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.

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.

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.

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.

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.

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.

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.

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。

电石渣和煤矸石对型煤固硫性能的影响及作用机制研究

研制高效低成本的耐高温固硫剂和添加剂有助于解决型煤高温燃烧环境下钙基固硫产物的分解问题。电石渣和煤矸石属于典型的工业固体废弃物,利用固废作为添加剂制备固硫型煤有助于降低固硫型煤成本和挖掘固废资源价值,发挥这两种固废中矿物组分协同作用可改善高温条件下型煤固硫效果。开展了电石渣和煤矸石分别作为固硫剂和添加剂制备环保型煤的研究,考察了固硫剂种类(碳酸钙、氧化钙、氢氧化钙和电石渣)、钙硫物质的量比(1.5~4.0)、燃烧温度(900℃~1300℃)、煤矸石用量(2%~7%)对型煤固硫效果的影响。通过型煤燃烧评价实验发现,仅用电石渣作为固硫剂,在钙硫物质的量比为3.0时制得的型煤在燃烧温度低于1000℃时固硫率能达到80%以上,燃烧温度提高到1300℃时型煤固硫率下降40%,结合分析表征数据发现主要原因是固硫产物硫酸钙的高温分解。添加的煤矸石在高温条件下被电石渣组分活化后起到辅助固硫作用,当添加的煤矸石的质量分数达到5%时型煤的固硫率能维持在60%以上,在此基础上增加煤矸石用量并不能明显提升型煤固硫率。通过固硫产物热稳定性研究并结合分析表征数据发现,高铝煤矸石灰渣活性组分发生高温反应生成硫铝酸钙、钙黄长石、硅酸三钙等耐高温稳定物相,在一定程度上抑制了CaSO_(4)的分解,从而提高了型煤的高温固硫率。

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。

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.

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。

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。

高频燃烧红外吸收法测定铜铅锌多金属矿中的碳、硫

铜铅锌多金属矿中的碳、硫元素对矿产开采、钢铁冶炼及环境保护等方面有着重要的影响,对碳、硫的准确、快速定量检测至关重要,但未见有对铜铅锌多金属矿中的碳、硫同时测定的研究。将铜铅锌多金属矿中碳、硫含量科学分为C1、C2、S1、S2四段,并分别对样品称样量、助熔剂加入比例及种类等因素进行探究,建立了高频燃烧红外吸收法测定铜铅锌多金属矿中的碳、硫的方法,并通过标准物质验证了方法的准确度、精密度与再现性。结果表明,C1、C2、S1、S2称样量分别为0.200 0、0.100 0、0.100 0、0.100 0 g,助熔剂组合方式为Fe+W=(0.6000+0.6000)、(0.6000+0.6000)、(0.9000+0.6000)、(0.6000+0.600 0) g为最佳实验条件。C1、C2、S1、S2曲线的相关系数分别为0.999 4、0.995 9、0.999 9、0.998 9,测定结果的相对标准偏差(RSD,n=11)分别为1.3%、1.5%、1.3%、1.3%,使用3种不同型号的红外碳硫仪进行对比实验,相对标准偏差(RSD,n=11)为0.56%~6.5%。结果均显示,方法准确、可靠,满足铜铅锌多金属矿中碳、硫的同时、准确快速定量检测的要求。