中国煤中硫的地球化学研究

燃烧过程中,煤中硫会以硫氧化物等形式释放出来,污染大气以至形成酸雨,对环境造成极大的影响。本文在对中国煤中硫全面分析的基础上．总结并分析了中国煤中硫在不同地区、不同煤层和不同形成环境中的含量与分布规律,阐述煤中硫形成的地质成因和影响因素．以及育机硫、无机硫和元素硫的赋存状态．概述了煤利用过程中硫的转化机理及其对环境的影响．提出了对煤中硫的研究趋势和今后研究方向与热点问题。     

中国煤中有机硫的分布及其成因

对来自全国26个省、市、自治区的290个煤样中有机硫的质量分数测试及研究,发现煤中有机硫质量分数基本分布在0%1.0%范围内。在低硫煤中硫分以有机硫为主,在高硫煤中以无机硫为主。中、高硫煤中,广西、湖南等地区很大一部分煤中硫分以有机硫为主。在所采集的样品中,高有机硫煤(有机硫>1%)均分布在华南、华北两大聚煤区,属于石炭、二叠纪煤。高有机硫煤中有机硫质量分数的变化与变质程度无明显关系。煤炭形成过程中海水作用的影响,是导致煤中有机硫含量偏高的最主要原因。      

贵州大方背斜南东翼煤中硫特征及成因分析

根据井田勘探施工钻孔采取的136个煤样的煤质测试结果,对贵州大方背斜南东翼可采煤层煤中硫的特征及其成因进行了分析。结果表明:该区可采煤层从特低硫煤—高硫煤均有,中上部煤中硫的质量分数较高,一般为中高硫煤,中下部以低中硫煤为主,底部煤中硫的质量分数变化大,从特低硫煤可到高硫煤;龙潭组中上部煤层煤中硫主要与硫的来源和沉积环境有关,而下部煤层煤中硫与其来源有关,与沉积基底中岩性发育也有一定关系,凝灰岩、玄武岩发育地段,煤中硫的质量分数低,反之则高。      

乌达矿区高硫煤层的聚积环境与煤中硫的分布

对乌达矿区高硫煤层的沉积相、煤相和煤中硫在平面上的分布进行了研究。结果表明,１０煤层泥炭聚积时的古水系对煤中硫的分布有明显的影响,９煤层泥炭聚积时的三环境决定了煤中硫的分布,浅水陆棚或分流间湾环境中形成的煤层具有较高ＧＩ、Ｖ／Ｉ值和硫含量,在障壁砂坝中形成的煤层具有高的硫含量、低的ＧＩ、Ｖ／Ｉ值,在泻湖中具有高ＧＩ、Ｖ／Ｉ值和相对较少的硫含量。     

沁水盆地晚古生代煤中硫的地球化学特征及其对有害微量元素富集的影响

煤中硫是多种有害微量元素的重要载体。基于形态硫分析、电感耦合等离子质谱及X射线衍射等方法分析沁水盆地晚古生代煤中硫和有害微量元素的分布规律,探讨了煤中硫对有害微量元素富集的影响,运用带能谱的扫描电镜和光学显微镜划分煤中硫化物的微观赋存特征。结果表明,沁水盆地煤中硫整体上以有机硫为主,平均占全硫的78%,只有在太原组个别高硫煤中以黄铁矿硫为占优势。显微镜和扫描电镜下可识别出煤中黄铁矿的微观赋存状态包括莓球状、薄膜状、晶粒状、结核状、团窝状黄铁矿和细粒黄铁矿集合体,白铁矿的微观赋存特征包括聚片状、板状和矛头状白铁矿,部分白铁矿与黄铁矿共生。沁水盆地煤中有害微量元素含量整体较低,黄铁矿是有害微量元素As、Se和Hg的重要载体,而有机硫决定了煤中U的富集。研究认为,成煤时期海水对泥炭沼泽的影响导致太原组煤中全硫和黄铁矿硫较高,太原组煤中硫的来源具有多样性,煤中黄铁矿具有多阶段演化的特点。     

