吸附法脱除废气中羰基硫的研究进展

羰基硫(COS)广泛存在于黄磷尾气、电石炉尾气等矿热冶炼废气中,但因其结构较稳定,极性和酸性较弱难以直接脱除.本文综述了吸附法脱除COS常用的吸附剂以及吸附剂改性方法,对负载改性所涉及的活性组分进行详细介绍,并分析影响吸附效果的主要因素及吸附机理,对比不同吸附剂的再生方式及再生效果.最后,分析吸附法脱除COS存在的不足...     

用活性炭纤维同时脱除二氧化碳中COS与H_2S的研究

采用固定床动态吸附实验考察了用NaOH、KOH、Na2CO3、K2CO3和Fe3+、CO2+等对活性炭纤维(ACF)进行改性,并分别对其脱除氧硫化碳(COS)和硫化氢(H2S)的性能进行了测试。重点是以N2和CO2为稀释气,对改性离子的种类、含量、反应气氛和反应温度等的脱硫性能进行研究,还考察了在COS和H2S同时存在的情况下,ACF脱除COS和H2S的性能。结果表明,碱改性ACF比空白ACF脱除效果好,金属离子改性ACF与碱改性ACF相比可以有效地提高活性炭纤维的硫容量。其中,用CO2+改性ACF能同时提高脱除COS和H2S的效果。     

γ-Al2O3的添加对MDEA溶液脱除COS效果的影响

通常石油炼厂气、煤制气和天然气中都含有羰基硫（COS）等有机硫化物，它们会污染环境，腐蚀设备，导致后续生产工艺的催化剂中毒．COS呈中性或弱酸性，化学性质比较稳定，难以用常规的脱硫方法脱除干净．氢解与水解都能将COS绝大部分转化为H2S然后用脱硫剂脱除．近年来国内外研究开发了常温COS水解催化剂，它们多以活性氧化铝为主要成分，     

石脑油中有机氯脱除的研究进展

石脑油中有机氯的脱除作为行业难题之一,国内外进行了大量有机氯脱除技术研究。现有有机氯脱除技术有吸附、催化加氢、萃取脱氯、微生物脱氯等,这些方法各有优缺点,但大部分技术处于实验室研究阶段,尚未实现工业化。本文综述了石脑油中有机氯化物的来源、危害,重点分析了吸附法、催化加氢法等有机氯脱除方法的反应机理和研究现状,并提出目前存在的问题及未来的研究方向。     

钾改性氧化铝基羰基硫水解催化剂及其失活机理

天然气、油田伴生气、高炉煤气等化工生产过程中伴生COS气体,不仅会腐蚀管道和毒害催化剂,还会严重污染环境并危害人类健康。COS催化水解反应可在温和条件下高效的将COS脱除,是最具应用前景的COS脱除技术之一。碱金属元素因其具有独特的电子供体性质、表面碱性和静电吸附等特性,常被用作助催化剂以提高Al₂O₃的COS催化水解性能。近年来,以钾为助剂改性的Al₂O₃催化剂(K₂CO₃/Al₂O₃)在COS催化水解反应中得到广泛的应用,但由于负载在Al₂O₃上的K物种的组成复杂,目前研究者对K₂CO₃/Al₂O₃催化剂上COS水解机理的理解仍存在一定的困惑和争议。本论文通过湿法浸渍法合成出一系列钾盐和钠盐改性的Al₂O₃催化剂,并利用各类先进的表征技术对这些催化剂进行分析。活性测试表明,以K₂CO₃、K₂C₂O₄、NaHCO₃、Na₂CO₃和NaC₂O₄改性Al₂O₃催化剂均有助于COS的水解。其中K₂CO₃/Al₂O₃拥有最佳的COS水解性能,连续运行20 h后其COS转化率仍高于~93%,远远优于未改性的Al₂O₃ (~58%)。我们利用原位红外光谱和X射线光电子能谱探明了反应过程中催化剂的化学结构特征,阐明了H₂O分子在K₂CO₃/Al₂O₃上的水解作用机制。原位红外表明COS在K₂CO₃/Al₂O₃上的水解过程中形成了硫代碳酸氢盐中间产物。X射线光电子能谱表征证明催化剂的失活主要是因为催化剂表面积累了硫酸盐和单质硫。此外,我们还研究了水蒸气含量对COS水解性能的影响,研究发现,由于H₂O和COS分子在催化剂表面存在竞争吸附,过量的H₂O会引起催化活性的下降。上述研究表明,K₂CO₃/Al₂O₃催化剂上COS水解性能的提高主要是形成了HO-Al-O-K界面活性位。更为重要的是,所制备的催化剂都是在模拟工业工况条件下进行的,这为后续的工业应用提供了宝贵理论指导。本工作为理解助剂钾在Al₂O₃催化剂上COS水解活性的增强提供了新的见解,这为未来设计稳定高效的COS水解催化剂打开了新的发展方向。     

