution.Analyses of the geochemical characteristics of the major elements indicate that thorium mineralization in the Main Ore Body was related to alkali metasomatism,which provided source material and favorable porosity for hydrothermal mineralization.Trace elements such as Sc,Nb,Zr,and Ta have higher correlation coefficients with thorium,which resulted from being related to the relevant minerals formed during thorium mineralization.In addition,correlation analysis of ThO2 and TFe,and REO and TFe in the six types of iron ore samples showed that ThO2 did not always account for the highest distribution rate in rare earth minerals,and the main occurrence minerals of ThO2 were closely related to iron ore types.

Analysis of the microstructure and elemental occurrence state of residual ash-PM following DPF regeneration by injecting oxygen into non-thermal plasma

Particulate matter(PM)capture tests were carried out on clean diesel particulate filters(DPFs)under different loads(25%,50%,75%and 100%).DPFs were regenerated by a non-thermal plasma(NTP)injection device.Raman spectroscopy and x-ray photoelectron spectroscopy were used to investigate changes in the microstructure and element occurrence state of the sediment in DPF channel before and after regeneration.The order of the PM samples decreased before NTP treatment as the load increased;the amorphous carbon content was high,and the oxidationactivity was higher.After NTP treatment,the carbon atoms at the edge of the microcrystalline structure in the ash-PM samples were oxidized,and the structure was reorganized;in addition,the amorphous carbon content decreased,and the structure was more diversified.Before NTP,the C element of PM samples was the main component,and the content of the O element was relatively low.The C element occurred in the form of C–C,C–OH,and O–C=O functional groups,and O atoms were mainly combined with C–O.After NTP,the content of Na,P,S,Ca,and other inorganic elements in ash-PM samples was prominent because C atoms were removed by NTP active substances.There were two forms of S element occurrence(SO42-and SO32-);the proportion of SO42-was approximately 40%,and the proportion of SO32-was approximately60%.Study of the microstructure and element occurrence of the residues in the DPF channels improved our understanding of the mechanism of the low-temperature regeneration of DPFfrom NTP.

Occurrence state and oil content evaluation of Permian Fengcheng Formation in the Hashan area as constrained by NMR and multistage Rock-Eval

The Hashan area,neighboring the Mahu Sag that is rich in the shale oil resources,showed commercial oil flow in the corresponding lacustrine shales of the Lower Permian Fengcheng Formation(P)with reserve scale approximately 789 million tons,presenting great potential for oil exploration.Despite their geographical proximity,the hydrocarbon occurrence and oil-bearing capacity of shale in the Hashan area and Mahu Sag greatly differ owing to the complex tectonic evolution.Therefore,understanding the occurrence state and oil content of the Pif in the Hashan area is crucial for ongoing shale oil exploration activities and the development of the northwestern margin of the Junggar Basin.In this study,an in-tegrated investigation,including petrological observations,scanning electron microscopy(SEM)obser-vation,analysis of nuclear magnetic resonance(NMR)Ti-T2 spectra,and conventional and multistage Rock-Eval pyrolysis methods were conducted to evaluate the occurrence state and oil content of the Pif shale in the Hashan area.The results indicate that plagioclase(average 30.7%)and quartz(24.1%)dominate the mineral compositions of the Pf shale samples.A method involving quartz-plagioclase-carbonate minerals is proposed to conduct lithofacies classification.In the Hashan area,the organic matter abundance in the Pf shale is scaled in fair to good range,the thermal maturity ranges from immature to early mature stage,and the primary organic matter types are Types I and Ilj.Intergranular and dissolution pores are the two most common pore types.The free oil is mostly found in the pores and microfractures of the mineral matrix,whereas the adsorbed oil is mostly adsorbed on the surfaces of kerogen and clay minerals.The high organic matter abundance,quartz content,and porosity account for substantial increase in the oil content,the area rich in shale oil resources coincides with that rich in free oil.The most favorable lithofacies in the Hashan area is the calcareous mudstone/shale,which hosts the highest free oil content(average 2.49 mg),total oil content(15.02 mg/g),organic matter abundance CTOC:1.88% and S_(1)+S_(2)=20.54mg/g and orositv(5.97%)

