Changes of Petroleum Acid Distribution Characterized by FT-ICR MS in Heavy Acidic Crude Oil after True Boiling Point Distillation

The molecular transformations of carboxylic acids in heavy acidic SL crude before and after true boiling point distillation were examined by ultra-high resolution negative-ion electrospray ionization(ESI) Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS). The acid class(heteroatom number), type(z numbers) and carbon number distributions were positively characterized. It was found out that the total acid number(TAN) of SL crude decreased after true boiling point distillation, and the abundance of O2 class in mass spectra was also found to be reduced from 67.6% to 34.5% in SL TBP mixed crude as measured by MS spectra, indicating to a potential carboxylic acid decomposition. However, it was interesting that the carboxylic acids type distribution in both oils was almost the same although their relative abundance in SL TBP mixed crude turned to be much lower, suggesting that various petroleum carboxylic acid types have the similar thermal decomposition reaction behavior. Furthermore, for each O2 type of acids in SL TBP mixed crude, the abundance of carboxylic acids with carbon number higher than 35 was reduced greatly, especially for those with carbon number higher than 60, the mass peaks of which were nearly totally removed, indicating that the large carboxylic acid molecules in heavy fractions decomposed more significantly because of longer heating time during the true boiling point distillation process. As a result, the reduction of TAN may be caused by the thermal decomposition of carboxylic acids especially those with high carbon number, suggesting that quick distillation or much lower pressure is required to avoid the thermal decomposition.

Research Progress in the Petroleum and Natural Gas Geological Theory of China

The Chinese landmass, as a composite region, consists of multiple small continental blocks, such as Sino-Korea, Yangtze, Tarim, etc., and orogenic belts. Because of its distinctive tectono-sedimentary evolution, China＇s oil/gas-bearing regions differ remarkably from that elsewhere in the world. For instance, in comparison to the Middle East oil/gas-bearing regions which are characterized by Mesozoic-Cenozoic marine oil/gas-bearing beds, early oil and gas discoveries in China are distributed mainly in Mesozoic-Cenozoic continental sedimentary basins. Generation of oil from terrestrial organic matter, or terrestrial oil generation, and the formation of large oil/gas fields in continental sedimentary basins were previously the major characteristics of petroleum geology of China. However, in the past 20 years, a series of major oil and gas discoveries from marine strata have been made. Marine oil/gas fields in China are mainly distributed in the Tarim, Sichuan, and Ordos basins, which are tectonically stable and covered with Mesozoic-Cenozoic deposits. In these basins, hydrocarbon-bearing strata are of old age and the oil/gas fields are commonly deeply-buried. Cumulatively, 995 oil/gas fields have been found so far, making China the fourth largest oil-producing country and the sixth largest gas-producing country in the world. In terms of petroleum and natural gas geology, theories of hydrocarbon generation from continental strata, such as terrestrial oil generation and coal-generated hydrocarbons, etc., have been established. Significant progress has been made in research on the sequence stratigraphy of continental strata, formation mechanisms of ultra-deep clastic reservoirs, and hydrocarbon accumulation in the continental subtle reservoir. Regarding research on the marine petroleum geology of China, with respect to the major characteristics, such as deeply-buried reservoirs, old strata, and multiple phases of transformation, important advances have been made, in areas such as the multiple-elements of hydrocarbon supply, formation of reservoirs jointly controlled by deposition, tectonic activities, and diagenetic fluid-rock reactions, and oil/gas reservoirs formed through superimposed multi-stage hydrocarbon accumulation. As more and more unconventional hydrocarbon resources are discovered, unconventional oil and gas reservoirs are under study by Chinese petroleum geologists, who endeavor to come up with new discoveries on their formation mechanisms.

