Research advances on the mechanisms of reservoir formation and hydrocarbon accumulation and the oil and gas development methods of deep and ultra-deep marine carbonates

Based on the new data of drilling, seismic, logging, test and experiments, the key scientific problems in reservoir formation, hydrocarbon accumulation and efficient oil and gas development methods of deep and ultra-deep marine carbonate strata in the central and western superimposed basin in China have been continuously studied.(1) The fault-controlled carbonate reservoir and the ancient dolomite reservoir are two important types of reservoirs in the deep and ultra-deep marine carbonates. According to the formation origin, the large-scale fault-controlled reservoir can be further divided into three types:fracture-cavity reservoir formed by tectonic rupture, fault and fluid-controlled reservoir, and shoal and mound reservoir modified by fault and fluid. The Sinian microbial dolomites are developed in the aragonite-dolomite sea. The predominant mound-shoal facies, early dolomitization and dissolution, acidic fluid environment, anhydrite capping and overpressure are the key factors for the formation and preservation of high-quality dolomite reservoirs.(2) The organic-rich shale of the marine carbonate strata in the superimposed basins of central and western China are mainly developed in the sedimentary environments of deep-water shelf of passive continental margin and carbonate ramp. The tectonic-thermal system is the important factor controlling the hydrocarbon phase in deep and ultra-deep reservoirs, and the reformed dynamic field controls oil and gas accumulation and distribution in deep and ultra-deep marine carbonates.(3) During the development of high-sulfur gas fields such as Puguang, sulfur precipitation blocks the wellbore. The application of sulfur solvent combined with coiled tubing has a significant effect on removing sulfur blockage. The integrated technology of dual-medium modeling and numerical simulation based on sedimentary simulation can accurately characterize the spatial distribution and changes of the water invasion front.Afterward, water control strategies for the entire life cycle of gas wells are proposed, including flow rate management, water drainage and plugging.(4) In the development of ultra-deep fault-controlled fractured-cavity reservoirs, well production declines rapidly due to the permeability reduction, which is a consequence of reservoir stress-sensitivity. The rapid phase change in condensate gas reservoir and pressure decline significantly affect the recovery of condensate oil. Innovative development methods such as gravity drive through water and natural gas injection, and natural gas drive through top injection and bottom production for ultra-deep fault-controlled condensate gas reservoirs are proposed. By adopting the hierarchical geological modeling and the fluid-solid-thermal coupled numerical simulation, the accuracy of producing performance prediction in oil and gas reservoirs has been effectively improved.

Insight into the oxidative desulfurization of high-sulfur petroleum coke under mild conditions:a journey of vanadium-substituted Dawson-type phosphotungstic acid

High-sulfur petroleum coke(HSPC),that is a by-product from slag oil in the coking process of refning,shows versatility values in practical applications and,however,concentrates the majority of organic sulfur.Herein,we design and construct a highly efective CTAB@HPA composites to be explored for the catalytic oxidative desulfurization of HSPC under mild conditions using hydrogen peroxide as the oxidant and 1-butyl-3-methylimidazole tetrafuoroborate ionic liquid as the extractant.The results demonstrate that the sulfur content of HSPC could be strikingly reduced from 4.46 wt%to 2.48 wt%under 60℃ and atmospheric pressure,and that the organic sulfur in HSPC is mainly oxidized to sulfoxide,sulfone and sulfate,which latter can be directly separated from petroleum coke.Moreover,the efect of reaction conditions on the desulfurization performance of HSPC as well as the catalytic oxidation reaction kinetic of HSPC desulfurization was systematically investigated.Furthermore,a mechanism for the oxidative desulfurization of HSPC over CTAB@HPA catalysts was proposed.Therefore,this work provides new insight into how to construct active catalysts for the desulfurization of HSPC under mild conditions.

Digestion mechanism and crystal simulation of roasted low-grade high-sulfur bauxite

Low-grade high-sulfur bauxite was pretreated via suspension roasting and muffle furnace roasting to remove sulfur and enhance digestion properties.The results show that sulfur can be efficiently removed,and the alumina digestion properties are significantly improved after suspension roasting.Under optimal conditions(t=70 min,T=280°C,w(CaO)=8%and Nk=245 g/L),the digestion ratios are 94.45%and 92.08%for the suspension-roasted and muffle-roasted ore,respectively,and the apparent activation energies are 63.26 and 64.24 kJ/mol,respectively.Two crystal models were established by Materials Studio based on the XRD patterns.The DFT simulation shows that the existing Al—O bands after suspension roasting can improve alumina digestion.The(104)and(113)planes of Al2O3 after suspension roasting are found to combine with NaOH more easily than those of Al2O3 treated in a muffle furnace.

