硫铁化物自燃性的研究

储罐内壁铁的腐蚀产物之一Fe2O3与湿H2S发生反应生成不同形式的硫铁化物,硫铁化物的氧化放热是引起含硫油品储罐着火的主要原因。研究了在75℃条件下,硫化时间对Fe2O3硫化产物的生成及其自燃性的影响。通过X-射线衍射对硫化时间为6h、3d．6d以及17d条件下生成的硫铁化物成分进行了鉴定,并对3d和6d条件下的硫铁化物进行了定量分析。结果表明,在高温条件下,随着硫化时间的延长,有更多的FeS2和Fe3S4生成,并且Fe3S4不断向FeS2转化,自燃性增强,对储罐安全运行构成威胁。     

自然环境条件下硫化铁的自燃倾向性

为了研究硫化铁的自燃倾向性,在自然环境条件下对硫化铁进行氧化实验,实验结果表明:Fe3O4、Fe2O3以及Fe(OH)3硫化后生成的硫铁化合物活性很高,具有较高的自然氧化活性,在室温下可迅速与空气中的氧气反应,同时放出大量的热量.以Fe2O3的硫化产物为典型样品,研究了硫化时间、水分、油品、硫及通风条件对硫化铁氧化升温特征的影响,结果表明,硫化时间长,适量的油品和硫以及良好的通风条件能够加速硫化铁升温过程,而一定的水分及不良的通风条件则降低了硫化铁的自燃倾向性.     

含硫油品储罐腐蚀产物自然氧化实验

为深入研究含硫油品储罐硫腐蚀产物FeS自然氧化倾向性,自建实验台模拟储罐FeS的生成及其自然氧化倾向性,同步热分析仪对FeS进行了热质量实验,通过TG曲线和DSC曲线分析了FeS粒径对其氧化性质的影响.结果表明,Fe3O4、Fe2O3、Fe(OH)3及其混合物经硫化所得FeS具有很强的自然氧化活性,Fe3O4硫化物的氧化速度最快,Fe2O3次之,混合物和Fe(OH)3较慢,温升速率分别达到0.64、0.45、0.34和0.11℃/s;TG曲线经历了质量增加和质量迅速损失的过程,DSC曲线上有明显的放热峰;粒径对FeS氧化性有明显影响,粒径越小,TG曲线向低温方向移动,氧化起始温度和氧化终止温度越低,DSC曲线上放热峰峰值温度越低.     

低温干燥H2S气体危害性研究

简述了低温干燥H2S气体与干燥铁氧化物硫化反应及硫化产物的自燃性,通过考察不同温度干燥H2S的自燃性,表明低温干燥H2S气体能与干燥Fe2O3在低温下发生硫化反应,且硫化产物自燃性较高,危险性大。     

利用除尘灰合成非正分铁的氧化物

为了研究N2H4·2H2O的用量及pH值对产物的影响,以除尘灰的H2SO4浸渍液经铁粉还原得到的FeSO4溶液为原料,采用一步水热法,用水合肼(N2H4·2H2O)在碱性介质中氧化合成非正分铁的氧化物(γ-Fe2O3)x(Fe3O4)1-x (0≤x<1).通过控制溶液的pH值可以得到纯Fe3O4组分,将其磁性能与Fe(Ⅲ)/ Fe(Ⅱ)比为2.0的浸渍液直接水热合成的Fe3O4的磁性能进行了比较,结果表明:除尘灰的H2SO4浸渍液中加入铁粉还原所得FeSO4,经N2H4·2H2O氧化制得的样品的磁性能优于后者.     

Fenton试剂-石英砂工艺处理高浓度铁锰地下水

针对高浓度铁锰地下水处理成本高且处理难度大问题,本试验采用研究了铁锰离子的去除效率与机理。结果表明：加入H2O2对铁锰的去除率明显提高,各因素最佳时铁去除率达到96%,锰的去除率达到83%。利用H2O2加入到高浓度铁锰地下水中巧妙的利用地下水中Fe2＋与H2O2形成Fenton试剂它产生的羟基自由基.OH氧化能力仅次于F-的强氧化物质,它可以把地下水中Mn2＋优先氧化成MnO2同时Fe2＋与H2O2反应生成Fe2O3可以被石英砂过滤去除,并且去除率很高。     

无机化学实验问题例析

就学生在无机化学实验教学过程中提出的问题作一解答.认为:(1)Cr3 与NH3·H2O作用主要是生成Cr(OH)3,而不是[Cr(NH3)6]3 离子;(2)在有NH4 时,Zn(OH)2易溶于NH3·H2O;(3)[Co(NO2)6]3-溶液中加入强酸,其分解产物是Co2 ,不是Co3 ;(4)[Fe(SCN)6]3-遇H2O2,血红色消失的原因是过量的H2O2氧化了SCN-.     

