STUDY ON CHEMICAL STABILITY OF ORGANIC SULFUR IN COAL AND ITS STRUCTURE*

In this paper, two high-sulfur coals were selected from Yazhou and Donglin mines of China. Inorganic sulfur was completely removed first, then the tested samples were experimented under various conditions: hydrolysis, oxidation, reduction, and supercritical extraction with methanol. The change in organic sulfur was investigated. It was found that approximately 40-60% organic sulfur in coal was released at the temperature of 350°C. The removed organic sulfur was thioalcohol and thioether, while the remaining part in coal was thiophenic sulfur.     

EFFECT OF MOISTURE IN COAL ON ITS ORGANIC SULFUR EXTRACTABILITY

Abstract

The extent of organic sulfur removed by the perchloroethylene desulfurization process depends upon several factors including the type of coal, the amount of catalyst present in it, and the temperature of organosulfiir extraction. Moisture in coal also plays a very important role in this extraction process. In this paper, the role played by moisture and its subsequent effect on the process efficiency has been investigated. It has been found that the moisture in coal affects the extraction process in two ways. Firstly, in presence of water, the temperature of the operation is reduced. This affects the organosulfiir extraction efficiency adversely. Secondly, the naturally available catalytic ingredients in coal, essential for the organosulfiir extraction, are soluble in water. Therefore, in presence of water, the catalytic potency of these catalytic species is lost, and thus reducing the organosulfiir extractability. The data presented in this paper are also important from the point of view of process development, because it has been experimentally established that the moisture content in coal has to be sufficiently reduced in order to improve the overall process efficiency.     

EFFECT OF MOISTURE IN COAL ON ITS ORGANIC SULFUR EXTRACTABILITY

The extent of organic sulfur removed by the perchloroethylene desulfurization process depends upon several factors including the type of coal, the amount of catalyst present in it, and the temperature of organosulfiir extraction. Moisture in coal also plays a very important role in this extraction process. In this paper, the role played by moisture and its subsequent effect on the process efficiency has been investigated. It has been found that the moisture in coal affects the extraction process in two ways. Firstly, in presence of water, the temperature of the operation is reduced. This affects the organosulfiir extraction efficiency adversely. Secondly, the naturally available catalytic ingredients in coal, essential for the organosulfiir extraction, are soluble in water. Therefore, in presence of water, the catalytic potency of these catalytic species is lost, and thus reducing the organosulfiir extractability. The data presented in this paper are also important from the point of view of process development, because it has been experimentally established that the moisture content in coal has to be sufficiently reduced in order to improve the overall process efficiency.     

EFFECT OF PYRITIC SULFUR AND MINERAL HATTER ON ORGANIC SULFUR REMOVAL FROM COAL

The perchloroethylene coal cleaning process uses perchloroethylene as the solvent to remove both organic and inorganic forms of sulfur without any significant loss to its calorific value. The process removes these forms of sulfur in two sequential unit steps. The objective of this investigation was to determine the exact sequence of operations in the Process. Hence, organosulfur was removed before and after depyriting and demineralizing the coal. The extent of total sulfur as well as organic sulfur removal were compared in both cases. It was found that the desulfurization is more efficient when organosulfur is extracted before pyritic sulfur and not vice versa, in the sequential removal of organic and inorganic forms of sulfur. The data presented in this paper reestablishes a fact that the mineral matter content in coal is quintessential to its organosulfur extractability.     

EFFECT OF PYRITIC SULFUR AND MINERAL HATTER ON ORGANIC SULFUR REMOVAL FROM COAL

Abstract

The perchloroethylene coal cleaning process uses perchloroethylene as the solvent to remove both organic and inorganic forms of sulfur without any significant loss to its calorific value. The process removes these forms of sulfur in two sequential unit steps. The objective of this investigation was to determine the exact sequence of operations in the Process. Hence, organosulfur was removed before and after depyriting and demineralizing the coal. The extent of total sulfur as well as organic sulfur removal were compared in both cases. It was found that the desulfurization is more efficient when organosulfur is extracted before pyritic sulfur and not vice versa, in the sequential removal of organic and inorganic forms of sulfur. The data presented in this paper reestablishes a fact that the mineral matter content in coal is quintessential to its organosulfur extractability.     

