天然气水合物储层泥质细粉砂挡砂介质堵塞规律与微观挡砂机制

中国南海海域部分天然气水合物储层中地层砂为高泥质含量细粉砂，开采防控砂难度较大。针对高泥质细粉砂挡砂机制问题，使用粒度中值为10.13 μm的泥质细粉砂样品，模拟单向气液携砂流动条件，使用绕丝筛板、金属烧结网、金属纤维、预充填陶粒4类挡砂介质在20~80 μm挡砂精度下进行挡砂模拟实验，采用显微成像系统观察挡砂介质内部及表面砂粒沉积与堵塞动态，分析介质流通性能和挡砂性能变化，总结堵塞规律、微观挡砂机制与形态及其控制因素。研究结果表明，不同类型和精度的挡砂介质对泥质细粉砂的堵塞总体呈现堵塞开始、堵塞加剧和堵塞平衡3个阶段。随着驱替进行，挡砂介质渗透率逐渐降低，幅度会高达90%以上；同时过砂速度减缓，最终过砂率为5%~10%。根据堵塞规律和微观图像分析，提出了粗组分分选桥架、局部砂团适度挡砂、整体砂桥阻挡等挡砂介质对泥质细粉砂的3种微观挡砂机制。以粗组分分选桥架挡砂机制为主的挡砂工况下，挡砂介质堵塞渗透率较高，但过砂率超过15%，挡砂效果较差；以整体砂桥挡砂机制为主时，过砂率在10%以下，挡砂性能较好，但各类挡砂介质的堵塞渗透率不足1 D，流通性能较差。局部砂团适度挡砂机制为主时介质挡砂性能及流通性能介于两者之间。挡砂介质对天然气水合物储层泥质细粉砂的微观挡砂机制和形态受挡砂介质类型、精度、地层砂特征以及流动条件等因素控制，其规律对于水合物泥质细粉砂防控砂优化有指导意义。     

水力空化改质对重质原油沥青质及性质的影响

利用水力空化过程产生局部的高温、高压、高射流以及强大的剪切力等极端化学物理条件改质处理沙特重质原油，试验结果表明：沙特重质原油经过水力空化改质后粘度由13.61降低至7.22mm2/s，残碳由7.16%降低至6.48%，实沸点蒸馏后减压渣油降低1个百分点。进一步采用APPI FT-IR MS、XRD、FT-IR、SEM和粒度分布等技术研究了水力空化改质对沙重原油分子组成，沥青质团聚体微晶结构、沥青质胶束粒径分布、沥青质官能团、沥青质形貌等方面的影响，从分子角度阐述空化改质重油的机理。研究结果表明：水力空化改质后沙重原油分子量分布、芳烃类化合物缔合作用变小；沥青质对低DBE化合物吸附性能降低；沥青质团聚体微晶结构更加松散；沥青质胶束粒度分布降低；沥青质分子相互团聚作用力减弱。进一步考察了水力空化改质前后减压渣油延迟焦化性能，改质处理后焦炭产率降低1.85个百分点，液体收率和气体产率分别增加1.52和0.33个百分点，水力空化改质对沥青质性质、结构特点的改善能够有效的提高其加工性能。     

Application of robust machine learning methods to modeling hydrogen solubility in hydrocarbon fuels