Types and Characteristics of the Lower Silurian Shale Gas Reservoirs in and Around the Sichuan Basin

This study analyzed the characteristics and types of the Lower Silurian shale gas reservoirs in and around Sichuan Basin through field observations, slices, Ar-ion-beam milling, scanning electron microscopy, and x-ray diffraction analysis of 25 black shale outcrops and samples. Two main types of shale gas reservoirs were determined, i.e., fractures and pores. Fractures were classified into five categories, i.e., giant, large, medium, small, and micro, according to the features of the shale gas reservoirs, effect of fracture on gas accumulation, and fracture nature. Pore types include organic matter pores, mineral pores（mineral surface, intraparticle, interparticle, and corrosional pore）, and nanofractures. The various fracture types, fracture scales, pore types, and pore sizes exert different controls over the gas storage and production capacity. Pores serve as a reservoir for gas storage and, the gas storage capacity can be determined using pores; fractures serve as pathways for gas migration, and gas production capacity can be determined using them.

Positive carbon isotope excursions:global correlation and genesis in the Middle-Upper Ordovician in the northern Tarim Basin,Northwest China

Stable carbon isotope ratio （δ13Ccarb） analysis has been widely applied to the study of the inter-conti- nental or global marine carbonate correlation. Large-scale Cambrian-Ordovician carbonate platforms were developed in the Tarim Basin. But research on fluctuation character- istics and global correlation of δ13Ccarb is still weak. Based on conodont biostratigraphy and whole-rock δ13Ccarb data in the Tahe oil-gas field of the northern Tarim Basin, the global correlation and genesis of positive carbon isotope excursions in the Darriwilian--Early Katian was exam- ined. Three positive excursions were identified in the Tahe oil-gas field including the middle Darriwilian carbon iso- tope excursion （MDICE）, the Guttenberg carbon isotope excursion （GICE）, and a positive excursion within the Pygodus anserinus conodont zone which is named the Early Sandbian carbon isotope excursion （ESICE） in this paper. Furthermore, these positive excursions had no direct relation with sea level fluctuations. MDICE and GICE could be globally correlated. The Middle-Upper Ordovi- cian Saergan Formation source rocks of the Kalpin outcrops were in accordance with the geological time of MDICE and ESICE. GICE had close relationship with the source rock of the Lianglitag Formation in the basin.Massive organic carbon burial was an important factor controlling the genesis of these positive excursions.

Modeling and Simulation of Ethylene Polymerization in Industrial Slurry Reactor Series

A five-site comprehensive mathematical model was developed to simulate the steady-state behavior of industrial slurry polymerization of ethylene in multistage continuous stirred tank reactors. More specifically, the effects of various operating conditions (i.e., inflow rates of catalyst, hydrogen and comonomer) on the molecular structure and properties of polyethylene (i.e.,Mw,Mn, polydispersity index (IPD), melt index, density, etc.) are fully assessed. It is shown that the proposed comprehensive model is capable of simulating the steady-state operation of an industrial slurry stirred tank reactor series. It is demonstrated that changing the catalyst flow rate, changes simultaneously the mean residence-time in both reactors, which plays a significant role on the establishment of polyethylene architecture properties such as molecular mass and IPD. The melt index and density of polyethylene are mainly controlled by hydrogen and comonomer concentration, respectively.

Poly(styrene-co-divinylbenzene)-PAMAM-IDA chelating resin: Synthesis, characterization and application for Ni(II) removal in aqueous

PS-PAMAM-IDA chelating resins were prepared by low-generations of polyamidoamine(PAMAM) and then chloroacetic acid functionalizing commercially available ammoniated polystyrene matrix, to preconcentrate Ni2+ from synthetic aqueous samples. Different generations of PAMAM were used to obtain different chelating resins, PS-IDA, PS-1.0G PAMAM-IDA and PS-2.0G PAMAM-IDA. The synthesized resins were characterized by FTIR and elemental analysis. The effect of solution pH, kinetic studies, resin loading capacity, matrix effects etc., on metal ion adsorption to adsorbent phase, were studied by batch method. The PS-1.0G PAMAM-IDA resin was the most excellent adsorbents, with a maximum adsorption capacity of(24.09±1.79) mg/g for Ni2+ ion at pH=7. The interpretation of the equilibrium data was given by Langmuir isotherms model, and the correlation coefficient values for PS-IDA, PS-1.0G PAMAM-IDA and PS-2.0G PAMAM-IDA resins were 0.992, 0.994 and 0.987, respectively.