氧化沉淀法制备纳米Fe3O4及其类Fenton催化活性

通过化学氧化沉淀法制备出球形和八面体形貌的Fe3O4纳米颗粒,对其进行XRD、Raman和SEM等表征。以合成的纳米Fe3O4催化H2O2氧化降解橙黄Ⅱ,考察了不同形貌Fe3O4的类Fenton催化活性。结果表明:使用化学氧化沉淀法制备Fe3O4,在低pH(8~9)条件下所得到的产物呈类球形,高pH(13)条件得到的产物为八面体形貌,其粒径均在210nm左右,并且结晶良好。Fe3O4/H2O2体系能有效降解橙黄II,并且催化反应主要发生在Fe3O4表面,最佳催化条件为pH 3.0、温度40℃。类球形Fe3O4纳米颗粒的催化活性高于八面体Fe3O4,并且Fe3O4具有良好的化学稳定性,重复使用4次效果稳定。     

Super304H奥氏体不锈钢的抗高温氧化性能

采用称重法测得了Super304H和Super304HS两种奥氏体耐热不锈钢在不同温度下的高温氧化动力学曲线,研究发现:两种不锈钢的氧化动力学曲线遵循抛物线规律,Super304HS的抗氧化性能明显优于Super304H,而且Super304H在900℃时氧化100 h后,氧化膜明显脱落.利用扫描电镜、X射线衍射的方法对Super304H不锈钢氧化膜表面的形貌及结构进行了研究,结果表明:在700℃和800℃时,两种材料氧化膜组成相似,都是Cr2O3和少量尖晶石结构的FeCr2O4,Su-per304H钢在900℃时的氧化产物主要由Cr2O3,Fe2O3和尖晶石FeCr2O4组成,Super304HS在900℃时的氧化膜主要由Cr2O3和尖晶石FeCr2O4组成.     

烧成温度对硫铁铝酸钡钙矿物形成和强度的影响

利用DTA和XRD方法,研究了烧成温度对硫铁铝酸钡钙矿物性能的影响。结果表明,C2.75B1．25A2.75Fe0．25最佳烧成温度为1300℃,其强度达到最大值,1d为49．8MPa,3 d为 64．4 MPa,28d为90 MPa。随着烧成温度的不断升高,CaO· Al2O3和BaSO4的含量有所减少,C2．75B1．25A2.75Fe0．25矿物晶体数量大幅度提高。烧成温度的升高可以促进CaO·Al2O3和 BaSO4转化生成C2．75B1.25A2．75Fe0.25矿物。该水泥矿物的主要水化产物为BaSO4,含铁C3AH6,CAH10,C2AH8,铁胶和铝胶。     

Evidence for iron, copper and zinc complexation as multinuclear sulphide clusters in oxic rivers

The availability and toxicity of trace metals in fresh water are known to be regulated by the complexation of free metal ions with dissolved organic matter. The potential role of inorganic sulphides in binding trace metals has been largely ignored because of the reduced persistence of sulphides in these oxic waters. However, nanomolar concentrations of copper and zinc sulphides have been observed in four rivers in Connecticut and Maryland. Here we report dissolved (< 0.2 microm particle diameter) sulphide concentrations ranging up to 600 nM, with more than 90% being complexed by copper, iron and zinc. These complexes account for up to 20% of the total dissolved Fe and Zn and 45% of the total dissolved Cu. Fourier transform mass spectrometry reveals that these complexes are not simple M(HS)+ protonated species but are higher-order unprotonated clusters (M3S3, M4S6, M2S4), similar to those found in laboratory solutions and bio-inorganic molecules. These extended structures have high stability constants and are resistant to oxidation and dissociation, which may help control the toxicity of these and other less abundant, but more toxic, trace metals, such as silver, cadmium and mercury.     