Control of micro-wettability of pore-throat on shale oil occurrence:A case study of laminated shale of Permian Lucaogou Formation in Jimusar Sag,Junggar Basin,NW China

The control of micro-wettability of pore-throat on shale oil occurrence in different types of reservoir spaces remains unclear.Take the shale oil reservoir of the Permian Lucaogou Formation in the Jimusar Sag,Junggar Basin as an example,the reservoir space in laminated shale and the control of micro-wettability of pore-throat on shale oil occurrence were studied by using scanning electron microscope(SEM),multi-stage pyrolysis,quantitative fluorescence,nuclear magnetic resonance(NMR)and other techniques.The results show that there are mainly two types of laminated shale in the Lucaogou Formation,namely laminated shale rich in volcanic materials+terrigenous felsic,and laminated shale rich in volcanic materials+carbonate.The former type contains feldspar dissolution pores and intergranular pores,mainly with felsic mineral components around the pore-throats,which are water-wet and control the free shale oil.The latter type contains carbonate intercrystalline pores and organic pores,mainly with oil-wet mineral components around the pore-throats,which control the adsorbed shale oil.The oil-wet mineral components around the pore-throats are conducive to oil accumulation,but reduce the proportion of free oil.In the Lucaogou Formation,free oil,with high maturity and light quality,mainly occurs in the laminated shale rich in volcanic materials+terrigenous felsic.

Study on the occurrence state of indium in sphalerite of Dulong Sn–Zn–In polymetallic deposit,Southwest China

The Dulong deposit,located in the Laojunshan area of southeastern Yunnan,China,is an important polymetallic deposit due to its high reserves of tin,zinc,and indium.The occurrence state of indium is critical for understanding its supernormal enrichment mechanism.Previous studies investigated the occurrence state of indium(including the valence state)based on the indium content in sphalerite and the correlation between metal concentrations.However,more evidence is needed to better constrain indium occurrence at the micro-,nano-,or even atomic scale.In this study,EPMA-FIB-SEM-TEM and XPS techniques were employed to investigate the indium distribution characteristics and occurrence state in sphalerite from the Dulong Sn–Zn–In polymetallic deposit.The maximum concentration of indium in the indium-rich sphalerite samples is 0.37%,and the results of the EPMA analysis showed a relatively homogeneous distribution of indium in sphalerite.The FIB-SEM-TEM results demonstrated that the lattice stripes of sphalerite were periodically and continuously distributed at the nanoscale,confirming that sphalerite in the deposit was an excellent single crystal structure,and the peak heights of the various characteristic peaks of indium in the EDX spectra were relatively close to each other,with no distinct peaks of high indium content.In addition,the XPS results indicate that the element valence state of indium in sphalerite is In^(3+),and it combines with S^(2-)to form a bond.These results indicate that indium in sphalerite of the Dulong deposit is uniformly distributed at both the micro-and nanoscale,and there is no indium-independent mineral.In^(3+)enters the crystal lattice of sphalerite by replacing Zn2+in the form of isomorphic substitution.

Mineral occurrence for Dachang gold deposit and its impact on gold recovery rate in Qumarleb County,Qinghai

Based on X-ray diffraction,optical microscopy and scanning electron microscopy analysis of the Dachang gold ore,it is showed that the sulfide of ore is the main carrier minerals of gold. A majority of gold is embedded in pyrite and tetrahedrite as the form of inclusion and a small amount intergrowth with pyrite and gangue mineral,occasionally the presence is in form of monomer natural gold. The main factors which influence the recovery rate are sulfide mineral particle size,and the fine grained sulfide is beneficial for the dissociation and flotation of gold bearing minerals. The monomer dissociation degree of gold bearing minerals can reach91. 3%,when the grinding fineness is less than 0. 074 mm and grain level accounts as 80%. It is not conducive to the flotation of sulfide if the grinding fineness is low or high. It is difficult to completely dissociate the monomer if there is a small amount of pyrite and arsenopyrite in the ore. Therefore,before leaching the gold,it must conduct pretreatment to reach the ideal recovery rate of the gold,like roasting oxidation,pressure oxidation and biological oxidation. The fine microscopic gold has little influence on the gold recovery rate.

