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.

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.

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.

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.

Matter Composition and Two Stage Evolution of a Liangshan Super High-Sulfur Coal Seam in Kaili,Eastern Guizhou

Super-high sulfur coal resultes in serious coal-derived pollution but might have a particular genesis. Thus,a columnar section of an Early Permian Liangshan Formation coal seam. weight average sulfur content 5.80%,from Kaili,eastern Guizhou,was studied using the methods of coal petrology and geochemistry. The results show that the seam was apparently formed in seawater-effected peat bogs that developed in two distinct stages. During the first stage various layers were formed in a supratidal bog and have a composition characteristic of a bog with a gradually decreasing sea-water effect,decreasing water dynamics,and an increasingly reductive environment. Layers in the upper seam formed during a second stage in an intertidal bog. These layers are very high in total and inorganic sulfur,the ratios of or-ganic/inorganic sulfur and V/I drop,they are high in coal ash yield and have a high ash component index,considerable barkinite,oxidized and detrital macerals,have a porphyroclatic micro-structure and are rich in pyrite,all of which indi-cate the coal-forming environment had higher oxidation potential,strong and roiling water dynamics,and intermittent exposure to a sulfur rich environment.

Separator coatings as efficient physical and chemical hosts of polysulfides for high-sulfur-loaded rechargeable lithium–sulfur batteries

Lithium-sulfur batteries(LSBs)are promising alternative energy storage devices to the commercial lithium-ion batteries.However,the LSBs have several limitations including the low electronic conductivity of sulfur(5×10^-30S cm^-1),associated lithium polysulfides(PSs),and their migration from the cathode to the anode.In this study,a separator coated with a Ketjen black(KB)/Nafion composite was used in an LSB with a sulfur loading up to 7.88 mg cm^-2to mitigate the PS migration.A minimum specific capacity(Cs)loss of 0.06%was obtained at 0.2 C-rate at a high sulfur loading of 4.39 mg cm^-2.Furthermore,an initial areal capacity up to 6.70 mAh cm^-2 was obtained at a sulfur loading of 7.88 mg cm^-2.The low Cs loss and high areal capacity associated with the high sulfur loading are attributed to the large surface area of the KB and sulfonate group(SO3^-)of Nafion,respectively,which could physically and chemically trap the PSs.

REE Geochemistry of Moderate-and High-Sulfur Coals from North Shanxi, China

Contents of the rare-earth elements (REE) in two coal seams from North Shanxi Province, China, were determined using the instrumental neutron activation method. Based on the REE distribution patterns, and correlation analysis and cluster analysis, the main conclusions were drawn as follows. The REE contents are controlled mainly by the coal-forming environments, but might be affected by acidic solution leaching after peat sedimentation. The REE distribution patterns should be nearly the same in the sublayers of the same coal seam, and the occurrence of abnormal patterns might indicate the geological effect during post-sedimentation. The REE in coals are present mainly in the inorganic phase, and might be derived mainly from terrigenous detrital minerals. Some harmful elements, such as V, P, Mo, Cr, Cu, Mo, Th and Cd, might have cleaning potential during processing and dressing by washing because they are associated with REE.

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

集中的处理高硫、高酸味粗略贡献了精制企业的油的全面经济好处的改进，但是也导致了粗略的乳化，过程单位的严重腐蚀和环境 protectionissues.The 长周期，过程单位的安全、光滑的操作在最佳的处理线路的选择和一系列技术措施的采纳以后被保证。

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.