粘度指数改进剂结构与性能之间的关系

考察了粘度指数改进剂的使用性能,综合了有关粘度指数改进剂的化学结构信息,讨论了已有的结构与性能之间的关系;在此基础上提出有待深入研究的课题:①采用神经网络及化学计量学的其它方法定量地关联化学结构和使用性能;②系统地研究粘度指数改进剂高温高剪切性能及压力对其行为的影响;③粘度指数改进剂暂时粘度损失的量子化学计算。     

不溶性硫磺的制备及其热稳定性

在熔融法制备不溶性硫磺的过程中,对3种卤化物稳定剂进行了考察。结果表明,稳定剂KCl用量0．6%,反应时间1h,反应温度260℃,不溶性硫磺收率为17．09%;稳定剂KBr用量0．8%,反应时间90min,反应温度280℃,不溶性硫磺收率为28．5%;稳定剂KI用量0．6%,反应时间1h,反应温度240℃,不溶性硫磺收率为29．3%。对3种稳定剂所制备的不溶性硫磺充环烷油、脂肪烃油、芳烃油处理,比较了工艺油的品种和稳定剂的协同作用对不溶性硫磺热稳定性的影响。在3种工艺油中,以充芳烃油的不溶性硫磺的热稳定性最高;以KI制备的不溶性硫磺充油后的热稳定性最好。同时初步讨论了工艺油种类和无机卤化物对抑制不溶性硫磺还原的作用机理。     

几种焦化蜡油化学组成与结构的研究

测定了大庆、胜利、辽河、管输等5种焦化蜡油的密度、平均分子量、折光指数、元素和1H－NMR核磁共振波谱等数据，研究了5种焦化蜡油的化学组成，包括饱和烃、轻芳烃、中芳烃、重芳烃和胶质5个组分的含量，并与直馏蜡油的数据进行了对比；采用改进的B－L法、n－d－M法和密度法计算了平均结构参数。提出了焦化蜡油的芳碳率（CA％）、总环数（RT）与H／C原子比的数学关联式。     

EFFECT OF FILTRATION TEMPERATURE ON ORGANIC SULFUR REMOVAL FROM COAL BY PERCHLOROETHYLENE COAL CLEANING PROCESS

The perchloroethylene extraction desulfurization process removes the organic sulfur in coal via a hybrid mechanism of solvent extraction and chemical reaction. The nature and extent of the reaction is controlled by the extraction time and temperature of operation. Although the extraction temperature is kept identical for all types of coals (120°C), the organosulfur extraction time still depends upon the type of coal. If the reaction mixture is left too long in the extraction environment, the intermediate labile sulfur released by the reaction forms cross-links with the organic matter in the macromolecule of coal. This is detrimental to the process efficiency. Constant temperature has to be maintained throughout the extraction, till coal is separated from the solvent. If not, the extracted labile sulfur re-enters the coal macromolecule to form inter-penetrating polymer networks with the organic matter in coal. In this paper, it has been established that the time required for separation and isothermality of the process are crucial to maintain the reaction progressing toward sulfur and organic sulfur liberation from the macromolecule. The data presented in this paper are important from the viewpoint of process development, because the process mandates the separation of coal and solvent at the operating temperature.     