Speciation and thermal transformation of sulfur forms in high-sulfur coal and its utilization in coal-blending coking process:A review

The utilization of high-sulfur coal is becoming more urgent due to the excessive utilization of low-sulfur,high-quality coal resources,and sulfur removal from high-sulfur coal is the most important issue.This paper reviews the speciation,forms and distribution of sulfur in coal,the sulfur removal from raw coal,the thermal transformation of sulfur during coal pyrolysis,and the sulfur regulation during coal-blending coking of high organic-sulfur coals.It was suggested that the proper characterization of sulfur in coal cannot be obtained only by either chemical method or instrumental characterization,which raises the need of a combination of current or newly adopted characterization methods.Different from the removal of inorganic sulfur from coal,the organic sulfur can only be partly removed by chemical technologies;and the coal structure and property,particularly high-sulfur coking coals which have caking ability,may be altered and affected by the pretreatment processes.Based on the interactions among the sulfur radicals,sulfur-containing and hydrogen-containing fragments during coal pyrolysis and the reactions with minerals or nascent char,regulating the sulfur transformation behavior in the process of thermal conversion is the most effective way to utilize high organic-sulfur coals in the coke-making industry.An in-situ regulation approach of sulfur transformation during coal-blending coking has been suggested.That is,the high volatile coals with an appropriate releasing temperature range of CH4 overlapping well with that of H2 S from high organic-sulfur coals is blended with high organic-sulfur coals,and the C–S/C–C bonds in some sulfur forms are catalytically broken and immediately hydrogenated by the hydrogencontaining radicals generated from high volatile coals.Wherein,the effect of mass transfer on sulfur regulation during the coking process should be considered for the larger-scale coking tests through optimizing the ratios of different coals in the coal blend.

Geochemical Characterization and Origin of High-Sulfur,Heavy Oils in Jiyang Sub-Basin,East China

High-sulfur,heavy petroleum is widely occurring in the Tertiary lacustrine Jiyang sub-basin, Bohai Bay Basin.They are differentiated into two families based on the bulk properties and biomarker compositions.Family 1 is characterized by high resins（40%-71%）and sulfur（2%-4%）,and low wax （l%-6%）,with n-alkanes removed by biodegradation,whereas family 2 is characterized by extremely abundant sulfur（3%-10%）,and high asphaltenes（7%-31%）and wax（2%-19%）,with no evidence of microbial attack.The oils of family 1 are distributed in the reservoir,lower than 1500 m throughout the sub-basin.Biomarker assemblages,such as low pristane/phytane ratios（1 Pr/Ph）and a high abundance of carotane,gammacerane,and dinosterane,suggest that they are derived from the calcareous mudstones and shales among the stratified,saline Es_4~u unit,in addition to the in situ biodegradation-concentrated sulfur content.However,the oils of family 2 are identified only in the western Zhanhua and eastern Chezhen depressions,with a depth deeper than 1700 m.Physical properties,together with biomarker ratios,including even-numbered n-alkanes,1 Pr/Ph,trace diasteranes,higher C35 homohopanes,and abundant dibenzothiophene series,with1 dibenzothiophene/phenanthrene,indicate an origin from carbonate source rocks.The X-ray diffraction analysis showed that the carbonate source rock is limited in the Es_4~u unit of the Bonan sag,which is different from most other source rocks in the same horizon.It is suggested that the high-sulfur,heavy oils are generated at the early stage of the oil window.Bacterial sulfate reduction might be responsible for the occurrence of sulfur species in the high-sulfur,heavy oils,while heavy biodegradation will enhance sulfur concentrations.

Removal and recovery of titanium(Ⅳ) from leach liquor of high-sulfur bauxite using calcium alginate microspheres impregnated with di-(2-ethylhexyl) phosphoric acid

In the leaching solution of high-sulfur bauxite roasted by sulfuric acid,a high concentration of aluminum presented along with titanium and iron.The present work was to remove Ti(IV)from the leach liquor by calcium alginate microsphere sorbent material(CA-P204)based on natural alginate impregnated with di-(2-ethylhexyl)phosphoric acid(D2EHPA)to purify leaching solution.Cation exchange and chelation make major contributions to the adsorption mechanism according to Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy analysis.The results showed that Ti(IV)was successfully removed by the CA-P204 adsorbent from the Ti(IV)-Al(III)-Fe(III)ternary system with a dynamic column experiment.The removal rate of titanium was nearly 95%under optimal conditions and the maximum adsorption capacity was 66.79 mg/g at pH 1.0.Reusability of CA-P204 was evaluated over three consecutive adsorption/desorption cycles.The adsorption process was simple,low-cost,and had no waste discharge,suggesting that the CA-P204 was promising,efficient,and economical for removing Ti(IV)from high-sulfur bauxite leaching solution.

