一种新的煤脱硫方法——加氢热解

大气中的二氧化硫是造成酸雨污染的最主要因素。有效脱除煤中的硫，控制二氧化硫的排放量是洁净利用高硫煤的关键。加氢热解是一种新的、具有很大潜力的煤综合利用途径和有效的脱硫方法。一系列的研究表明：加氢热解可以脱除煤中９０％以上的硫，同时可获得有广泛用途的煤气、焦油和半焦产品。加氢热解过程中，不同形态硫的变迁以及矿物质与硫之间的相互作用研究，对于脱除煤中的硫有重要的理论指导意义。     

煤燃烧过程中各形态硫析出规律的研究

利用改进的自动测硫仪,以高有机硫北宿烟煤和高黄铁矿硫阳泉无烟煤作为研究对象,在不同温度下对原煤和脱无机硫煤在煤燃烧过程中硫析出特性进行了研究,另外对原煤和脱无机硫煤在热解和燃烧时硫形态的变化进行了研究．实验表明：黄铁矿硫、有机硫、煤中有机硫的分布在不同温度下具有不同的析出能力;煤热解和燃烧过程中各形态硫可以向其它形态转移,使硫的析出变得十分复杂．其结果对研究煤燃烧过程中硫的析出规律及燃中固硫有一定帮助．     

煤浆法烟气脱硫过程中二硫化铁浸出的研究

煤浆洗涤法烟气脱硫基于液相催化氧化原理.实验通过分析含SO2烟气与煤浆中二硫化铁作用后浆液中铁离子浓度及pH的变化,重点探讨了浆液量、煤样粒径等对煤中二硫化铁浸出量的影响规律.实验结果表明,煤浆上清液中的铁离子浓度随反应进行而增加;在反应进行约60 min后,铁离子析出速率相对较快.故此法在脱除烟气中二氧化硫的同时也可降低煤中黄铁矿硫含量.随脱硫过程的进行,pH值逐渐下降,在反应最初30 min内下降较快,随后下降幅度减小.     

Desulfurization of a Turkish lignite at various gas atmospheres by pyrolysis. Effect of mineral matter

An investigation was made of the removal of pyritic and organic sulfur by pyrolysis at ambient pressure of a Turkish lignite under nitrogen and carbon dioxide atmospheres and the effect of mineral matter on the sulfur removal in pyrolysis of HCl and HCl/HF-treated coal under carbon dioxide atmosphere. Results obtained indicated that both pyritic and organic sulfur removal increased with increasing pyrolysis temperature. The pyrolysis in carbon dioxide atmosphere had more effect on the organic sulfur removal at high temperatures. As a consequence of treatment of coal with HCl, pyritic sulfur removal increased but organic sulfur removal decreased. This implies that the removal of carbonates from coal negatively affects the organic sulfur removal. The observed decrease in organic sulfur removal may be related to the decrease in pyrolytic conversion. It was observed that HCl/HF treatment has an increased effect on the pyritic removal and organic sulfur removal during pyrolysis. The increase in organic sulfur removal after HF-treatment therefore might be due to the removal of clay minerals in the raw coal structure. In addition, it may be said that the presence of silicate minerals in the coal matrix can be induced that the easily removable organic sulfur compounds are converted to thermally stable and non-removable organic sulfur compounds (thiophenic or condensed thiophenic compounds) at these temperatures. Increase in the pyritic sulfur removal of HCl-treated and HCl/HF-treated coal samples may be attributed to the fact that increase of mass and/or heat transport in comparison with untreated coal as a result of elimination of mineral matter.     