考虑硫沉积影响的水平井稳产能力预测

水平井是高效开发高含硫气藏的主要井型。高含硫气藏在开发过程中,井筒附近压力下降,导致水平井井筒周围形成不规则的硫沉积区,严重的可能导致部分井筒单元没有气体流入。为了更好地对该类气藏进行气井稳产能力预测,构建了水平井分段渗流双区复合物理模型,建立了不稳定渗流数学模型,并采用Laplace积分变换、边界元和压降叠加对井底压力进行了求解。结合不稳定渗流数学模型与高含硫气藏物质平衡方程,构建气井稳产能力预测模型,分析了不同参数对稳产时间和井底压力的影响。研究结果表明:含硫饱和度、堵塞段与渗流段长度比值和水平段长度等对稳产时间和井底压力有着非常明显的影响,含硫饱和度和水平段长度与气井稳产时间呈指数变化关系。通过对元坝气藏某水平井进行实例分析,验证了该方法的准确性,该模型和方法的建立为高含硫气藏水平井稳产能力预测提供了理论依据。

高含硫气田集输SCADA安全评估方法

油气能源基础设施安全越来越受到组织化攻击威胁,因此,对能源基础设施尤其是对高含硫气田集输SCADA系统安全状态识别就显得尤为必要。为了揭示高含硫气田集输SCADA系统安全评估中随机性和不完全性对安全状态评估结果的影响,提出了基于云模型改进白化权函数的灰云安全评估方法。首先,对评估结果进行等级划分,设计了组合权重优化模型;然后,按照专家评分细则确定出样本矩阵,利用云模型改进白化权函数,形成灰色评估权矩阵;最后,结合优化后的权重通过逐级评估得到系统最终的风险值并确定系统风险评估状态。以3个实际应用场景为例,验证了方法的有效性。研究结果表明,与层次分析法、变异系数法、线性加权和乘法加权法比较,组合优化赋权方法的离散度为0.456,线性加权和乘法加权的离散度为0.514和0.860,层次分析法和变异系数法的离散度为1.294和1.225,提出的组合优化赋权模型的离散度最小,表明此方法比其他方法更有效;将SCADA安全评估中风险指标信息不完全性与专家知识的不完全性和随机性结合起来,不仅能定性评估和预测整体SCADA系统的安全状态,而且实现二级指标风险量化;该模型能揭示各风险指标的脆弱程度,为下一步安全加固提供方向。本研究不仅有利于识别高含硫气田SCADA系统安全状态,而且为其他行业安全评估提供了参考。

典型高含硫气井分离器低效分离问题探究

天然气气井在开发生产后期的过程中,通常伴随气田水、细小颗粒等产出,采用分离装置进行初处理,由于分离装置中各相不可能实现完全分离,分离效果不佳,进而对下游装置平稳运行产生不利影响,并可能造成严重经济损失。通过现场试验分析某高含硫气井分离器低效率分离的现象,发现了分离器进气口流速增大,无足够稳定空间,内部液滴夹带严重,分离效果差的问题。提出了高含硫气井分离器低效分离问题的解决措施:正确选用入口元件并校核入口管嘴动压能;采用Ishii-Grolmes准则估算卧式气液分离器气相初始夹带速度;校核捕雾器的安装要求及淹没点(flooding point);选用可拆卸型内构件,设置内构件压差监测、建立定期清洗作业规程;井口一级气液分离器也可不配置捕雾器,简化设计,减少维护工作量。以上措施对高含硫气井分离器的设计、生产过程管理有一定指导意义。

掺杂秸秆的高硫煤气化脱硫行为研究

通过热重分析法研究高硫肥煤与玉米秸秆混合物的热解动力学,并利用Coats-Redfern法计算混合物的活化能、指前因子。通过对其混合物的热解实验,发现掺杂玉米秸秆对高硫煤有明显的脱硫作用。