Having accurate information about the hydrogen solubility in hydrocarbon fuels and feedstocks is very important in petroleum refineries and coal processing plants. In the present work, extreme gradient boosting (XGBoost), multi-layer perceptron (MLP) trained with Levenberg–Marquardt (LM) algorithm, adaptive boosting support vector regression (AdaBoost?SVR), and a memory-efficient gradient boosting tree system on adaptive compact distributions (LiteMORT) as four novel machine learning methods were used for estimating the hydrogen solubility in hydrocarbon fuels. To achieve this goal, a database containing 445 experimental data of hydrogen solubilities in 17 various hydrocarbon fuels/feedstocks was collected in wide-spread ranges of operating pressures and temperatures. These hydrocarbon fuels include petroleum fractions, refinery products, coal liquids, bitumen, and shale oil. Input parameters of the models are temperature and pressure along with density at 20 °C, molecular weight, and weight percentage of carbon (C) and hydrogen (H) of hydrocarbon fuels. XGBoost showed the highest accuracy compared to the other models with an overall mean absolute percent relative error of 1.41% and coefficient of determination (R²) of 0.9998. Also, seven equations of state (EOSs) were used to predict hydrogen solubilities in hydrocarbon fuels. The 2- and 3-parameter Soave-Redlich-Kwong EOS rendered the best estimates for hydrogen solubilities among the EOSs. Moreover, sensitivity analysis indicated that pressure owns the highest influence on hydrogen solubilities in hydrocarbon fuels and then temperature and hydrogen weight percent of the hydrocarbon fuels are ranked, respectively. Finally, Leverage approach results exhibited that the XGBoost model could be well trusted to estimate the hydrogen solubility in hydrocarbon fuels.     

Hydrogen wettability in carbonate reservoirs: Implication for underground hydrogen storage from geochemical perspective

Hydrogen has been considered as a promising renewable source to replace fossil fuels to meet energy demand and achieve net-zero carbon emission target. Underground hydrogen storage attracts more interest as it shows potential to store hydrogen at large-scale safely and economically. Meanwhile, wettability is one of the most important formation parameters which can affect hydrogen injection rate, reproduction efficiency and storage capacity. However, current knowledge is still very limited on how fluid-rock interactions affect formation wettability at in-situ conditions. In this study, we thus performed geochemical modelling to interpret our previous brine contact angle measurements of H₂-brine-calcite system. The calcite surface potential at various temperatures, pressures and salinities was calculated to predict disjoining pressure. Moreover, the surface species concentrations of calcite and organic stearic acid were estimated to characterize calcite-organic acid electrostatic attractions and thus hydrogen wettability. The results of the study showed that increasing temperature increases the disjoining pressure on calcite surface, which intensifies the repulsion force of H₂ against calcite and increases the hydrophilicity. Increasing salinity decreases the disjoining pressure, leading to more H₂-wet and contact angle increment. Besides, increasing stearic acid concentration remarkably strengthens the adhesion force between calcite and organic acid, which leads to more hydrophobic and H₂-wet. In general, the results from geochemical modelling are consistent with experimental observations that decreasing temperature and increasing salinity and organic acid concentration increase water contact angle. This work also demonstrates the importance of involving geochemical modelling on H₂ wettability assessment during underground hydrogen storage.     

Microstructures and properties of nickel-titanium carbide composites fabricated by laser cladding

In this work, Ni/TiC composites were synthesized by the laser cladding technique (LCT). A scanning electron microscope (SEM), X-ray diffractometer (XRD), microhardness meter, electrochemical workstation, and friction and wear tester examined the microstructure, surface morphology, phase structure, microhardness, wear, and corrosion resistances of the Ni/TiC composites. These results indicated the Ni/40TiC composite contained finer equiaxed crystals than the Ni and Ni/20TiC composites. In addition, numerous TiC particles in the Ni/40TiC composite impeded growth of the nickel crystals, which resulted in the fine microstructure of the Ni/40TiC composite. The Ni, Ni/20TiC, and Ni/40TiC composites exhibited face-centered cubic (f c c) lattices. The average microhardness values of the Ni/20TiC and Ni/40TiC composites were approximately 748 HV and 851 HV, respectively. The Ni/40TiC composite had the lowest friction coefficient (0.43) among all three coatings, and only some shallow scratches appeared on the surface of the Ni/40TiC composite. The corrosion potential (E) of Ni/40TiC exceeded the Ni/20TiC composite, and both were larger than the Ni composite, which indicated the Ni/40TiC composite had outstanding corrosion resistance and the Ni composite had poor corrosion resistance. The corrosion current densities (i) of Ni, Ni/20TiC, and Ni/40TiC composites were 5.912, 4.405, and 3.248 μA/cm², respectively.     