Large laboratory scale demonstration of combined bacterial and physical coal depyritization

An optimum coal depyritization process may combine the physical removal of large liberated inclusions and the microbial degradation of the micropyrite. This was demonstrated in a 1501 aerated trough slurry reactor divided into six sections. An Illinois No. 6 coal containing 1.02% pyritic sulfur and ground to 80% — 100 mesh was fed into section 2. Any solids settling out in sections 2 through 6 were transferred to section 1, which acted as a rougher section for physical separation and an inoculum generator for the microorganisms. Slurry leaving the reactor was dewatered on a screen and part of the liquid was recycled to provide Fe³⁺, bacteria and biosurfactants needed to initiate the process on the feed coal. With a five day reactor residence time, and a slurry concentration of 20%, pyritic sulfur was reduced 89% and ash by 30 to 40%, with 90% recovery of heating value. Approximately 16% of the pyrite and other mineral matter appeared in the solid waste drained from section 1, and the remainder is due to microbial pyrite oxidation and solubilization of basic minerals in the coal. Increasing slurry concentration to 35% reduced pyritic sulfur removal to 78%. A slight (5%) reduction in the heating value of the product coal remains unexplained.     

Microbial desulfurization of coal by Thiobacillus ferrooxidans and thermophilic archaea

Several different microorganisms have been suggested for coal desulfurization. In the present investigation, the thermophilic archaea Acidianus brierleyi (DSM 1651), Sulfolobus acidocaldarius (DSM 639) and Sulfolobus solfataricus (DSM 1616) were compared with the mesophilic bacterium Thiobacillus ferrooxidans (DSM 583) concerning their capability of removing sulfur from coal. The desulfurization rate as well as the amount of sulfur removed by the microorganisms was studied.

Two of the investigated microorganisms, Thiobacillus ferrooxidans and Acidianus brierleyi, were capable of oxidizing pure pyrite as well as oxidizing sulfur in coal. A kinetic analysis was performed assuming first order reactions. The rate constant for oxidation of pure pyrite by A. brierleyi was observed to be higher than for T. ferrooxidans. The values of the rate constants for sulfur removal from coal were comparable for the two microorganisms, but were higher than for oxidation of pure pyrite.     

煤中黄铁矿的电化学脱硫及动力学研究

为了降低煤的脱硫费用和提高脱硫效率，以硫酸为介质，以硫酸锰为脱硫催化剂，在以石墨为电极的无隔膜电解池中研究了煤的电化学催化脱硫。研究表明，在特定的电解电位下，煤中无机硫脱硫率随着锰离子的浓度增加，煤浆浓度的降低和电解温度的提高而提高。进而对这些数据进行了动力学分析。结果表明：煤中黄铁矿脱硫速率与煤中活性黄铁矿（易接近）和惰性黄铁矿（难接近）及脱硫反应有关，脱硫模型符合Langmuir-Hinshelwood近似，脱硫表观活化能为10.44kJ/mol。     

煤及其模型化合物电解氧化脱硫的热力学分析

根据煤的分子结构理论及热力学原理，对铁矿和有机含硫模型化俣物在标准状态下电解氧化硫的理论分解电压进行了计算，分析了电化学法脱除煤中有机硫和黄铁矿的可能性及脱硫深度，讨论了提高脱硫效率和选择性的可能途径。     

应用油团聚(SGHFF)技术高效脱除煤炭中黄铁矿硫的研究

介绍了应用油团聚（ＳＧＨＦＦ） 技术高效脱除煤炭中硫的过程， 探讨了煤炭粉碎粒度及水量对煤炭中硫的脱除率的影响。实验结果表明， 硫含量为２．１６ ％ 的烟煤， 脱除率可达到６７ ％ 。     

Removal of sulfur from Assam coal by bacterial conditioning and froth flotation

Reduction of sulfur by bacterial leaching from a high sulfur‐bearing coal sample from Assam was attempted. Flotation of the sample with light diesel oil could not depress the pyrite and also the Thiobacillus ferrooxidans was found to be ineffective in leaching the sulfur from the flotation concentrate. Conditioning of the same coal sample with Thiobacillus ferrooxidans was found to assist in selectively depressing the pyrite, thereby reducing nearly 60% of the pyritic sulfur present in the sample. © 1999 Society of Chemical Industry     