Multi-objective optimization of high-sulfur natural gas purif ication plant

There exists large space to save energy of high-sulfur natural gas purification process.The multi-objective optimization problem has been investigated to effectively reduce the total comprehensive energy consumption and further improve the production rate of purified gas.A steady-state simulation model of high-sulfur natural gas purification process has been set up by using ProMax.Seven key operating parameters of the purification process have been determined based on the analysis of comprehensive energy consumption distribution.To solve the problem that the process model does not converge in some conditions,back-propagation(BP)neural network has been applied to substitute the simulation model to predict the relative parameters in the optimization model.The uniform design method and the table U21(107)have been applied to design the experiment points for training and testing BP model.High prediction accuracy can be achieved by using the BP model.Nondominated sorting genetic algorithm-II has been developed to optimize the two objectives,and 100 Pareto optimal solutions have been obtained.Three optimal points have been selected and evaluated further.The results demonstrate that the total comprehensive energy consumption is reduced by 13.4%and the production rate of purified gas is improved by 0.2%under the optimized operating conditions.

Problems Encountered and Countermeasure Adopted During Processing of Shengli High-sulfur and High-acidity Crude

The centralized processing of high-sulfur and high-acidity crude has contributed to improvement of the overall economic benefits of the oil refining enterprise, but has also resulted in crude emulsification, severe corrosion of process units and environmental protection issues. The long-cycle, safe and smooth operation of process units were guaranteed after selection of optimal processing routes and adoption of a series of technical measures.

Comprehensive study on the spatial distribution of heavy metals and their environmental risks in high-sulfur coal gangue dumps in China

The accumulation of coal gangue(CG)from coal mining is an important source of heavy metals(HMs)in soil.Its spatial distribution and environment risk assessment are extremely important for the management and remediation of HMs.Eighty soil samples were collected from the high-sulfur CG site in northern China and analyzed for six HMs.The results showed that the soil was heavily contaminated by Mn,Cr and Ni based on the Nemerow index,and posed seriously ecological risk depended on the geo-accumulation index,potential ecological risk index and risk assessment code.The semi-variogram model and ordinary kriging interpolation accurately portrayed the spatial distribution of HMs.Fe,Mn,and Cr were distributed by band diffusion,Ni was distributed by core,the distribution of Cu had obvious patchiness and Zn was more uniform.The spatial autocorrelation indicated that all HMs had strong spatial heterogeneity.The BCR sequential extraction was employed to qualify the geochemical fractions of HMs.The data indicated that Fe and Cr were dominated by residual fraction;Cu,Ni and Zn were dominated by reducible and oxidizable fractions;Mn was dominated by reducible and acid-extractable(25.38%-44.67%)fractions.Pearson correlation analysis showed that pH was the main control factor affecting the non-residue fractions of HMs.Therefore,acid production from high sulfur CG reduced soil pH by 2-3,which indirectly promoted the activity of HMs.Finally,the conceptual model of HMs contamination at the CG site was proposed,which can be useful for the development of ecological remediation strategies.

Spectral narratives of microstructural restyling and their controls on hydrocarbon generation potential from coal

The low to medium-rank Tertiary coals from Meghalaya,India,are explored for the first time for their comprehensive micro-structural characterization using the FTIR and Raman spectroscopy.Further,results from these coals are compared with the Permian medium and high-rank coals to understand the microstructural restyling during coalification and its controls on hydrocarbon generation.The coal samples are grouped based on the mean random vitrinite reflectance values to record the transformations in spectral attributes with increasing coal rank.The aliphatic carbon and the apparent aromaticity respond sharply to the first coalification jump(R:0.50%)during low to medium-rank transition and anchizonal metamorphism of the high-rank coals.Moreover,the Raman band intensity ratio changes during the first coalification jump but remains invari-able in the medium-rank coals and turns subtle again during the onset of pregraphitization in high-rank coals,revealing a polynomial trend with the coal metamorphism.The Rock-Eval hydrogen index and genetic potential also decline sharply at the first coalification jump.Besides,an attempt to comprehend the coal microstructural controls on the hydrocarbon poten-tial reveals that the Tertiary coals comprise highly reactive aliphatic functionalities in the type I-S kerogen,along with the low paleotemperature(74.59-112.28℃)may signify their potential to generate early-mature hydrocarbons.However,the presence of type II-II admixed kerogen,a lesser abundance of reactive moieties,and overall moderate paleotemperature(91.93-142.52℃)of the Permian medium-rank coals may imply their mixed hydrocarbon potential.Meanwhile,anchizonal metamorphism,polycondensed aromatic microstructure,and high values of paleotemperature(~334.25 to~366.79℃)of the high-rank coals indicate a negligible potential of producing any hydrocarbons.

