用热解还原法生产硫磺的工业实验研究

本文采用热解还原法对“低品位硫铁矿采用二段硫化床与劣质高硫煤还原反应生产硫磺的工艺”进行了改进.使用本改进工艺,可使吨磺煤耗比改进前降低50％,操作更加稳定.用低品位硫铁矿中的硫与铁资源和高硫煤中的煤与硫资源生产硫磺和还原铁粉,达到了资源的充分利用;该研究工艺使资源利用达到最大化,符合循环经济的法则;为弥补我国硫、铁资源短缺,多方法寻求资源的来源不失为一种有效的途径.     

我国硫铁矿资源开发利用现状和进展

本文概述了我国硫铁矿资源开发利用的历史和现状,评述了资源量浪费以及对生态环境的影响,针对我国低品位硫铁矿资源的特点与现今工艺技术的发展现状,总结了采用重-浮选、全浮选工艺生产高品位硫精砂(S％＞45％)方案,提出了低品位硫铁矿和高硫煤综合开发利用生产硫磺的工艺技术方案,对资源综合利用及资源、经济、环境协调发展提出了有益见解.     

硫铁矿及多金属硫化矿脱硫制硫磺技术及产业化

介绍了硫铁矿及多金属硫化矿用无烟煤热解-还原制硫磺技术的原理及工艺流程。针对w(S)15%~20%低品位硫铁矿和w(S)40%的硫精砂原料开展中试研究,在100 t/a在硫铁矿及多金属硫化矿脱硫制硫磺中试装置上进行半年多时间试验研究,结果表明:沸腾炉炉渣w(S)≤1.0%,硫烧出率大于或等于98%;还原炉进口φ(SO_2)7.0%~10.0%,还原炉出口φ(SO_2)≤0.5%,还原率大于93%;粗硫w(S)≥95%;收硫尾气CS_2、COS、H_2S等微量。在工业试验的基础上,研究探讨建设一期20 kt/a硫磺联产30 kt/a铁精粉项目和二期100 kt/a硫磺联产150 kt/a铁精粉项目的工业化方案,并对项目进行了经济效益估算,该项目实施后具有良好的经济效益。     

芬兰拟向中国出口硫精砂

芬兰的硫精砂ω(S)高达50%-53%,经过焙烧的矿渣ω(Fe)超过66%,是很好的炼铁原料。近来国际市场硫磺价格飞涨,铁精矿的价格也很高,而且供应紧张。在目前的情况下,掺烧硫磺的硫铁矿制酸厂使用进口硫精砂代替硫磺并将回收的矿渣卖给钢铁厂,已经可以获得可观效益。采用国产硫铁矿为原料的硫酸厂,只要能够充分回收矿渣,也能获得额外效益。新建的硫酸装置,采用进口硫精砂为原料,综合利用硫精砂中的硫和铁,也是经济的。芬兰有关公司表示愿意向中国出口硫精砂,     

贫硫铁矿资源综合利用技术概述

简要介绍了采用浮选技术将含硫品位为8%~15%(以S计,质量分数)的低品位硫铁矿加工成含硫品位为46%的硫精砂的工艺技术和特点、硫铁矿制酸烧渣及余热蒸汽综合利用情况。浮选技术的应用,不仅满足了制酸工艺对硫品位的要求,而且提高了硫铁矿的开采率和利用率;硫铁矿制酸烧渣及余热蒸汽的综合利用,取得了明显的经济和社会效益。     

江铜-瓮福硫铁矿烧渣综合利用生产实践

江铜-瓮福400 kt/a硫铁矿制酸装置酸原料硫精砂硫含量高、砷、氟含量低,针对硫铁矿烧渣铁含量高[w（Fe）〉55%]的特点,采用硫精砂选矿富集-返渣配高品位硫精砂焙烧副产高品位烧渣的综合利用方案,烧渣w（Fe）在62%以上、有效硫w（S）在0.3%以下,完全满足炼铁原料质量要求。近一年多的生产实践表明,江铜-瓮福硫铁矿烧渣综合利用是成功的,硫酸装置各项工艺指标正常。w（Fe）62%烧渣产量达到191 kt/a,经济效益可观。     