煤炭高梯度磁选-浮选脱硫降灰试验

通过分析煤样性质,说明原煤中无机硫主要以硫化铁硫为主,有机硫较高,仅依靠物理方法很难达到理想脱除效果。通过煤粉高梯度磁选试验研究了磁介质、磁通密度、脉冲对煤炭磁选效果的影响。结果表明:聚磁介质选用不加铜套细网介质,当磁通密度为1.295 T,脉冲为25次/min时,煤粉湿法高梯度磁选脱硫效果最好,此时硫分为1.59%,精煤产率为85.44%,脱硫率为31.87%,脱灰率为38.17%,黄铁矿硫脱除率为45.02%。通过正交试验确定了最佳高梯度磁选条件为:煤粉粒度0.075 mm,磁通密度1.295 T,脉冲25次/min,可得到硫分1.35%,灰分10.37%的磁选精煤产品。最后对磁选精煤进行再浮选试验,得到最佳浮选条件为:石灰500 g/t,捕收剂1360 g/t,起泡剂90 g/t,可获得产率76.29%,硫分1.28%,灰分8.14%的精煤,产品脱硫率为57.73%,脱灰率为58.52%,黄铁矿硫脱除率为84.56%。采用磁选-浮选综合流程,煤粉基本达到理想的脱硫降灰效果,可作为煤种脱硫降灰技术方案的参考。     

黄铁矿化学脱硫的热力学分析

应用热力学方法对煤中黄铁矿脱硫反应进行了较系统的计算与分析．结果表明,黄铁矿具有较高的热稳定性,黄铁矿的干法还原脱硫和热解脱硫属热力学控制反应,脱硫应在高温下进行;黄铁矿湿法脱硫可在常温下进行,其主要方法是氧化法和碱液浸取法．     

煤中硫的赋存状态及成因

煤中硫的赋存形态和结构对煤的脱除效率有很大影响,重点对煤中硫的化学形态进行了综述,详细讨论了煤中黄铁矿、有机硫的赋存状态、结构及成因,以加深对硫的认识,为脱除硫提供可靠的理论依据。     

酸性体系H_2O-NaBr混合溶剂中煤的电化学脱硫研究

对贵州地宗高硫煤在酸性条件下 ,H2 O- Na Br混合溶剂中电化学脱硫规律进行了研究 ,讨论了电解电流、温度、煤浆浓度、Na Br浓度、p H值及电解时间等主要因素对煤的脱硫率的影响 ,获得无机硫脱除率为 5 6 .71% ,有机硫脱除率为 38.0 3% ,硫的总脱除率为 4 5 .6 2 %的较好效果     

脱硫微生物的菌种驯化培养

生物脱硫具有低成本、可脱有机硫等优点,不足之处是菌种生长不稳定,需要不断进行驯化培养以提高菌种的脱硫活性。实验采用不同的硫源对脱硫微生物进行了驯化,考察了不同培养基中的微生物的驯化和生长,再将微生物菌种分别接种到煤、黄铁矿和柴油培养基中进行培养。结果表明,在以煤为硫源的培养基中,微生物生长具有较大起伏,不利于菌种的驯化,8d后的脱硫率为10.2%;而在柴油和黄铁矿中培养的微生物则较单一,有利于菌种的驯化,8d后的脱硫率分别为23%和17.4%。     

内蒙古乌达矿区高硫煤中硫的成因

在分析内蒙古乌达矿区高硫煤9、10煤层中硫的来源基础上,阐述了煤中有机硫和黄铁矿的形成机理,指出高硫煤中硫的形成可划分为同生阶段、成岩阶段(成岩阶段早期和成岩阶段晚期)和后生阶段,并详细解释了各阶段中硫的赋存特征.     