China's shale gas exploration and development: Understanding and practice

Through detailed analyses of the distribution characteristics of organic-rich shale, appearance features of high-quality shale, microscopic characteristics of shale reservoir rocks, fracability, and the relationship between preservation conditions and shale gas enrichment in Upper Ordovician Wufeng Formation-Lower Silurian Longmaxi Formation in Sichuan Basin, theoretical understandings and specific suggestions with respect to the exploration and development of shale gas in China are summarized and proposed respectively. Important geological understandings in the exploration and development of shale gas of the Wufeng Formation–Longmaxi Formation in the Sichuan Basin can be summarized into the following aspects: depositional environment and depositional process control the distribution of organic-rich shale; high quality shale in "sweet spot segments" are commonly characterized by high content of organic carbon, high brittleness, high porosity and gas content; organic pores are important storage space for the enrichment of shale gas; preservation conditions are the key factor for the geological evaluation of shale gas in structurally complex regions; shale gas can be considered as "artificial gas reservoirs" and the fracability assessment is essential for high-production; nanoscale storage space and the mode of occurrence control the special seepage characteristics of shale gas. The following suggestions are proposed for the development of China's shale gas industry:(1) focus more on fundamental research to achieve new breakthrough in the geological theory of shale gas;(2) emphasize exploration practices to have all-round discoveries in multiple strata;(3) study the regularities of development and production to establish new models of shale gas development;(4) think creatively to invent new technologies to tackle key problems;(5) explore the management innovation to create new mechanisms in shale gas development.

Estimation of Extreme Marine Hydrodynamic Variables in Western Laizhou Bay

Laizhou Bay and its adjacent waters are of great importance to China's marine oil and gas development. It is therefore crucial to estimate return-period values of marine environmental variables in this region to ensure the safety and success of maritime engineering and maritime exploration. In this study, we used numerical simulations to estimate extreme wave height, sea current velocity and sea-level height in western Laizhou Bay. The results show that the sea-level rise starts at the mouth of the bay, increases toward west/southwest, and reaches its maximum in the deepest basin of the bay. The 100-year return-period values of sea level rise can reach 3.4–4.0 m in the western bay. The elevation of the western part of the Qingdong Oil Field would remain above the sea surface during extreme low sea level, while the rest of the oil field would be 1.6–2.4 m below the sea surface. The return-period value of wave height is strongly affected by water depth; in fact, its spatial distribution is similar to the isobath's. The 100-year return-period values of effective wave height can be 6 m or higher in the central bay and be more than 1 m in the shallow water near shore. The 100-year return-period values of current velocity is about 1.2–1.8 m s-1 in the Qingdong Oil Field. These results provide scientific basis for ensuring construction safety and reducing construction cost.

Synthesis and Aqueous Solution Viscosity of Hydrophobically Modified Xanthan Gum

Two xanthan gum derivatives hydrophobically modified by 4 or 8 tetradecyl chains per 100 xanthan gum structure units were synthesized. The derivatives were studied by scanning electron microscope and pyrene fluorescence spectrometry. And the aqueous solution apparent viscosity of the derivatives was investi- gated. The results indicate that the network of the derivatives with more hydrophobic groups is closer and tighter. With increasing of alkyl chain substitution degree, the hydrophobically associating interactions enhance in aqueous solution. Aqueous solution apparent viscosity of the derivatives increases with increasing of polymer concentration and alkyl substitution degree, and decreases with the increase of temperature. In the brine solution, the strong viscosity enhancement phenomenon appears. The interaction between the derivatives and surfactant sodium dodecylbenzene sulfonate is strong.