EFFECT OF FILTRATION TEMPERATURE ON ORGANIC SULFUR REMOVAL FROM COAL BY PERCHLOROETHYLENE COAL CLEANING PROCESS

Abstract

The perchloroethylene extraction desulfurization process removes the organic sulfur in coal via a hybrid mechanism of solvent extraction and chemical reaction. The nature and extent of the reaction is controlled by the extraction time and temperature of operation. Although the extraction temperature is kept identical for all types of coals (120°C), the organosulfur extraction time still depends upon the type of coal. If the reaction mixture is left too long in the extraction environment, the intermediate labile sulfur released by the reaction forms cross-links with the organic matter in the macromolecule of coal. This is detrimental to the process efficiency. Constant temperature has to be maintained throughout the extraction, till coal is separated from the solvent. If not, the extracted labile sulfur re-enters the coal macromolecule to form inter-penetrating polymer networks with the organic matter in coal. In this paper, it has been established that the time required for separation and isothermality of the process are crucial to maintain the reaction progressing toward sulfur and organic sulfur liberation from the macromolecule. The data presented in this paper are important from the viewpoint of process development, because the process mandates the separation of coal and solvent at the operating temperature.     

烷基水杨酸盐的胶体结构与其稳定性关系研究

介绍了国内外几种不同碱值烷基水杨酸钙盐金属清净剂的性能,考察了不同碱值烷基水杨酸盐产品的胶体粒子结构及粒子分布状态、胶体粒子的稳定性以及与高碱值磺酸钙的复合效果,结果表明,添加剂中胶体粒子的结构是影响其胶体稳定性的重要因素,胶体粒子的粒径越小,粒子分散越均匀,其胶体稳定性越好,兰炼已全面生产的改性中碱值产品及高碱值产品,与磺酸盐相容性良好,混兑后无沉淀生成。     

原油及其馏分油的硫含量关联的研究

汇集了83种国内外原油共110次的硫含量分析数据,对原油及其各馏分硫含量进行了分析比较。找出了各馏分硫含量与原油硫含量的关联关系。结果表明,轻馏分硫含量与原油硫含量的关联性较差,重馏分硫含量与原油硫含量的关联性较好。在装置设计和生产控制过程中,可以用原油和馏分油硫含量的线性关系来预测原油各馏分油的硫含量。     

SELECTIVE REMOVAL OF ORGANIC SULFUR FROM COAL BY TRICHLOROETHANE EXTRACTION

ABSTRACT

Desulfurization of coal involves removal of both organic and inorganic forms of sulfur. In this paper, the process feasibility of organic desulfurization of coal using 1,1,1-trichloroethane (TCA) as the solvent, is established. Sulfur solubility curve in tnchloroethane was obtained. The process conditions of this novel process were critically assessed. From the solubility curve it was concluded that the process should be carried out at or near the normal boiling point of the solvent. Comparisons between the TCA extraction and the perchloroeihylene (PCE) process have been presented. Since the boiling point of tricbloroethane is quite low, the process conditions are very mild in comparision to the PCE process. It was found that the TCA process is capable of removing organosulfur from coal more selectively than the PCE process. The sulfur containing organic species in the extract obtained from     

SELECTIVE REMOVAL OF ORGANIC SULFUR FROM COAL BY TRICHLOROETHANE EXTRACTION

Desulfurization of coal involves removal of both organic and inorganic forms of sulfur. In this paper, the process feasibility of organic desulfurization of coal using 1,1,1-trichloroethane (TCA) as the solvent, is established. Sulfur solubility curve in tnchloroethane was obtained. The process conditions of this novel process were critically assessed. From the solubility curve it was concluded that the process should be carried out at or near the normal boiling point of the solvent. Comparisons between the TCA extraction and the perchloroeihylene (PCE) process have been presented. Since the boiling point of tricbloroethane is quite low, the process conditions are very mild in comparision to the PCE process. It was found that the TCA process is capable of removing organosulfur from coal more selectively than the PCE process. The sulfur containing organic species in the extract obtained from     

SELECTIVE REMOVAL OF ORGANIC SULFUR FROM COAL BY PERCHLOROETHYLENE EXTRACTION

ABSTRACT

Desulfurization of coal involves the removal of both the inorganic and organic forms of sulfur. Several physical methods are available for the removal of inorganic sulfur which is normally represented by pyritic and sulfatic sulfur. Removal of organic sulfur requires the use of chemical cleaning methods. This paper presents the results of an organic sulfur removal technique which employs an organic solvent. This desulfurization technique is selective enough to reject organic sulfur without significantly reducing the calorific value of the treated coal. The sulfur containing organic species in the liquid product from the desulfurization procedure have been completely characterized using GC/MS techniques. These results provide further insights into the nature of the sulfur forms in the parent coal as well as the metamorphism of sulfur species in the coal, and the selective nature of the desulfurization process.     