贵州金沙安洛勘探区北段煤中硫及其控制因素

根据地质勘探资料和煤心煤样的分析结果,对贵州金沙安洛区北段煤中硫的时空分布以及煤中硫与沉积环境的关系进行了研究。结果表明,该区形成于以潮坪为主的过渡相环境,由于沉积过程中受海水影响,煤中硫的质量分数总体偏高;但由于海水对煤层作用的强度不一,使不同煤层或同一煤层不同部位硫的质量分数差异很大,而且煤中硫的质量分数变化与煤层顶底板的古地理环境有关。      

煤中硫的作用

煤中的硫通常呈有机硫和无机硫的方式存在，笔者利用理论方法、化学反应方程式、计算公式和实例阐述了煤中硫的存在方式与含量对评价煤的工业用途、计算煤的发热量、分析煤的沉积环境等方面的指导作用。     

参照镜煤反射率用电子探针测定煤中有机硫

根据镜煤反射率与碳含量的关系,估计出煤中碳及相应的氢、氦、氧的含量,再将电子探针所测煤中有机硫与标样疏的X射线强度比值作为硫含量的近似值,计算出煤中有机硫的ZAF校正因子。最后用ZAF,法得到有机硫的含量。实验表明其结果与化学分析一致。     

四川晚二叠世煤中硫与成煤环境的关系

本文从沉积学、成煤环境、地球化学等方面研究了煤中硫的分布规律，并详细阐明了煤中硫与成煤环境的关系。研究表明:煤中硫的赋存状况，不仅受成煤环境的影响，而且受其顶板沉积环境的影响。成煤环境奠定了煤中硫的分布基础，而顶板环境则是促使煤富硫、高硫的重要因素。微咸水浑水潮坪的顶板沉积环境，导致了下伏煤高黄铁矿硫，而咸水的清水潮坪顶板环境则导致下伏煤高有机硫。     

贵州马依西二井田煤中硫特征和沉积环境探讨

依据井田地质勘查资料及煤质测试结果,对马依西二井田内可采煤层中硫的特征及与沉积环境的关系进行了探讨。结果表明,区内各煤层煤中硫含量变化较大,自下而上以底部30、29煤为高硫煤,煤中硫分最高可达7.2%,下部19至26为中高硫-高硫煤,17-1煤层为低硫煤,上部3至12-1煤层为中高硫煤;在平面上总体呈东南高、北西低的分布态势。聚煤环境是造成煤中硫差异的主要因素,17-1煤发育于泛滥平原相中,以成煤植物所含的原生硫为主,煤中硫含量低,而其它煤层形成环境因受海水影响较大,存在更多以硫化铁硫为主的次生硫而使硫含量较高。     

Protocol for Quantitative Detection of Elemental Sulfur and Polysulfide Zero-Valent Sulfur Distribution in Natural Aquatic Samples

A HPLC-based protocol has been developed for the determination of zero-valent sulfur (ZVS) speciation, including solid, colloidal elemental sulfur and individual inorganic polysulfides in natural aquatic samples. The protocol includes four experimental procedures: (1) determination of polysulfide speciation by rapid single-phase derivatisation with methyl trifluoromethanesulfonate; (2) determination of the sum of polysulfide and colloidal sulfur by reaction with hydrogen cyanide (cyanolysis); (3) determination of total zero-valent sulfur by treatment with zinc chloride followed by extraction with chloroform; and (4) chromatographic determination of polythionates without sample pre-treatment. With proper sampling and preservation techniques in the field or on board ship, this combination of methods allowed the quantitative determination of: (a) individual polysulfide species; (b) dispersed colloidal sulfur; (c) dispersed solid elemental sulfur; and (d) tetra-, penta- and hexathionates. With minor modification, the method could be expanded to include other polythionates. Sixteen various wet chemical and liquid chromatographic methods were tested on nine synthetic reference samples (including solid elemental sulfur, colloidal elemental sulfur, inorganic polysulfides and polythionates) to establish the optimal protocol. The protocol was further evaluated by analysing the zero-valent sulfur content in microbially-produced sulfur and in sulfur from two natural samples of sulfide-rich seawater from tidal flats pools of the Wadden Sea (Germany).     