烧成镁-铝-铁系耐火砖中铁的存在形式

水泥窑烧成带用镁铬砖残砖产生的铬污染已经引起人们的重视,本文主要研究一种可替代镁铬砖在水泥窑上使用的新型耐火材料Mg O-Al2O3-Fe2O3(Fe O)系耐火材料。利用XRD和SEM分别研究了以高纯镁砂与电熔铝铁尖晶石制备的镁-铁铝尖晶石砖和烧结镁铁砂与电熔铝镁尖晶石制备的镁铁砖烧成后铁的存在状态。结果发现:铁铝尖晶石在高温下分解出Fe2+与Al3+,与Mg O相互扩散,Fe2+与Mg O反应生成(Fe,Mg)Oss固溶体,Al3+与Mg O反应,形成Mg Al2O4,试样中Fe2+的扩散速度大于Al3+;在高温状态下,烧结镁铁砂中Mg Fe2O4的Fe3+不稳定转变为Fe2+,Fe2+扩散到镁铝尖晶石表面,取代了部分Mg2+的位置,形成镁铁铝固溶体。     

Solid FeS lubricant:a possible alternative to MoS2 for Cu-Fe-based friction materials

Molybdenum disulfide (MoS₂) is one of the most commonly used solid lubricants for Cu-Fe-based friction materials. Nevertheless, MoS₂ reacts with metal matrices to produce metal sulfides (e.g., FeS) and Mo during sintering, and the lubricity of the composite may be related to the generation of FeS. Herein, the use of FeS as an alternative to MoS₂ for producing Cu-Fe-based friction materials was investigated. According to the reaction principle of thermodynamics, two composites-one with MoS₂ (Fe-Cu-MoS₂ sample) and the other with FeS (FeS-Cu₂S-Cu-Fe-Mo sample), were prepared and their friction behaviors and mechanical properties were compared. The results showed that MoS₂ reacted with the Cu-Fe matrix to produce FeS, metallic ternary sulfides, and Mo when sintered at 1050℃. The MoS₂-Cu-Fe and FeS-Cu₂S-Cu-Fe-Mo samples thereby exhibited similar characteristics with respect to phase composition, density, hardness, and tribological behaviors. Micrographs of the worn surfaces revealed that the stable friction regime for both composites stemmed from the iron sulfides friction layers rather than from the molybdenum sulfides layers.     

CaO--TiO2--Fe2O3三元系中Ca3TiFe2O8的生成机理

钒钛磁铁矿是烧结矿重要的原料之一,Ca3TiFe2O8作为钒钛烧结矿中矿物被发现之后,其生成机理尚不明确.本文采用X射线衍射分析、元素能谱分析和TG--DSC分析相结合的方法,研究了Ca3TiFe2O8的生成机理以及不同温度、CaO与TiO2含量下Ca3TiFe2O8的生成规律.实验结果表明,Ca3TiFe2O8由Ca2Fe2O5和CaTiO3反应生成,即CaO和Fe2O3反应生成Ca2Fe2O5;其后,与CaTiO3反应生成Ca3TiFe2O8.反应时间越长,Ca3TiFe2O8的生成量越大,但反应温度对Ca3TiFe2O8生成的影响并不明显.另外,还发现 CaO含量越高,Ca3TiFe2O8越易于生成,而且等摩尔 Fe2O3和 CaO下只要存在 TiO2,就会有Ca3TiFe2O8生成.     

钢坯高压水除鳞后的表面氧化铁皮形貌及内部组织演变

在不同温度和时间条件下对钢坯进行加热,出炉后利用高压水去除钢坯表面氧化铁皮,然后利用光学显微镜和扫描电镜观察钢坯表面形貌及内部组织,利用XRD分析除鳞后钢坯表面氧化物相组成。结果表明,除鳞后的钢坯表面残留一层氧化铁皮,该层氧化物相组成取决于加热温度和保温时间。低温短时加热时,残留氧化铁皮相组成中含有单质Fe;提高加热温度和延长保温时间使钢基体表面被完全氧化成Fe3O4和Fe2O3。钢坯在炉中长时间高温加热使残留氧化铁皮晶粒粗大,钢坯基体内部出现过热、晶界氧化以及脱碳等问题,加热温度越高、加热时间越长,氧化烧损越严重。     

