Theoretical investigation of intrinsic point defects and the oxygen migration behavior in rare earth hafnates

In this work, the composition-dependent point defect types and formation energies of RE₂Hf₂O₇ (RE = La, Ce, Pr, Nd, Pm, Sm, Eu and Gd) as well as the oxygen diffusion behavior are systematically investigated by first-principles calculations. The possible defect reactions and dominant defect complexes under stoichiometric and non-stoichiometric conditions are revealed. It is found that O Frenkel pairs are the predominant defect in stoichiometric pyrochlore hafnates. Hf-RE cation anti-site defects, accompanied by RE vacancies and/or oxygen interstitials, are stable in the non-stoichiometric case of HfO₂ excess. On the other hand, RE-Hf anti-site defects together with oxygen vacancies and/or RE interstitials are preferable in the case of RE₂O₃ excess. The energy barriers for the migration along the V_O48f - V_O48f pathway of pyrochlore hafnates were calculated to be between 0.81 eV and 0.89 eV. Based on these results, a defect engineering strategy is proposed and the pyrochlore hafnates investigated here are predicted to exhibit potential oxygen ionic conductivity.     

Efficient utilization of silanol group in rice husk to promote the synthesis of Ni-phyllosilicate for CO2 methanation

It is a challenge to prepare Ni-phyllosilicate catalysts deriving from the reaction of nickel salts and biomass-based silica with high Ni contents. In order to efficiently synthesize nickel phyllosilicate, the acid-treated rice husk without calcination (P-R) was directly used as the raw material. The as-synthesized Ni-phyllosilicate (N/P-R) exhibited high nickel content of 46.7 wt% owing to utilization of the abundant silanol group in the fresh rice husk. On the contrary, the Ni content of Ni-phyllosilicate sample (N/R–S) prepared using the calcinated rice husk-based silica was only 4.8 wt% because of the loss of silanol group during calcination process. As a result, N/P-R displayed much higher catalytic activity for CO₂ methanation than N/R–S. It was found that the silanol group was in favour of forming the important intermediate Si(OH)₄, and thereby facilitated the formation of nickel phyllosilicate. In addition, the N/P-R catalyst demonstrated superior stability and excellent anti-sintering ability in the long lifetime test. In short, the proposed method in this work could not only efficiently synthesize nickel phyllosilicate with high Ni content, but also reduce energy consumption and operation steps compared to the one prepared using biomass-based silica.     

Numerical study on laminar burning velocity of ammonia flame with methanol addition

The combustion characteristics of ammonia/methanol mixtures were investigated numerically in this study. Methanol has a dramatic promotive effect on the laminar burning velocity (LBV) of ammonia. Three mechanisms from literature and another four self-developed mechanisms constructed in this study were evaluated using the measured laminar burning velocities of ammonia/methanol mixtures from Wang et al. (Combust.Flame. 2021). Generally, none of the selected mechanisms can precisely predict the measured laminar burning velocities at all conditions. Aiming to develop a simplified and reliable mechanism for ammonia/methanol mixtures, the constructed mechanism utilized NUI Galway mechanism (Combust.Flame. 2016) as methanol sub-mechanism and the Otomo mechanism (Int. J. Hydrogen. Energy. 2018) as ammonia sub-mechanism was optimized and reduced. The reduced mechanism entitled ‘DNO-NH3’, can accurately reproduce the measured laminar burning velocities of ammonia/methanol mixtures under all conditions. A reaction path analysis of the ammonia/methanol mixtures based on the DNO-NH3 mechanism shows that methanol is not directly involved in ammonia oxidation, instead, the produced methyl radicals from methanol oxidization contribute to the dehydrogenation of ammonia. Besides, NO_x emission analysis demonstrates that 60% methanol addition results in the highest NO_x emissions. The most important reactions dominating the NO_x consumption and production are identified in this study.     