Recent insights in synthesis and energy storage applications of porous carbon derived from biomass waste: A review

In the last few decades, global warming, environmental pollution, and an energy shortage of fossil fuel may cause a severe economic crisis and health threats. Storage, conversion, and application of regenerable and dispersive energy would be a promising solution to release this crisis. The development of porous carbon materials from regenerated biomass are competent methods to store energy with high performance and limited environmental damages. In this regard, bio-carbon with abundant surface functional groups and an easily tunable three-dimensional porous structure may be a potential candidate as a sustainable and green carbon material. Up to now, although some literature has screened the biomass source, reaction temperature, and activator dosage during thermochemical synthesis, a comprehensive evaluation and a detailed discussion of the relationship between raw materials, preparation methods, and the structural and chemical properties of carbon materials are still lacking. Hence, in this review, we first assess the recent advancements in carbonization and activation process of biomass with different compositions and the activity performance in various energy storage applications including supercapacitors, lithium-ion batteries, and hydrogen storage, highlighting the mechanisms and open questions in current energy society. After that, the connections between preparation methods and porous carbon properties including specific surface area, pore volume, and surface chemistry are reviewed in detail. Importantly, we discuss the relationship between the pore structure of prepared porous carbon with surface functional groups, and the energy storage performance in various energy storage fields for different biomass sources and thermal conversion methods. Finally, the conclusion and prospective are concluded to give an outlook for the development of biomass carbon materials, and energy storage applications technologies. This review demonstrates significant potentials for energy applications of biomass materials, and it is expected to inspire new discoveries to promote practical applications of biomass materials in more energy storage and conversion fields.     

Experimental research on combined effect of obstacle and local spraying water fog on hydrogen/air premixed explosion

In order to reveal the mechanism of water fog explosion suppression and research the combined effect of water fog and obstacle on hydrogen/air deflagration, multiple sets of experiments were set up. The results show that the instability of thermal diffusion under lean combustion conditions is the main influencing factor of hydrogen/air flame surface instability, and the existence of water fog will aggravate the hydrogen/air flame surface instability. When obstacle is not considered, 8 μm, 15 μm, 30 μm water fog can significantly reduce the flame velocity and explosion overpressure of hydrogen/air, 45 μm fine water fog plays the opposite role. When considering the relative position of the water fog release position and the obstacle, the 8 μm, 15 μm, 30 μm water fog has almost no suppression effect when released near the obstacle, but a significant suppression effect occur, when using the 45 μm water fog. In the field of theoretical research, the research results not only provide an experimental basis for the fine water fog to reduce the consequences of hydrogen explosion accidents, and the optimal diameter range used by the water fog, but also provide experimental reference for the numerical simulation of hydrogen/air explosion suppression in semi-open space, and promote the development of hydrogen explosion suppression theory. In terms of engineering applications, this study can provide a theoretical basis for the layout of fire fighting equipment in the engine room of nuclear power plants or hydrogen-powered ships.     

Stabilization of natural gas foams using different surfactants at high pressure and high temperature conditions