基于含水层介质中铁的类Fenton技术去除地下水中硝基苯

为了将Fenton氧化技术氧化能力强的优势引入到硝基苯污染地下水的原位化学修复中,通过实验模拟在地下环境温度为8~10℃、pH为中性条件下,以含水层介质中铁为催化剂的类Fenton技术去除地下水中硝基苯的过程,比较不同浸提剂对含水层介质中铁的浸提效果,并对氧化硝基苯的反应中自由基生成规律和催化氧化机理进行研究。研究结果表明:浸提剂强化了介质中各形态铁的释放,浸提作用存在滞后性,浸提36 h后铁在浸提液中浓度达到峰值;浸提剂DCB对介质中Fe3+和Fe2+的浸提效率最高,分别为62.92%和30.17%。催化氧化反应中硝基苯与H2O2的最佳摩尔比为1:200,该条件下硝基苯去除率最大为80.2%;催化氧化反应过程中HO.的变化可分为3个阶段,即0~30 min的快速生成阶段,30~120 min的生成速率降低阶段和120~240 min的稳定阶段。     

Advances in research of sulphide ore textures and their implications for ore genesis

Important advances in research of sulphide ore textures in recent years have deepened our understanding of ore genesis of related mineral deposits. Pressure solution of sulphide minerals has been suggested as a mechanism for remobilization of ore materials, whereas pressure solution of the gangues is believed to raise the grade of the primary ores. We have known that precipitation of base metal sulphides from fluids prefers crystal and crack surfaces of pyrite to form overgrowth. Therefore, pyrite-bearing embryo beds in a sedimentary sequence can be acted as effective crystal seed beds and are favorable for fluid overprinting to form huge statabound deposits. Texture studies of various sulphides can be used to interpret the entire history of sedimentation, diagenesis, deformation and metamorphism of the ores. The study of chalcopyrite disease in sphalerite has brought about the idea of zone refining, and given a new explanation to metal zonation in massive sulphide deposits. Ductile shearing of sulphide ores may form ore mylonites, which will become oreshoots enriched in Cu, Au and Ag during late-stage fluid overprinting. Despite that various modern analytical techniques are being rapidly developed, ore microscopy remains to be an unreplaceable tool for ore geologists. Combined with these modern techniques, this tool will help accelerate the development of theories on ore genesis.     

Non-chondritic distribution of the highly siderophile elements in mantle sulphides

The abundances of highly siderophile (iron-loving) elements (HSEs) in the Earth's mantle provide important constraints on models of the Earth's early evolution. It has long been assumed that the relative abundances of HSEs should reflect the composition of chondritic meteorites--which are thought to represent the primordial material from which the Earth was formed. But the non-chondritic abundance ratios recently found in several types of rock derived from the Earth's mantle have been difficult to reconcile with standard models of the Earth's accretion, and have been interpreted as having arisen from the addition to the primitive mantle of either non-chondritic extraterrestrial material or differentiated material from the Earth's core. Here we report in situ laser-ablation analyses of sulphides in mantle-derived rocks which show that these sulphides do not have chondritic HSE patterns, but that different generations of sulphide within single samples show extreme variability in the relative abundances of HSEs. Sulphides enclosed in silicate phases have high osmium and iridium abundances but low Pd/Ir ratios, whereas pentlandite-dominated interstitial sulphides show low osmium and iridium abundances and high Pd/Ir ratios. We interpret the silicate-enclosed sulphides as the residues of melting processes and interstitial sulphides as the crystallization products of sulphide-bearing (metasomatic) fluids. We suggest that non-chondritic HSE patterns directly reflect processes occurring in the upper mantle--that is, melting and sulphide addition via metasomatism--and are not evidence for the addition of core material or of 'exotic' meteoritic components.     

沉淀法制备FePO4的形貌控制

分别以FeCl3·6H2O,FeSO4·7H2O和Fe（NO3）3·9H20为铁源,NH4H2PO4,H3PO4和（NH4）3PO4·3H2O为磷源,用沉淀法制备了FePO4．研究了沉淀过程中原料、pH值以及表面活性剂对FePO4形貌的影响．采用X射线衍射、扫描电镜分别对样品的物相、形貌进行表征．研究结果表明,FePO4的形貌控制可以通过铁源、磷源、表面活性剂的选择和pH值等的控制来实现．H3PO4为磷源,以FeCl3·6H2O为铁源,当pH〈l时,制备的样品为均匀的铁皮石斛形,加入PEG后为自组装的圆片状,当pH〉1时,形貌为鸟巢形;以FeSO4·7H2O为铁源制备的样品形貌也以鸟巢形为主;以Fe（NO3）3·9H2O为铁源制备的样品表现为花状;以FeCl4·6H2O为铁源、（NH4）3PO4·3H2O为磷源制备的样品为不规则的片状;以FeSO4·7H2O为铁源、NH4H2PO4为磷源时制备的样品为类球形．表面活性剂及其用量在一定程度上有助于片状FePO4的制备．