THE ORIGIN OF DOLOMITE IN THE ASMARI FORMATION (OLIGOCENE-LOWER MIOCENE), DEZFUL EMBAYMENT, SW IRAN

Dolomitisation is an important factor controlling reservoir quality in the Asmari Formation in many producing fields in SW Iran. Dolostones have higher average porosities than limestones. Petrographic and geochemical studies have been used to determine the causes of Asmari dolomitisation at the Bibi Hakimeh and Marun fields and at the Khaviz anticline. The formation is generally characterized by a large‐scale trend of upward‐decreasing accommodation. Basal strata were deposited under relatively open‐marine, high‐energy conditions, whereas the Middle to Upper Asmari succession was deposited in relatively protected settings with more frequent evidence of exposure and evaporitic conditions. There is a general upward increase in the abundance of both anhydrite (occurring as nodules and cement) and dolomite. Two main types of dolomite fabric are recognised, reflecting the textures of the precursor limestones: (1) finely crystalline pervasive dolomite (commonly <20μ) replacing mud‐rich facies; and (2) combinations of finely crystalline replacive dolomite and surrounding areas of coarser dolomite cement (crystals up to 100μ) in grain‐supported facies. Fluid inclusion data indicate that finely crystalline dolomites formed at low temperatures (ca. <50°C), while the coarser dolomite formed at higher temperatures (50–;140°C). Whole rock‐carbonate oxygen and carbon isotope analyses of pure dolostone samples show no apparent correlation with either depositional or diagenetic textures: δ¹⁸O is generally 0 to 2.7‰ PDB, and δ¹³C is ?1 to 4‰ PDB. The importance of evaporated seawater to Asmari dolomitisation is indicated by the ubiquitous occurrence of felty‐textured anhydrite nodules in dolostone beds and the presence of high‐salinity fluid inclusions in dolomite. The derivation of dolomitising fluids from contemporaneous seawater is supported by the general correspondence between age estimates derived from the strontium isotope composition of anhydrites and dolomites and those derived from stratigraphic considerations. This suggested synsedimentary dolomitisation. Dolomitisation of the upper half of the Asmari Formation may have occurred as a result of two syn‐sedimentary mechanisms: (1) by the reflux of evaporative brines concentrated in shallow lagoons or sabkhas, through immediately underlying strata (mainly during highstands); and (2) by the flushing of platform‐top carbonates by basinal evaporated waters during lowstand/early transgression. Continued dolomitisation during deeper burial is supported by the presence of high‐temperature fluid inclusions and iron‐rich crystal rims. Dolomite within the lower part of the Asmari Formation probably mostly formed during burial as a result of compaction of, and fluid exclusion from, the underlying Pabdeh marls and shales.     

PREDICTING THE TIMING AND CHARACTERISTICS OF PETROLEUM FORMATION USING TAR MATS AND PETROLEUM ASPHALTENES: A CASE STUDY FROM THE NORTHERN NORTH SEA

The Northern Viking Graben area in the Norwegian North Sea was studied in order to investigate the petroleum formation characteristics of the Upper Jurassic Draupne Formation. In this area, the organofacies of the Draupne Formation, and consequently its petroleum generation characteristics, show significant variations. These variations represent a major risk, particularly in the context of basin modelling studies. Therefore, tar‐mat asphaltenes, oil asphaltenes and source‐rock samples from this area were studied in order to evaluate the use of migrated asphaltenes from petroleum reservoirs and tar mats in basin modelling. The samples were studied using bulk kinetic analysis, open‐system pyrolysis‐gas chromatography and elemental analyses, and the results were integrated into a basin modelling study. The results from these different sample materials were compared both to each other and to natural petroleum, in order to assess their significance for future petroleum exploration activities. We show that in cumulative petroleum systems, the transformation characteristics of the asphaltenes incorporate those of the individual source rock intervals which have contributed to the relevant reservoir system. Thus, the petroleum formation window predicted by the use of asphaltene kinetics is broad, and covers the majority of the formation windows predicted from the individual source rock samples. In addition, the molecular characteristics of asphaltene‐derived hydrocarbons show that compositional characteristics, such as aromaticity, correspond more closely to natural oils than to the respective source‐rock products. Our results confirm that the heterogeneous nature of the Draupne Formation results in a significantly broader petroleum formation window than is conventionally assumed. We propose that oil and tar‐mat asphaltenes from related reservoirs represent macromolecules which account for this heterogeneity in the source rock, since they represent mixtures of charges from the different organofacies. One conclusion is that the use of oil and tar‐mat asphaltenes in kinetic studies and compositional predictions may significantly improve definitions of petroleum formation characteristics in basin modelling.     