Surface Modified TiO2 Nanoparticles-an Effective Anti-wear and Anti-friction Additive for Lubricating Grease

The surface modified TiO_2 nanoparticles were prepared by using 12-hydroxystearic acid chemically modified on the TiO_2 surface. The average size of the TiO_2 particles is about 30 nm. The optimum ratio of tetrabutyl titanate to 12-hydroxystearic acid was 1/0.5. The bonding form between 12-hydroxystearic acid and TiO_2 nucleus was investigated by FTIR, DSC, TGA and XRD techniques. The lubricating grease containing the surface modified TiO_2 nanoparticles possesses excellent anti-wear and anti-friction properties. Compared with the grease without TiO_2, the PB value can be increased by 52% as the best performance of the grease containing surface modified TiO_2 nanoparticles, while the friction coefficient can be reduced by 33% with the addition of a small amount of TiO_2 nanoparticles, and meanwhile the wear scar diameter decreases by 25%.

Theories and practices of carbonate reservoirs development in China

Carbonate reservoirs in China have the characteristics of diversified accumulation pattern, complex structure and varying reservoir conditions. Concerning these characteristics, this article tracks the technical breakthroughs and related practices since the 1950 s, summarizes the developed theory and technologies of carbonate reservoir development, analyzes their adaptability and problems, and proposes their development trend. The following theory and technologies have come into being:(1) carbonate reservoir formation mechanisms and compound flow mechanisms in complex medium;(2) reservoir identification and description technologies based on geophysics and discrete fracture-vuggy modeling method;(3) well testing analysis technology and numerical simulation method of coupling free flow and porous media flow;(4) enhanced oil recovery techniques for nitrogen single well huff and puff, and water flooding development techniques with well pattern design in spatial structure, changed intensity water injection, water plugging and channel blocking as the core;(5) drilling and completion techniques, acid fracturing techniques and its production increasing techniques. To realize the efficient development of carbonate oil and gas reservoirs, researches in four aspects need to be done:(1) complex reservoir description technology with higher accuracy;(2) various enhanced oil recovery techniques;(3) improving the drilling method and acid fracturing method for ultra-deep carbonate reservoir and significantly cutting engineering cost;(4) strengthening the technological integration of information, big data, cloud computation, and artificial intelligence in oilfield development to realize the smart development of oilfield.

Overpressure development and oil charging in the central Junggar Basin,Northwest China:Implication for petroleum exploration

The Junggar Basin is one of the largest and most petroliferous superimposed petroleum basins in China. The central depression area has become the frontier field for petroleum exploration. The characteristics of potential source rocks and reservoir sandstones, and the pressure regime in the central Junggar Basin were studied. Permian shales are dominated by hydrogen-rich, oil-prone algal organic matter, and Jurassic mudstones are dominated by hydrogen-poor, higher-plant derived organic matter. These source rocks are widespread and have been mature for hydrocarbon generation, suggesting good to excellent exploration potential, both for crude oils and for natural gases. The deeply buried Jurassic sandstones usually have low porosity and permeability. However, sandstones beneath the Jurassic/Cretaceous unconformity display relatively high porosity and permeability, suggesting that meteoric water leaching had improved the quality of the sandstones. Overpressure developed over much of the central Junggar Basin. The overpressured rocks are characterized by slightly increased interval transit time, low sandstone permeability, increased organic matter maturity, and high relative hydrocarbon-gas contents. Mudstones in the overpressured system have quite the same clay mineral compositions as mudstones in the lower part of the normally pressured system. Overpressure generation in the central Junggar Basin is best to be explained as the result of hydrocarbon generation and fluid retention in low-permeability rocks. Petroleum generated from Permian and Jurassic source rocks could migrate laterally through preferential petroleum migration pathways and accumulated in structural traps or lithological traps in the overpressured system, or migrate vertically through faults/ hydraulic fractures into the overlying, normally pressured system and accumulate in structural or lithological traps. Therefore, commercial petroleum reservoirs could be potentially found in both the overpressured system, and in the normally pressured system.