炼焦过程中硫元素迁移规律研究

以华北地区的峰峰低硫肥煤和山西中硫焦煤为原料,利用1 kg热解试验装置进行模拟炼焦试验,并对所得焦炭、煤焦油和煤气产品中硫元素形态和质量进行测定,揭示了炼焦煤中硫元素的迁移规律。结果表明:两种炼焦煤挥发分差别不大,硫元素迁移规律基本相同;炼焦过程中,不但原料煤中硫酸盐硫得以保留,还有其它形态硫经过复杂的热解化合反应生成新的硫酸盐硫;无机硫中的黄铁矿硫和有机硫中的脂肪硫、硫醚、硫醇等在炼焦过程中以H2S形式转移到煤气中,转移效率一般低于50%;原料煤中黄铁矿硫含量越高,H2S的转移率也越高;其他噻吩硫等在炼焦过程中不分解,留在焦炭中。     

Reductive pyrolysis study of sulfur compounds in different Tabas coal samples (Iran)

A comparative study of the effects of mineral and pyrite removal on the determination of organic sulfur functionalities in representative, as well as its low and high sulfur analogue samples of Tabas coal (C1 seam) were studied by atmospheric pressure-temperature-programmed reduction (AP-TPR) method. The AP-TPR investigation showed the presence of di-aryl sulfides, aryl-alkyl sulfides, simple and complex thiophenic structure in all representative, low and high sulfur samples. There is no indication of the presence of pure di-alkyl sulfides, disulfides or thiols, nor oxidised sulfur forms in the samples. Only minor differences in sulfur functionalities were detected qualitatively between the three analogue samples. Quantitatively differences in sulfur forms were found to be more pronounced. The presence of CH fragments on gases emitted during AP-TPR investigation of demineralised and demineralised pyrite-free samples, shows evidence for the formation of shorter CH chains and of polyaromatic compounds, and lower molecular weight material in the demineralization and pyritic sulfur removal stages.     

碱性体系中煤中有机硫的电化学脱除研究

以高硫煤为原料,用化学法将其无机硫脱除后,再以此作为电解煤样,在碱性条件下研究了煤中有机硫的电化学脱硫规律。讨论了电解电流、煤浆浓度、NaOH浓度等主要因素对煤中有机硫脱硫率的影响,并确定了适宜电解脱硫条件:NaOH质量浓度4.0mol/L,煤浆质量浓度0.04g/mL,反应温度70℃,电流强度1.0A,电解时间5h,获得了有机硫脱除率为32.50%的较好效果。     

Sulfur variability and element geochemistry of the No. 11 coal seam from the Antaibao mining district,China

The roof, bottom and 24 coal ply samples were collected by finely partitioning No. 11 coal seam from Antaibao mining district, Shanxi, China in terms of lithotypes. Proximate and sulfur analyses, ICP-AES, ICP-MS, AFS, XRD, SEM–EDX techniques were used on these samples, in order to investigate the vertical variability and origin of sulfur and also the geochemistry of major and trace elements in the seam. The weighted mean content of total sulfur of the 24 coal plies is 2.4 wt%, belonging to the medium-sulfur coal, but there are great differences in the contents of total sulfur and forms of sulfur between the 24 plies: total sulfur content >3.0 wt% for 5 plies, organic sulfur content >1.0 wt% for 13 plies and pyritic sulfur content >2.0 wt% for 4 plies. It is found that the differences were mainly caused by the degree of marine influences and the contents of clay minerals as well as the organic matter. The ply 21 has an abnormal high content of inorganic sulfur (pyritic sulfur 9.45 wt% and sulfate sulfur 5.97 wt%). This was caused by the presence of bauxite minerals-bearing kaolinite in the underlying ply 22 blocking the further infiltration of sulfate from the overlying plies during the deposition. The seam is dominated in kaolinite and, to a lesser extent, in pyrite, and there also exist minor amounts of szomolnokite, diaspore, boehmite, calcite, siderite, dolomite, magnesite, feldspar, gypsum. Szomolnokite and gypsum possibly resulted from the oxidation of pyrite. The seam is greatly characterized by finely-grained pyrite concentrating in cutinite. Hazardous trace elements Hg, Pb and As are mainly concentrated in pyrite, so that they can be partially removed by physical coal cleaning with an aim of removal of sulfur, while thalassophile elements Br, Ca, Cl, Mg and Sr, are clearly associated with the organic sulfur, reflecting that their contents can be decreased by coal blending means due to a partial organic affinity.