四川盆地及邻区上二叠统一下三叠统海槽的深水沉积特征

四川盆地及邻区广元-旺苍、城口-鄂西、开江-梁平海槽是上二叠统一下三叠统飞仙关组（P3-T1f）的深水碳酸盐沉积区。该区上二叠统上部大隆组是硅质岩、硅质泥岩、硅质灰岩组合，含放射虫、有孔虫等化石，厚125—29．0m，为海槽裂陷期凝缩沉积。三叠系飞仙关组下部为远洋沉积的暗色泥岩、微晶碎屑灰岩和重力流沉积的浊积岩、角砾灰岩组成的深水碳酸盐沉积，厚50．0～300．0m，是裂陷期后的海槽充填沉积。海槽相区沉积在晚二叠统世末达到最大海泛面沉积了大隆组。海平面缓慢下降期沉积了补偿充填性质的飞仙关组深水碳酸盐岩。海槽相区上二叠统一下三叠统飞仙关组构成了一个完整的三级层序。深水沉积物的有机碳平均值高达6．21％，是良好的烃源岩。但在海槽相区上二叠统不发育生物礁，飞仙关组缺乏鲕粒岩。     

东海西湖凹陷平湖油气田花港组高分辨率层序地层特征

通过岩心观察、测井与录井资料,对平湖油气田花港组河流相地层进行了高分辨层序地层分析,识别出2个中期旋回(MSC1与MSC2)与20个短期旋回,建立了研究区的层序地层格架。短期旋回分4种类型并以非对称旋回为主。两个中期旋回为非对称旋回,但MSC2对称性更大,反映了可容纳空间的持续增加。在基准面旋回的控制下,沉积相呈现有规律的辫状河曲流河辫状河曲流河交替演化,在每个中期旋回均以辫状河开端,以曲河流结束,由于中期旋回在长期旋回中的位置不同,曲流河的特征也有所不同。位于中期旋回上升半旋回中部的曲流河及底部的辫状河是研究区的有利砂体,尤其是前者最为有利。     

孤岛油田馆1+2砂层组湖相沉积的发现及其意义

分析胜利油区孤岛油田馆陶组上段连续取心井段的岩心,发现了存在浅水湖泊沉积的证据,据此认为馆1＋2砂层组属于浅水湖泊沉积,而非单一的河流相沉积.沉积期间,湖盆地形平坦、水体极浅,湖平面受气候影响频繁振荡式升降变化,沉积物表现为氧化、还原环境交替的红灰相间的细粒结构,湖泊沉积构造（如波状层理、浪成沙纹层理和波痕等）发育.根据岩性、沉积等特征,划分为水道、砂坪、混合坪、泥坪和沼泽等5种沉积微相类型,洪水期和枯水期各微相的发育特点和平面展布不同.馆1＋2砂层组属于湖相的观点为该区的勘探开发提供了新思路.图5参9     

乙烯齐聚催化剂研究进展

乙烯齐聚是合成直链低碳α-烯烃最先进的方法，直链低碳α-烯烃可用于生产低密度聚乙烯和高密度聚乙烯等多种精细化学品。本文综述了乙烯齐聚催化体系的研究进展，重点介绍了镍、锆、钛催化剂的组成以及反应时间、反应温度、溶剂、助催化剂等因素对乙烯齐聚活性和选择性的影响，并讨论了典型镍的催化机理。     

任丘油田雾迷山油藏抽油机井系统效率初步探讨

总公司1996年对任丘雾迷山油藏抽油机井进行测试,系统效率高达51%~68%,其结果出乎意料。从影响抽油机系统效率的几大因素入手,分析出任丘雾迷山油藏抽油机井系统效率高的主要原因。任丘雾迷山油藏属裂缝性破酸盐岩油藏(即灰岩油战),由于其裂缝发育、渗透性好、油层厚度大、地层温度高、油气比小、饱和压力低等,使得抽油机井生产呈现如下特点:()大泵径,长冲程,低冲次大排量采油;(2)中浅京挂,小沉没度;(3)抽汲流体为液体单相,泵充满程度高;(4)部分井为连抽"带喷"状态,抽油系活塞底部受力大;(5)井液粘度低,油井不结蜡,摩阻损失小。由于这些特点以及近年来使用的新型节能抽油机,使得抽油机井系统效率大大高于其它油田抽油机井系统效率。