硫及硫化氢后续产品开发

一、硫磺后续产品的开发 我国是硫资源贫乏的国家，硫磺资源主要来自以下几个方面：天然硫铁矿、含硫金属矿（如硫铁矿、有色金属硫化物矿）与含硫天然气、冶炼厂含硫废气、燃高硫煤发电厂排出烟气、加工含硫原油所回收的硫等。每年约生产350万t硫磺，其中硫铁矿土法炼硫约占200万t，天然气回收硫璜约占60万-70万t，其余由石油炼制和合成氨原料气脱硫回收以及由天然硫矿提炼生产。     

《中国资源综合利用技术政策大纲》颁布实施

国家发改委等六部委于2010年7月23日发布了《中国资源综合利用技术政策大纲》,并于发布之日起施行。其中涉及硫与硫酸工业的技术包括：推广从石油和天然气中回收硫资源生产硫磺技术;推进煤系硫铁矿资源综合利用技术的产业化;研发低品位硫铁矿选矿富集技术;     

市场行情

我国硫资源不足需求量较大我国硫资源包括硫铁矿、伴生硫磺矿、天然硫磺矿以及从冶炼烟气中回收的硫酸和从石油、天然气中回收的硫磺。此外 ,以煤为原料的合成氨厂、炼焦厂在生产合成氨和煤气的同时也回收少量的硫磺。我国可供开发利用的硫资源有限。我国硫资源中 ,硫铁矿占 5 3%、伴生硫铁矿占 2 7%、天然硫矿及其他硫资源占 2 0 %。硫铁矿1.可利用资源少硫铁矿是我国主要硫资源 ,目前我国硫酸生产大约5 0 %是以硫铁矿为原料。未来硫铁矿在我国硫酸生产中仍将占有较重要的地位。我国硫铁矿资源主要集中在安徽、广东、内蒙古、四川和山西等…     

硫酸亚铁制硫酸联产铁精粉技术综述

硫酸亚铁是钛白粉副产物,也一种硫、铁资源,2006—2016年国内钛白粉硫酸亚铁折硫资源量(以S计)约为7.4 Mt,折铁资源量(以Fe计)约为12.6 Mt;预测2017—2020年折硫资源量(以S计)约为4.9 Mt,折铁资源量(以Fe计)约为8.1 Mt。介绍了硫酸亚铁热分解原理及干燥、焙烧和制酸技术进展,硫精砂和硫磺掺烧一水硫酸亚铁可以生产w(H_2SO_4)98%硫酸和w(Fe)≥60%铁精粉产品,从而实现硫、铁资源综合利用,探讨了高含碳硫精砂掺烧一水硫酸亚铁、含硫废物与硫酸亚铁混烧、低温热回收、循环流化床焙烧炉等技术趋势。     

Study of the effect of ultrasonic treatment on the surface composition and the flotation performance of high-sulfur coal

This paper highlighted the use of X-ray diffraction, scanning electron microscopy and X-ray fluorescence spectroscopy to investigate the changes on the surface composition of high-sulfur coal and pyrite before and after ultrasonic conditioning. The results showed that ultrasonic conditioning resulted in a decrease in the contents of iron and sulfur in coal, an increase in the content of element carbon, and an increase in the purity of the coal. Conversely, ultrasonic conditioning led to an increase in the content of iron and sulfur in pyrite, a decrease in the impure content of calcium, and a relative increase in the purity of the pyrite after ultrasonic conditioning. This study verified that on the one hand, ultrasonic conditioning can promote the pyrite separation from the high-sulfur coal, with the separated pyrite taking the form of FeS; on the other hand, it can produce a cleaning effect on the surface of coal and pyrite with the consequent increase both in hydrophobicity of coal and hydrophilicity of pyrite. The paper introduced ultrasonic pre-treatment of the slurry and stepped froth removal tests of high-sulfur coal and the study on the yield, ash and sulfur content of clean coal in different phases. The results gave further evidence of the increases both in the rate and the selectivity of flotation. This study shows that ultrasonic conditioning can enhance the performance of de-sulphurization of high-sulfur coal flotation.     

高硫煤粉永磁干法强磁选试验研究

以平顶山庚组高硫煤粉为煤样,利用实验室自制的永磁强磁选机进行分选试验,发现:随着颗粒粒径的增大,其灰分、硫分也随之增加;该磁选机的最佳分选粒度范围为0.25～0.5mm;磁选脱除的主要是煤中黄铁矿硫,而硫酸盐硫和其他有机硫则变化不大。     

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 CH_4 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.     