Spinifex Texture of Native Sulfur: A Cooling Product of Sulfur Flow Eruptions at Shiretoko-Iwozan Volcano, Hokkaido, Japan

Abstract: Several native sulfur specimens, collected from Shiretoko-Iwozan volcano, eastern Hokkaido, Japan, exhibit spinifex texture, which appears to resemble that often observed in komatiite. The spinifex texture is exhibited by yellow-colored elongated skeletal native sulfur crystals up to 5 cm long settled in medium gray-colored fine–grained clayey matrix. One surface of a specimen is coated by layers of micro pillow lava of native sulfur. Such specimens were rarely found as clasts or fragments around the 1936 No. 1 crater that erupted native sulfur flows, together with the most common monomineralic native sulfur fragments of native sulfur flows having pahoehoe surface and of native sulfur dikes. The elongated spinifex native sulfur crystals presently consist of aggregated polygrains of orthorhombic sulfur crystals formed through crystallo-graphic transition from the single crystal of monoclinic sulfur initially crystallized. The spinifex texture exhibited by elongated skeletal native sulfur crystals is a product of rapid cooling of sulfur melt. Many lithic fragments of altered country rocks are present in the specimens exhibiting native sulfur spinifex texture. This suggests that segregation of the sulfur melt from the mixture of lithic fragments and sulfur melt was incomplete because the mixture was chilled before the melt segregation. Elongated skeletal native sulfur crystals may have nucleated and crystallized directly from the molten sulfur liquid. Lithic fragments mixed in the melt are supposed to have acted as nuclei for the nucleation of the native sulfur crystals. On the other hand, the most of native sulfur flows consist of monomineralic massive native sulfur with very scarce lithic fragments. Such massive monomineralic native sulfur crystallized from the supercooled, solidified amorphous sulfur. Such supercooled amorphous state may have been attained due to the lack of nuclei because of the scarcity of lithic fragments. The unique structures exhibited by native sulfur lava flow, including pahoehoe surface and spinifex texture, are due to the characteristic physical property of molten sulfur liquid, that is, low viscosity.     

蒋家坪矿区高硫煤中有机硫的特性研究

运用煤岩学、煤化学、地球化学等学科的理论与方法,对湖南蒋家坪矿区煤质、煤岩特征和形态硫进行分析,结果显示：所测样品全硫含量为8％～10．1％,其中有机硫含量高达6％,属高有机硫煤;煤样的显微组分以镜质组为主,含量接近80％,惰质组中以丝质体、半丝质体和碎屑惰质体为主,矿物则多以黄铁矿和黏土矿物为主。通过对煤中成煤植物类型、凝胶化程度、镜惰比和氧化指数的研究,认为矿区高硫煤形成于比较潮湿的弱氧化条件下。     

滇东北镇雄硫磺矿区环境地质问题及其对策与意义

硫磺渣是硫磺矿区主要的矿业固废,其随意堆放可产生一系列的环境地质问题,并对山水林田湖草等自然资源、环境及人的健康构成较大危害。滇东北地区长期以硫铁矿为原料、以煤炭为燃料,土法炼硫生产硫磺,导致巨量硫磺渣堆积,产生了严重的环境地质问题。本文针对该地区镇雄县硫磺矿区,调查了小硫磺生产形成硫磺渣的规模和特征,梳理了该硫磺矿区主要环境地质问题及其对当地生态环境的影响,认为目前镇雄硫磺矿区存在的环境污染、自然资源破坏及可能形成的矿渣性泥石流等环境地质现状与过去40多年的小硫磺生产密切相关。基于以上认识,强调应结合矿业固废无害化、减量化和资源化技术政策,从资源回收利用、生态环境恢复、地质灾害防治和文化遗产保护方面探讨和提出镇雄硫磺矿区矿渣治理和生态修复的新理念和新对策。     