Interaction of sulfur with iron compounds in sodium aluminate solutions

Reaction behaviors of sulfur and iron compounds in sodium aluminate solutions were investigated. The results show that iron compounds can remarkably remove the S2 but cannot get rid of S2Oc2-, SO^2- and SO4^-2 in sodium aluminate solutions. The removal efficiency of S^2- using ferrous compound and ferric compound can reach 86.10% and 92.70% respectively when the iron compounds were added with a molar ratio of 2：1 compared with the sulfur in liquors at 100℃. Moreover, several same compounds are formed in those two desulfurization processes with ferrous or ferric compounds, including erdite, hematite, amorphous ferrous sulfide, polymerized sulfur-iron compounds and ferric sulfate. The major difference between these two processes is that the erdite generated from ferrous compounds at the initial reaction stage will convert to a sodium-free product FeS2 at the subsequent stage.

常减压装置加工高硫高酸原油腐蚀分析与对策

随着加工原油中硫含量增加和酸值上升,常减压蒸馏装置存在较为严重的腐蚀问题。本文通过对常减压装置原油加工情况及主要存在的腐蚀问题进行分析,并结合其腐蚀机理研究,针对性地提出应对措施及建议。

Comparison of deep desulfurization methods in alumina production process

Several methods of deep desulfurization in alumina production process were studied, and the costs of these methods were compared. It is found that most of the S2- in sodium aluminate solution can be removed by adding sodium nitrate or hydrogen peroxide in digestion process, and in this way the effect of S2- on alumina product quality is eliminated. However, the removal efficiency of 2?32OS in sodium aluminate solution is very low by this method. Both S2- and 2?32OS in sodium aluminate solution can be removed completely by wet oxidation method in digestion process. The cost of desulfurization by wet oxidation is lower than by adding sodium nitrate or hydrogen peroxide. The results of this research reveal that wet oxidation is an economical and feasible method for the removal of sulfur in alumina production process to improve alumina quality, and provide valuable guidelines for alumina production by high-sulfur bauxite.

Effects of iron-containing phases on transformation of sulfur-bearing ions in sodium aluminate solution

Sulfides in the high-sulfur bauxite lead to serious steel equipment corrosion and alumina product degradation via theBayer process,owing to the reactions of sulfur and iron-containing phases in the sodium aluminate solution.The effects ofiron-containing phases on the transformation of sulfur-bearing ions(S2?,223S O?,23SO?and24SO?)in sodium aluminate solutionwere investigated.Fe,Fe2O3and Fe3O4barely react with23SO?and24SO?,but all of them,particularly Fe,can promote theconversion of223S O?to23SO?and S2?in sodium aluminate solution.Fe can convert to3Fe(OH)?in solution at elevatedtemperatures,and further react with S2?to form FeS2,but Fe2O3and Fe3O4have little influence on the reaction behavior of S2?insodium aluminate solution.Increasing temperature,duration,dosage of Fe,mole ratio of Na2Ok to Al2O3and caustic sodaconcentration are beneficial to the transformation of223S O?to23SO?and S2?.The results may contribute to the development oftechnologies for alleviating the equipment corrosion and reducing caustic consumption during the high-sulfur bauxite treatment bythe Bayer process.

Well-controlled stirring tank leaching to improve bio-oxidation efficiency of a high sulfur refractory gold concentrate

For the high sulfur refractory gold concentrate with 41.82%sulfur and 15.12 g/t gold,of which 82.11%was wrapped in sulfide,a well-controlled stirring tank leaching was carried out to improve the bio-oxidation efficiency.Results show that bio-oxidation pretreatment can greatly improve the gold recovery rate of high-sulfur refractory gold concentrate,and at the optimum pH 1.3 in this study,compared with the process without pH control,the oxidation rate of sulfur increased from 79.31%to 83.29%,while the recovery rate of gold increased from 76.54%to 83.23%;under this condition the activity of mixed culture could be sustained and the formation of jarosite could diminish.The results also displayed that for the high sulfur refractory gold concentrate,the recovery of gold is positively correlated with the oxidation rate of sulfur,and the recovery rate of gold increases with the increase of sulfur oxidation rate within a certain range.