Experimental study on the oil production characteristics during the waterflooding of different types of reservoirs in Ordos Basin, NW China

Waterflooding experiments were conducted in micro-models(microscopic scale)and on plunger cores from low permeability,extra-low permeability and ultra-low permeability reservoirs in the Ordos Basin under different displacement pressures using the NMR techniques to find out pore-scale oil occurrence state,oil production characteristics and residual oil distribution during the process of waterflooding and analyze the effect of pore structure and displacement pressure on waterflooding efficiency.Under bound water condition,crude oil mainly occurs in medium and large pores in the low-permeability sample,while small pores and medium pores are the main distribution space of crude oil in extra-low permeability and ultra-low permeability samples.During the waterflooding,crude oil in the medium and large pores of the three types of samples are preferentially produced.With the decrease of permeability of the samples,the waterflooding front sequentially shows uniform displacement,network displacement and finger displacement,and correspondingly the oil recovery factors decrease successively.After waterflooding,the residual oil in low-permeability samples is mainly distributed in medium pores,and appears in membranous and angular dispersed phase;but that in the extra-low and ultra-low permeability samples is mainly distributed in small pores,and appears in continuous phase formed by a bypass flow and dispersed phase.The low-permeability samples have higher and stable oil displacement efficiency,while the oil displacement efficiency of the extra-low permeability and ultra-low permeability samples is lower,but increases to a certain extent with the increase of displacement pressure.

Quantitative evaluation model of shale oil adsorption:A case study of the first member of Cretaceous Qingshankou Formation in northern Songliao Basin,NE China

A quantitative evaluation model that integrates kerogen adsorption and clay pore adsorption of shale oil was proposed,and the evaluation charts of adsorption-swelling capacity of kerogen(Mk)and adsorbed oil capacity of clay minerals(Mc)were established,taking the 1st member of Cretaceous Qingshankou Formation in the northern Songliao Basin as an example.The model and charts were derived from swelling oil experiments performed on naturally evolved kerogens and adsorbed oil experiments on clays(separated from shale core samples).They were constructed on the basis of clarifying the control law of kerogen maturity evolution on its adsorption-swelling capacity,and considering the effect of both the clay pore surface area that occupied by adsorbed oil and formation temperature.The results are obtained in four aspects:(1)For the Qing 1 Member shale,with the increase of maturity,Mk decreases.Given Ro of 0.83%–1.65%,Mk is about 50–250 mg/g.(2)The clay in shale adsorbs asphaltene.Mc is 0.63 mg/m^(2),and about 15%of the clay pore surface is occupied by adsorbed oil.(3)In the low to medium maturity stages,the shale oil adsorption is controlled by organic matter.When Ro>1.3%,the shale oil adsorption capacity is contributed by clay pores.(4)The oil adsorption capacity evaluated on the surface at room temperature is 8%–22%(avg.15%)higher than that is held in the formations.The proposed evaluation model reveals the occurrence mechanisms of shale oils with different maturities,and provides a new insight for estimating the reserves of shale oil under formation temperature conditions.

The study on exploitation potential of original low-oil-saturation reservoirs

It is preliminary estimated that the proved geological reserves of original low-oil-saturation reservoirs(OLOSRs)of 54 blocks in China are more than 820 million tons.As same as the high water-cut stage of a reservoir after water flooding,the initial water cut of OLOSRS is higher than 80%.The industrial application of EOR technology could efficiently enhance oil recovery rate from 8.4% to 20.1% of reservoirs after water flooding.The suitable measurements of EOR to the OLOSRs probably have a profound impact on achieving higher oilfield reserves and production.In this paper,the main characteristics and reserves potential of OLOSRs have been studied by investigations and laboratory experiments.The relationship between initial oil saturation and displacement efficiency is also analyzed.The feasibility of EOR technologies for different OLOSRs is discussed.The results show that the OLOSRs could be divided into two categories(primary and secondary)by origin of low oil saturation.The two categories contain abundant reserves in China’s major oilfields,but their occurrence states of crude oil are quite different.If the average oil saturation of the OLOSR is defined at 40%,there are 13.1%-54.2%crude oil that could be recovered by using the existing EOR technology,especially in the primary OLOSRs with low permeability and the secondary OLOSRs with high permeability.