喀斯特坡地石灰土硫形态分布及其同位素组成特征

土壤中S形态及各形态硫化物的稳定S同位素组成的分布特征对于土壤S循环研究具有重要意义。利用S形态连续提取方法测定了喀斯特坡地石灰土总S、SO4^2- -S、S^0-S、FeS—S、FeS2-S和有机S含量及其δ^34S值。有机S是石灰土主要的S形态,占总S的76．5％～93．6％。总S和有机S含量随土壤深度加深而降低,这与有机S矿化有关,对应有机S的δ^34S值逐渐增大。总体来看,FeS2是石灰土主要的无机S形态,其次为SO4^2-、FeS和S^0。石灰土表层以下深度FeS2-S增加与SO4^2-异化还原反应速率增大有关,对应SO4^2-和FeS2的δ^34S值平行增大。深层土壤FeS2-S降低则主要与SO4^2-异化还原反应速率减小及无机S厌氧氧化有关。土壤各形态S含量及其δ^34S值的分布特征,可以记录与深度相关的S形态转化过程。值得注意的是,受石灰土类型、植被状况及地形特征等因素的影响,喀斯特坡地石灰土中SO4^2-、FeS2和有机S组分容易迁移,这也是石灰土中各形态S分布变异的主要原因。     

韩城石炭——二叠系原煤的自身固硫率和硫的烧失率

对陕西韩城矿区的石炭－－二叠系4个主采煤层的原煤自身固硫率和硫的烧失率进行了研究，其中11号煤96％的煤，5号煤98％，3号煤92％和2号煤94％的硫在800－850℃温度下的灼烧2h已分解释放。其燃渣中的硫主要以硫酸盐的形式存在。煤自身的固硫率和灰分含量密切相关，特别是与煤灰分中的氧化钙关第最为密切，原煤中硫的烧失率与煤中全硫、有机硫和无机硫的含量关系密切。     

Sulfur Isotopic Characteristics of Coal in China and Sulfur Isotopic Fractionation during Coal—burning Process

The determined results of the sulfur contents and isotopic composition of coal samples from major coal mines in 15 provinces and regions of China show that the coal mined in the north of China is characterized by higher ^34S and lower sulfur content, but that in the south of China has lower ^34S and higher sulfur content.During the coal-burning process in both indrstrial and daily use of coal as fuel the released sulfur dioxide is always enriched in lighter sulfur isotope relative to the corresponding coal;the particles are always enriched in heavier sulfur isotope.The discussion on the environmental geochemical significance of the above-mentioned results also has been made.     

Quantitative Recovery of Elemental Sulfur and Improved Selectivity in a Chromium-Reducible Sulfur Distillation

Chromium-reducible sulfur (CRS) distillations are intended to recover only reduced inorganic sulfur compounds (RIS) including elemental sulfur. However, the quantitative recovery of elemental sulfur is not ensured in common CRS-distillations. The new method presented here was designed to remedy this deficiency. An increase in ethanol concentration assured the quantitative recovery of elemental sulfur in various forms and, in addition, all other RIS-compounds were quantitatively recovered. Furthermore, the selectivity of the procedure was improved by an additional filtration step to eliminate zinc particles from the Cr(II)-solution. Thus, the recovery of sulfates and organic sulfur compounds was significantly decreased by a factor of up to 35, depending on the compound analysed. Exhaustive testing with a variety of pure phases, rock and soil samples demonstrated the precision and accuracy of the new method. The new protocol eliminated the constraints of previous procedures. The improved distillation efficiency for elemental sulfur ensured the quantitative recovery of all RIS-compounds in a single-step distillation.     

莱芜潘西煤矿降低高硫煤含硫量的几点措施

根据目前国内煤炭脱硫技术的发展现状,该文分析研究了潘西煤矿的煤质特征和硫的赋存状态特征。为了降低商品煤中的硫分,潘西煤矿采取了筛选和捡选原煤中黄铁矿结核降低商品煤硫分,上下组煤合理配采降低商品煤硫分,洗选法降低硫分等措施,使煤的质量明显提高,获得了较好的经济效益。     

安徽安庆铜矿床硫同位素地球化学

安徽安庆铜矿床的硫同位素组成复杂，不能用单一硫源或物理化学条件的变化来解释，本文依据区域成矿地质背景及矿床地质特征，研究了硫从硫源地质体转移到成矿热液中的６种可能机理（模型），并确定了矿床的硫源。