SELECTIVE REMOVAL OF ORGANIC SULFUR FROM COAL BY PERCHLOROETHYLENE EXTRACTION

Desulfurization of coal involves the removal of both the inorganic and organic forms of sulfur. Several physical methods are available for the removal of inorganic sulfur which is normally represented by pyritic and sulfatic sulfur. Removal of organic sulfur requires the use of chemical cleaning methods. This paper presents the results of an organic sulfur removal technique which employs an organic solvent. This desulfurization technique is selective enough to reject organic sulfur without significantly reducing the calorific value of the treated coal. The sulfur containing organic species in the liquid product from the desulfurization procedure have been completely characterized using GC/MS techniques. These results provide further insights into the nature of the sulfur forms in the parent coal as well as the metamorphism of sulfur species in the coal, and the selective nature of the desulfurization process.     

减压渣油中胶状沥青状物质的化学结构研究

利用对芳香碳有高选择性转化能力的钌离子催化氧化法研究了减压渣油中轻、中、重胶质和戊烷沥青质的化学结构,定量了与芳香环相连的正构烷基侧链和桥链的分布,并了芳香环系的缩合型式,结果表明,这些石油重质组分中均存在碳数为Ｃ１￣Ｃ３０的与芳香 相连的正构烷基侧链,其摩尔浓度随链长的增加而下降,也存在由正构烷基桥连接的至少具有两个芳香环系的芳香性分子,在芳香结构中存在着渺位缩合,迫位缩合以联苯型结构,其中联苯     

准噶尔盆地侏罗纪煤有机岩石学研究

有机岩石学方法是研究煤成油的重要方法之一。显微镜下反射光及荧光分析研究认为，准噶尔盆地侏罗纪煤中存在大量的生烃组分，大部分基质镜质体都发一定强度的荧光。煤的生烃性与主要生烃组分的含量密切相关。本区相当数量的煤有机质类型为Ⅱ２型，部分为Ⅱ１型。成熟度研究表明，本区侏罗纪煤已达到或超过生烃门限并产出大量的液态烃，是准噶尔盆地重要的烃源岩之一。     

破乳剂结构与其破乳效果及界面行为的关系

通过考察不同结构类型的破乳剂对孤岛油田模拟采出液破乳脱水及界面张力的影响,研究了破乳剂的构效关系。结果表明:油溶性破乳剂破乳效果明显优于水溶性破乳剂,非离子型破乳剂优于阳离子型及两性破乳剂;破乳剂EO/PO值、分子链长、支化度均影响破乳剂的破乳效果。对于同类型中同结构系列的破乳剂,油水界面张力越低,其脱水率越高;同种类型破乳剂使原油的界面张力降低值与脱水率之比r呈现规律:非离子型0.20.4;且直线型破乳剂r值大于支链型破乳剂。不同类型破乳剂对原油极性四组分界面张力降低值之和与脱水率之比有固定的比值范围;对于非离子型破乳剂,使四组分界面张力降低值之和越大,其对应的脱水率越高。     

渣油中硫化物类型分布与化学转化性能

用X射线光电子能谱（XPS）定量研究了Athabasca渣油及其加氢裂化渣油，流化焦化渣油中的硫化物类型，用超临界流体萃取分馏将3种渣油分别分离成9－14个窄馏分及残渣，测定其中的硫醚，噻吩，亚砜和砜类硫原子的分布，讨论了加氢裂化和热裂化反应脱除硫化物的反应性能。