内蒙古某含碳高硫锌锡矿石选矿试验研究

内蒙古某含碳高硫锌锡矿石锌品位1.02%、锡品位0.86%,硫和碳含量分别为14.02%、1.68%。矿石矿物组成较复杂,主要有用矿物为闪锌矿、锡石和黄铁矿,脉石矿物主要为石英、绿泥石和绢云母等。为确定矿石合理的开发利用工艺,采用预先脱碳—浮重联合工艺流程开展选矿试验研究。结果表明,矿石经预先脱碳、1粗1扫1精锌硫混选、1粗1扫3精锌硫分离浮选流程处理,闭路试验可得到Zn品位为45.16%、Zn回收率为71.19%的锌精矿,S品位为46.92%、S回收率81.91%的硫精矿;浮选尾矿采用摇床重选,经粗选、精选、复选和中矿再选,可获得Sn品位45.52%、Sn回收率81.99%的锡精矿,以及Sn品位3.13%、Sn回收率11.09%的锡中矿。所设计试验流程较好地解决了矿石中有机碳对浮选的不利影响,综合回收了有价矿物,可为同类矿石的开发利用提供理论借鉴。

高含硫天然气净化装置腐蚀特征与典型腐蚀案例分析

相关高含硫天然气净化装置的工程建设、设备制造、材料选型等标准规范较少,多采用或借鉴石油炼制行业标准。普光气田天然气净化厂自2009年投产至今,因高酸性气体腐蚀,以及酸性气体、制造缺欠、材料缺陷等多因素耦合腐蚀,引发装置设备或设施多次泄漏,成为制约工厂安全、高效、长周期运行的主要问题。通过统计分析历年异常事件、设备检维修台账、压力容器管道检测台账等,归纳了高含硫净化装置重点腐蚀区域、影响因素、腐蚀机理,得出湿硫化氢腐蚀、高温硫腐蚀、二氧化硫腐蚀、垢下腐蚀为主要腐蚀形式;从区域、类别、诱因等不同角度归纳了腐蚀分布规律,脱硫、硫磺回收系统腐蚀占比达80%以上;重点剖析了基于硫化氢、液硫、制造缺欠等因素的典型腐蚀案例,提出了高含硫天然气净化装置腐蚀防控措施,为同类酸性气田装置、设备腐蚀监检测和防控提供了借鉴。

天然气生产企业碳排放核算与预测方法研究--以四川盆地天然气开发为例

碳中和已成全球共识,世界能源体系正加速向低碳化演变。中国能源发展进入新时代,“双碳”目标成为经济社会发展根本遵循,作为碳排放主要来源的能源行业正大力实施绿色低碳发展战略,但要实现“双碳”目标,需建立统一规范的碳排放统计核算体系,并对碳排放量进行科学预测。选取天然气生产企业的碳排放核算及预测方法作为研究对象,基于天然气生产企业作业链,系统性梳理出天然气勘探、开发、处理、输送各环节的碳排放特征,并归类为化石燃料燃烧排放、火炬系统燃烧排放、工艺放空排放、电力消耗隐含排放等四大碳排放源,建立起碳排放核算与预测方法。通过选取四川盆地典型的常规气、页岩气、高含硫气藏进行实例测算与分析,研究结果表明:①鉴于不同类型气藏生产的碳排放结构和强度存在较大差异,为保证核算和预测结果的可靠性,对于涉及到多种类型气藏开发的企业,在碳排放核算和预测时要分类进行,并加强基础数据的统计与监测;②在能耗双控向碳排放双控转变的大趋势下,为促进油气行业的高质量发展,在建立碳排放双控指标时,应以碳排放强度指标为核心,以碳排放总量指标为辅,针对不同类型的气藏、建立不同的碳排放强度动态标准;③天然气生产企业既是甲烷的主要生产供应者、也是甲烷排放者,应加强对甲烷减排控排措施的研究。结论认为,该研究成果可以为天然气行业建立更为科学合理的碳排放核算与预测方法体系提供参考和借鉴。

燃用高硫煤锅炉空预器选型分析

为有效解决2×660MW燃用高硫煤超超临界机组空预器堵塞问题,研究了回转式空预器和管式空预器特性,分析了机组特点,提出了回转式空预器和管式空预器两级换热器串联方案,并探究了该方案对机组锅炉效率的影响。研究表明,相比于常规回转式空预器方案,采用回转式空预器和管式空预器两级换热器串联方案时,回转式空预器的出口排烟温度高于烟气酸露点,有效解决了机组空预器腐蚀堵塞问题,同时在保证设备安全下使锅炉效率提高1%。