The uplifting and denudation of main Huangshan Mountains,Anhui Province,China

The Huangshan Mountain Geopark is an important geological landmark and tourist attraction.In this paper,we apply fission track dating to examine the uplift and exhumation processes that created the Huangshan Mountains and provide a timeline for their development.In addition to being an important scientific contribution,this information can be used on guided tours and to promote tourism.The results of eight apatite fission-track analyses suggest three age groups:56,45-30,and 15 Ma.These age groups are related to the uplifting-erosion processes involved in forming ancient multilevel denudation planes at 85-50,45-30,and 24-5 Ma,respectively.The scenic area has experienced three stages of thermal evolution.The first stage occurred before 80 Ma and the third stage after 13 Ma.The three stages had varying cooling rates:2.69,0.62,and 4.23°C/Ma,respectively.Uplifting rates also varied:0.08,0.02,and 0.12 mm/a.The uplifting ranges were also variable:1.14,1.57,and 4.00 km,respectively.Significant uplifting differences between diverse areas are obvious and there were four magnitudes of cumulative uplifting range:4060-3950,3760-3490,3190-3070,and 2650 m.The surface uplifting range varied from 450 to 2230 m.Denudation and uplifting amount averaged 2340 and 3400 m,respectively.The 1060 m difference between them is the average elevation at present.

Fission Track Thermochronology Evidence for Multiple Periods of Mineralization in the Wulonggou Gold Deposits, Eastern Kunlun Mountains, Qinghai Province

It is a puzzle to determine metallogenetic ages in the world. This article uses zircon fission track （FT） dating to probe the mineralizing epochs of Wulonggou （五龙沟） gold ore deposits in eastern Kunlun （昆仑） Mountains. Total of six zircon FT ages have been obtained and can be divided into groups of 235-216 and 197-181 Ma, as well as 162 and 124 Ma, revealing multiple epochs of metalloge- netic processes took place in Wulonggou area, mainly first two age groups. The mineralizing ages be- come lower from northeast Yanjingou （岩金沟） to southwest Hongqigon （红旗沟）. The second epoch of 197-181 Ma is first achieved by this work. It is shown that the FT ages consist with other isotopic data and reflect different regional thermotectonic events.

A new paleoenvironmental index for anoxic events—Mo isotopes in black shales from Upper Yangtze marine sediments

This paper investigates the high-solution of Mo isotopes and uses trace-element analyses for fresh and representative black shales and siliceous shales collected from the transition between the Late Ordovician and the Early Silurian at the Wangjiawan section in Yichang and the Late Permian Dalong Formation in the Shangsi Section of Sichuan. The applicability of different geochemical parameters used as paleo-oxygenation indices are also compared. The preliminary results show that V/(V+Ni), U auth (auth U), V/Cr, Ce anom and U/Th have a scattered variation range, but most samples plot within the suboxic-anoxic fields. The suboxic-anoxic environment was dominant during the deposition and formation of the two anoxic facies. These redox indicators show little correspondence to the δ 98 Mo values. The U/Mo ratio can be used as a potential proxy for the paleo-redox conditions due to the possibility that Mo is enriched relative to U at different redox gradients during early diagenesis. This evidence is more significant for the euxinicity condition and corresponds to positive δ 98 Mo (>1.5‰) values with low U/Mo ratios. This evidence is likely related to the depositional conditions near the boundary between anoxic and euxinic environments, which are characterised by low bioturbation or water circulation. Other samples reveal a wide scatter of U/Mo ratios and δ 98 Mo <1.5‰. These results are likely due to punctuated improvements in oxygenation with intense bioturbation or water circulation, which led to the redistribution of trace element.