Process Mineralogy of Iranian High Sulfur Iron Ore

Processing of Iranian high sulfur iron ore is problematic in minerals industry. The iron ores were studied by the means of polarizing microscopy, chemical analysis, X-ray diffraction. The study shows that the iron ores have high grade of iron, and complex structures. XRD showed that the iron ore consists of metallic minerals such as magnetite with a small amount of hematite and limonite and non-metallic minerals as serpentine, chlorite, and talc. The average particle size of magnetite crystals is 0.182 mm. The ore contains 1.62% sulfur as harmful impurity in form of pyrite mineral. Due to the isomorphism of magnesium and iron, magnetite mono crystal grade is lower than 68%, and difficult to be physically upgraded to a higher-grade iron concentrate using the available mineral processing technologies.

Thermodynamic analysis of Na−S−Fe−H_(2)O system for Bayer process

Thermodynamic diagrams of Na−S−Fe−H_(2)O system were constructed to analyze the behavior of sulfur and iron in the Bayer process.After digestion,iron mainly exists as Fe_(3)O_(4) and Fe_(2)O_(3) in red mud,and partial iron transfers into solution as Fe(OH)_(3)^(−),HFeO_(2)^(−),Fe(OH)_(4)^(−)and Fe(OH)_(4)^(2−).The dominant species of sulfur is S^(2−),followed by SO_(4)^(2−),and then SO_(3)^(2−)and S_(2)O_(3)^(2−).The thermodynamic analysis is consistent with the iron and sulfur species distribution in the solution obtained by experiments.When the temperature decreases,sulfur and iron can combine and precipitate.Controlling low potential and reducing temperature are beneficial to removing them from the solution.XRD patterns show that NaFeS_(2)·2H_(2)O,FeS and FeS_(2) widely appear in red mud and precipitates of pyrite and high-sulfur bauxite digestion solution.Thermodynamic analysis can be utilized to guide the simultaneous removal of sulfur and iron in the Bayer process.

Synthesis of ZnS from organic sulfur in petroleum coke and its photocatalysis properties

Organic sulfur in high sulfur petroleum coke was treated as the S source for synthesis of ZnS photocatalyst. Experimental results showed that with ball milling and subsequent heating treatment, ZnS compound could be successfully synthesized and showed considerable photocatalysis activity for decomposing industrial pollutants. The concentration of methyl orange or ethylene blue may be lowered to less than 5% after being decomposed by the synthesized-ZnS photocatalysis. Results of this study suggested a potential technique of turning high sulfur petroleum cokes from industrial wastes into useful products for environment improvement.

Preliminary study on washability and composition analysis of high- sulfur coal in some mining areas in Guizhou

Preliminary sink-float experiments on high-sulfur coal was done in some mining areas and carried on elementary analysis, industrial analysis, and ashcontent analysis. Through the experiments, definite middlings, and gangue, the phase analysis of sulfur was carried on, by which a good understanding of sulfur characters in raw coal was achieved.

Quantitative effects of phase transition on solute partition coefficient,inclusion precipitation, and microsegregation for high-sulfur steel solidification

Segregation and inclusion precipitation are the common behaviours of steel solidification, which are resulted from the redistribution and diffusion of the solute elements at the solid-liquid interface. The effect of the phase transition of high-sulfur free-cutting steel is quantified in the present work for the solute partition coefficient(ki), inclusion precipitation, and microsegregation by establishing a coupling model of microsegregation and inclusion precipitation, wherein the quantified dependencies of ki in terms of temperature, phase and carbon(C) content were applied. Results showed that the solidification temperature range and phase transition of high-sulfur steel that under different solidification paths and C contents were quite different, leading to differences in ki and eventually in microsegregation. kC,kP, and kS were mainly affected by phase composition and kSi was primarily by temperature, while kMn depended on both phase composition and temperature during solidification. Increasing the C content within the interval 0.07-0.48 wt%, the ‘proportion of the δ phase maintained temperature region during solidification’(Pδ), kave Pand kave S(kiave, the average value of the ki across the whole stages of solidification)decreased monotonically, whereas kave Cincreased linearly. The peritectic reaction impacted on the phase composition and ki, leading to the change in microsegregation. Such effect of the peritectic reaction was more significant at the last stage of solidification. When the Pδ was between 75% and 100%(corresponding to 0.07-0.16 wt% C), the solidification path resulted in a greater effect on the microsegregation of solutes C, P, and S because of the peritectic reaction. The microsegregation of solutes Mn and S were comprehensively influenced by kMn, kS and Mn S precipitation as well. The studies would help reveal the solute redistribution at the solid-liquid interface, and improve the segregation of high-sulfur steel by controlling the solidification and precipitation in practice.