高载量锂硫电池正极设计优化

高载量硫正极是研发高能量密度锂硫电池的必要先决条件。然而,硫载量的提高不可避免地会引起正极导电性不良、多硫化物转化动力学缓慢,穿梭效应加剧等问题。本文从化学工程的角度出发,重点关注高载量硫正极中的传质和反应过程,综述了性能优良的高载量锂硫电池正极设计思路。具体而言,从增强电子传导、改善锂离子传质、优化反应动力学、抑制多硫化物穿梭这四种研究思路出发,对比了不同优化策略之间的优劣性,并提出下一代高硫载量硫正极设计的探索方向。分析表明,基于吸附-催化双重功能的三维高导电正极具有巨大发展前景。从应用层面考虑,本文还关注了高载量正极设计中常被忽视的安全性问题,探讨了削弱正极诱导并从源头降低热失效风险的可行性,旨在为研究人员优化高载量(≥4mg/cm^(2))正极设计方案时提供实用指导。

高压辊磨对某铜矿浮选指标影响的研究

为了研究高压辊磨破碎对国内某低品位铜矿石后续浮选指标的影响,采用单因素分析方法进行了高压辊磨破碎试验、浮选优化条件试验和浮选开路对比试验。结果表明,在磨矿细度-0.074 mm占65%,粗选氧化钙用量1000 g/t、MAC-12用量20 g/t、丁基黄药用量10 g/t,扫选MAC-12用量10 g/t、丁基黄药用量5 g/t条件下,经1粗1扫浮选流程,常规破碎产品浮选可获得铜、硫品位分别为4.31%和22.46%,铜、硫回收率分别为74.382%和79.053%的粗精矿;辊压产品浮选粗精矿铜、硫品位分别为4.76%和23.06%,铜、硫回收率分别为88.137%和87.082%。铜、硫品位分别提高0.45和0.60个百分点,铜、硫回收率分别提高13.755和8.029个百分点。由此可知,通过高压辊磨破碎作业,可提高该铜矿石浮选精矿的铜、硫品位和回收率。

高硫高铁铝土矿悬浮焙烧同步脱硫除铁试验研究

中国铝土矿资源质量每况愈下,高品位铝土矿资源日渐枯竭,资源问题已成为中国铝工业发展的重要难题,而尚未得到工业规模开发利用的高硫高铁铝土矿属于难利用资源,具有巨大的潜在工业价值,对高硫高铁铝土矿开展脱硫除铁基础研究具有重要的理论与实际意义。针对广西高硫高铁铝土矿综合开发利用难题,采用“悬浮氧化焙烧—还原焙烧—磁选”工艺进行了系统的铝土矿脱硫除铁试验,并利用X射线衍射分析(XRD)、化学物相分析和X射线光电子能谱分析(XPS)等方法,研究了焙烧过程中矿物物相的转化。结果表明,矿物中主要含硫和含铁矿物为黄铁矿,采用“悬浮氧化焙烧—还原焙烧—磁选”工艺可同步实现硫元素的高效脱除和铁元素的富集分离。当悬浮氧化焙烧条件为焙烧温度700℃、焙烧时间40min、O2浓度40%、总气量600mL/min,可获得St为0.396%、脱硫率为98.10%的氧化焙烧产品;然后进行悬浮还原焙烧条件为焙烧温度550℃、焙烧时间20min、CO浓度20%、总气量600mL/min、磁场强度150kA/m时,可获得TFe为54.79%的铁精矿和St为0.248%、TFe为4.37和Al2O3含量为75.27%的富铝矿。此技术大幅度提高了高硫高铁铝土矿的Al2O3含量,有利于后续铝土矿溶出,达到了脱硫除铁提铝的技术目标。该工艺为该类难选高硫高铁铝土矿资源的高效利用提供了一种新的技术途径。