Influences of water media on the hydrogen isotopic composition of natural gas/methane in the processes of gaseous hydrocarbon generation and evolution

The influences of water media on the hydrogen isotopic composition of organic-thermogenic natural gas were tested in three series of experiments on coal pyrolysis, with no water, deionized water (δDH2O=?58‰), and seawater (δDH2O=?4.8‰) added, respectively. The experimental results show that the productivities of H2 and CO2 obviously increased under hydrous condi tions and that the productivity of CH4 also remarkably increased in the high-evolution phase of hydrous experiments. Water was involved in the chemical reaction of hydrocarbon generation, and then the hydrogen isotopic composition of methane was affected. There is a linear correlation between the hydrogen isotopic composition of methane and its productivity, as reflected in the three series of experiments. In the case of the same CH4 productivity, the hydrogen isotopic composition of the methane produced in anhydrous experiments was the heaviest, that of the methane produced in seawater-adding experiments came se cond, and that of the methane produced in deionized water-adding experiments was the lightest. The hydrogen isotopic com position of natural gas/methane is affected by the following factors: 1) the characteristics of hydrogen isotopic composition of organic matter in source rocks, 2) the thermal evolution extent of organic matter, and 3) fossil-water media in the natural gas-generation period. The experimental results show that the influence of the fossil-water medium in the natural gas-generation period was lower than that of the other factors.

Adsorption of Isobutene on NanZSM-5 Type Zeolite with Various Si/Al Ratios： Molecular Simulation Study

Frameworks of NanZSM-5 type zeolites with various Si/A1 ratios have been constructed and optimized with molecular dynamic quench simulation. The results show that the structure parameters of NanZSM-5 type zeolite, including the bond length and atomic charges, are consistent with those predicted by ab initio cluster calculations. It was also observed that atomic charges of Si atoms were shifted to higher field in NanZSM-5 type zeolite with lower Si/Al ratio. Then, the adsorption of isobutene on NanZSM-5 with various Si/Al ratios has been investigated using grand canonical ensemble Monte Carlo simulation and Cvff-300-1.01 forcefield. The simulated adsorption amount was in good agreement with the experimental data. Based on these facts, the effects of Si/Al ratio on the adsorption amount and adsorption isotherms of isobutene on NanZSM-5 were predicted. The results indicated that Si/Al ratio was important for the adsorption of isobutene and the adsorption amount was decreased as the Si/Al ratio was increased, which can be explained that the atomic charge of Na^＋ cation would influence greatly the π electrons of the isobutene double bond due to the Coulomb force. In addition, the adsorption sites of isobutene and interaction energy of isobutene with NanZSM-5 were also discussed.

Thermal simulation experiment on the hydrocarbon regeneration of marine carbonate source rock

Hydrocarbon regeneration of marine carbonate source rock was simulated with thermal experiments in a laboratory. The results reveal that hydrocarbon regeneration does not simply continue the primary hydrocarbon generation process, and that, for marine carbonate source rock, discontinuous hydrocarbon generation differs greatly from the continuous generation. Several different features of hydrocarbon regeneration were observed in the experiments. First, the liquid hydrocarbon generation peak was always observed no matter what the initial maturity of the sample was. Moreover, the maturity and the liquid hydrocarbon yield corresponding to the peak varied with the sample’s initial maturity. Second, the hydrocarbon regeneration started earlier than the continuous one. In the experiments, the hydrocarbon could be re-generated when the sample maturity did not rise to any great extent. Third, the accumulative hydrocarbon-generating quantity during discontinuous generation was always more than that during continuous generation. And the hydrocarbon-generating quantity varied with the discontinuous generation history. Chemical kinetic analysis suggests that discontinuous hydrocarbon generation should not only be explained by the parallel reaction mechanism but also by the consecutive reaction mechanism which has been ignored in the traditional chemical kinetic model for continuous hydrocarbon generation.

Bimodal PE prepared with combined iron (II) and nickel (II) olefin polymerization catalysts

Combined iron (II) and nickel (II) olefin polymerization catalysts could produce a kind of PE having the characters of ideal bimodal PE with ap- propriate conditions and catalysts. In the ethylene homopolymerization with triethylalkylaluminum (AlEt3) as the activator, the prepared bimodal PE contained not only branched PE of high molecular weight, but also linear PE of low molecular weight. And the amounts of both fractions were similar. Ideal bimodal PE resin was prepared in one polymerization reactor.