煤的含硫率对煤中汞的分布特性影响模型研究

通过对全国部分省市(地区)煤田煤样中总硫和汞含量的研究分析,以及对煤中硫与汞的赋存状态、不同成煤时期硫与汞的含量分布进行探究,发现高硫煤中的汞与硫化物关系密切,且与黄铁矿存在密切的伴生关系.结果表明,煤中汞的含量一般为100 ng/g～450 ng/g,平均含量220 ng/g.利用数学统计分析方法和数学软件等对煤样中的总硫与汞含量进行相关性模型研究,探索了煤中总硫与汞含量的数学模型,结果表明,在置信度为0.95条件下(α=0.05),煤样中的汞含量与含硫量存在很好的相关关系.     

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.     

Catalytic activity of iron compounds for coal liquefaction

The catalytic activity of pyrite and synthesized -FeOOH in coal liquefaction was investigated using batch autoclaves with the aim of developing an industrial iron catalyst. The results indicate that the presence of H₂S helps gaseous hydrogen transferring and prevents deactivation so that the catalyst promotes hydrocracking of coal and hydrogenation of the products. The activity converges with excess H₂S and sulfur addition equivalent to an S/Fe molar ratio of 2.0 being reasonable for the activation. The active site is located on the outer surface, with finely divided catalysts exhibiting high activity. Both pulverized pyrite and synthesized -FeOOH are sufficiently fine as to exhibit high activity in the process. Pulverized pyrite is an industrially feasible iron catalyst for coal liquefaction process, because it is inexpensive and does not require sulfur addition.     

高硫煤加氢热解脱硫研究

在常压固定床上,温度450—750℃,氢气流速300—900 mL/m in和升温速度15℃/m in的实验条件下,对沟底高硫煤加氢热解脱硫的影响因素进行了研究。实验结果表明,适当增加氢气的流速,提高反应最终温度和延长停留时间,对高硫煤加氢热解脱硫效率的提高和降低残留物中的硫质量分数都是有利的;利用气相色谱研究了硫化氢气体的逸出规律,随着热解温度的提高,硫化氢气体逸出曲线表现为2个峰。研究认为,高温峰源于硫铁矿和噻吩类含硫化合物中硫的脱除,而低温峰源于脂肪族含硫化合物硫的脱除。煤脱硫反应的热力学也表明,随热解温度升高煤加氢热解脱硫分为2段。     

污泥与高硫煤共水热碳化过程中硫氮形态转化规律

采用高温高压反应釜进行了污泥(SS)和高硫煤(CS)的共水热碳化实验。分别考察了混合比和温度对水热炭中硫氮元素形态转化规律的影响。研究结果表明,经过水热处理后,SS中蛋白质氮(N-A)转化为杂环类氮,CS中吡咯氮(N-5)和吡啶氮氧化物(N-X)转化为吡啶氮(N-6)和季氮(N-Q);SS与CS中硫元素逐渐转化为噻吩硫和硫酸盐。随着CS混合比例和温度的升高,水热炭中含氮芳族杂环(例如N-6、N-5和N-Q)占比增加。另外,随着CS混合比例和温度升高,水热炭中噻吩硫含量分别逐渐增加至22.61%和24.98%;升高温度提高了水热炭中硫酸盐含量,而增加CS混合比例却降低了硫酸盐含量。本研究可为后续SS和CS的资源化清洁利用提供理论基础。     

Electrochemical reduction of pyrite in aqueous NaCl solution

Optimum conditions for pyrite removal from a high-sulfur coal by electrochemical reduction during flotation are determined by orthogonal experiments. The electrochemical reduction process of pure pyrite is examined with XRD, electrochemical and chemical analysis. The results show that the electrochemical reduction products of pyrite are FeS and S²⁻. During this process, the reactions at cathode are: FeS₂+2e→FeS+S²⁻ and 2H⁺+2e→H₂. The corresponding electrode potentials and kinetic equation are determined. The conversion of hydrophobic pyrite to hydrophilic FeS and S²⁻ by electrochemical reduction is beneficial to desulfurization from coal in floatation process.