Natural gas foam can be used for mobility control and channel blocking during natural gas injection for enhanced oil recovery, in which stable foams need to be used at high reservoir temperature, high pressure and high water salinity conditions in field applications. In this study, the performance of methane (CH₄) foams stabilized by different types of surfactants was tested using a high pressure and high temperature foam meter for surfactant screening and selection, including anionic surfactant (sodium dodecyl sulfate), non-anionic surfactant (alkyl polyglycoside), zwitterionic surfactant (dodecyl dimethyl betaine) and cationic surfactant (dodecyl trimethyl ammonium chloride), and the results show that CH₄-SDS foam has much better performance than that of the other three surfactants. The influences of gas types (CH₄, N₂, and CO₂), surfactant concentration, temperature (up to 110°C), pressure (up to 12.0 MPa), and the presence of polymers as foam stabilizer on foam performance was also evaluated using SDS surfactant. The experimental results show that the stability of CH₄ foam is better than that of CO₂ foam, while N₂ foam is the most stable, and CO₂ foam has the largest foam volume, which can be attributed to the strong interactions between CO₂ molecules with H₂O. The foaming ability and foam stability increase with the increase of the SDS concentration up to 1.0 wt% (0.035 mol/L), but a further increase of the surfactant concentration has a negative effect. The high temperature can greatly reduce the stability of CH₄-SDS foam, while the foaming ability and foam stability can be significantly enhanced at high pressure. The addition of a small amount of polyacrylamide as a foam stabilizer can significantly increase the viscosity of the bulk solution and improve the foam stability, and the higher the molecular weight of the polymer, the higher viscosity of the foam liquid film, the better foam performance.     

Catalytic behavior in CH4 decomposition of catalysts derived from red mud: Impact of residual Na2O

Catalyst samples for CH₄ decomposition were prepared from red mud (RM) by an acid-leaching neutralization precipitation approach. Water-washing the resultant precipitates multiple times, followed by drying at 105 °C and calcination at 500 °C, resulted in a threshold of residual Na₂O, equivalent to 96% Na₂O removal. Drying the precipitate at a higher temperature of 200 °C, followed by repeated water washing, provided a deeper Na₂O removal of 99% and made the resultant samples more active for the targeted reaction. Subsequently, four catalyst samples with a simulated red mud composition and NaOH contents from 0 to 0.3 wt% were prepared and the catalytic test results revealed that the Na₂O remaining in the RM-derived catalysts did not only inhibit their activation in CH₄ but also lower their maximal activities for CH₄ decomposition. Finally, two catalysts with the same simulated red mud composition and their Na impregnated respectively on Fe₂O₃ and a mixture support of Al₂O₃-SiO₂-TiO₂ were prepared and tested to explore the effect of Na distribution on the activation behavior of RM-derived catalysts for CH₄ decomposition. The activity testing results showed that it was the Na residual dispersed on iron oxides in the RM-derived samples to significantly inhibit the activation of CH₄ decomposition.     

近源成藏——来自鄂尔多斯盆地延长组湖盆东部“边缘”延长组6段原油的地球化学证据

延安以东和以北的鄂尔多斯盆地东北部地区曾被认为位处三叠纪延长组7段（长7段）沉积期古湖盆的"边缘"，一些学者认为该区延长组烃源岩不发育，因而其油藏原油系湖盆中心生成的原油经长距离侧向运移而来；但也有研究认为，包括盆地边缘在内的整个鄂尔多斯盆地致密油藏均为近源成藏。为明确盆地东部地区延长组原油来源，对三叠纪湖盆"东缘"七里村油田的主力油层延长组6段（长6段）原油开展了原油地球化学和油源对比研究。七里村油田长6段原油具有高饱和烃、高饱芳比、低非烃和低沥青质的特征，正构烷烃呈前高单峰型，主峰碳为C₁₉，生物标志化合物分析显示长6段原油为同源成熟原油，生油母质以藻类等低等水生生物为主，混有陆源高等植物，母源沉积环境为偏还原性的淡水湖泊。七里村油田长6段原油与本地区长7段黑色泥页岩和暗色泥岩2种烃源岩均具有明显亲缘关系，而与志丹、富县等湖盆中心地区的长7段烃源岩在族组成、生物标志化合物和稳定碳同位素特征上均存在明显区别。综合分析认为七里村油田长6段原油并非湖盆中心长7段优质烃源岩所生油气经长距离运移而来，而主要为原位长7段烃源岩生成的原油经垂向运移和短距离侧向运移在长6段等储层中聚集成藏，属于近源成藏。