Cu-MOFs的生长调控及其催化水解羰基硫的性能

羰基硫(COS)广泛存在于以煤、焦炭、渣油和天然气等为原料生产的化工原料气中,不仅腐蚀管道设备,使下游催化剂发生硫中毒,而且还会造成环境污染.因此,COS脱除具有重要意义.在各种方法中,催化水解COS(COS+H2O→CO2+H2S)由于具有反应条件温和、转化率高和副反应少等优点越来越受重视.其关键在于发展高效的催化剂.近年来,金属-有机骨架材料(metal-organic frameworks,MOFs)由于其独特的物理化学性质引起人们广泛关注.与传统材料相比,MOFs不仅拥有超高的比表面积和规则的孔道结构,而且其结构具有可设计性强和易调变等特点,是一类非常有潜力的多相催化剂.然而,目前MOFs在催化水解COS方面的研究应用未见报道.此外,MOFs的合成方法主要有水/溶剂热法、扩散法和微波辅助加热法等.近年来新发展的电化学法具有合成效率高、操作方便和环境友好等优点,在材料合成中显示出巨大的优越性,但利用电化学法合成MOFs相关研究还较少. 本文采用快速温和的电化学方法制备了典型的Cu-MOFs(HKUST-1).该方法可以有效缩短反应时间,通过调节反应电压(15–30 V),在室温下电解3 h,可得到一系列HKUST-1样品.根据合成中设置的电压值,样品分别命名为HKUST-1-E15,HKUST-1-E20,HKUST-1-E25和HKUST-1-E30.XRD表征结果显示,不同电压下合成样品的XRD谱图与通过晶体数据拟合的HKUST-1图出峰位置基本一致.SEM结果表明,合成电压对样品形貌的影响很大.HKUST-1-E15主要呈长棒状结构,长约为15μm.随着电压的增大,HKUST-1-E20的形貌逐渐转变为较短的四棱柱体.当电压为25 V时,所得HKUST-1-E25呈八面体状.进一步提高合成电压,HKUST-1-E30颗粒变小,没有特殊形貌,并出现明显的团聚.COS水解测试结果显示,不同电压下合成样品的活性差异大,这主要是由于样品的形貌及比表面积差异引起的.其中,HKUST-1-E25样品的活性较好.在150°C下,该样品对COS的转化率接近100%,比水热法合成的HKUST-1-Hy的活性更高.在此基础上,进一步对活性测试过程的条件进行优化,发现当原料气流速为30 mL/min,水温为40°C时,催化剂的COS水解性能最优.此外,样品的活性稳定性测试结果显示,相比传统的氧化铜材料,HKUST-1是一类较稳定的COS水解催化剂.     

甲醛低温催化氧化动力学研究: Ⅰ 本征动力学

甲醛是室内空气污染的主要物种之一[1]。甲醛被吸入人体后,破坏人体的DNA结构,从而引起基因突变,产生潜在的致癌性。因此,脱除甲醛具有一定的现实意义。甲醛的脱除方法主要有催化氧化法、热氧化法、吸附法、生物脱除法等。催化氧化法由于具有很高的脱除效率,是研究较多的脱除甲     

Cu-MOFs的生长调控及其催化水解羰基硫的性能（英文）

羰基硫(COS)广泛存在于以煤、焦炭、渣油和天然气等为原料生产的化工原料气中,不仅腐蚀管道设备,使下游催化剂发生硫中毒,而且还会造成环境污染.因此,COS脱除具有重要意义.在各种方法中,催化水解COS(COS+H_2O→CO_2+H_2S)由于具有反应条件温和、转化率高和副反应少等优点越来越受重视.其关键在于发展高效的催化剂.近年来,金属-有机骨架材料(metal-organic frameworks,MOFs)由于其独特的物理化学性质引起人们广泛关注.与传统材料相比,MOFs不仅拥有超高的比表面积和规则的孔道结构,而且其结构具有可设计性强和易调变等特点,是一类非常有潜力的多相催化剂.然而,目前MOFs在催化水解COS方面的研究应用未见报道.此外,MOFs的合成方法主要有水/溶剂热法、扩散法和微波辅助加热法等.近年来新发展的电化学法具有合成效率高、操作方便和环境友好等优点,在材料合成中显示出巨大的优越性,但利用电化学法合成MOFs相关研究还较少.本文采用快速温和的电化学方法制备了典型的Cu-MOFs(HKUST-1).该方法可以有效缩短反应时间,通过调节反应电压(15–30 V),在室温下电解3 h,可得到一系列HKUST-1样品.根据合成中设置的电压值,样品分别命名为HKUST-1-E15,HKUST-1-E20,HKUST-1-E25和HKUST-1-E30.XRD表征结果显示,不同电压下合成样品的XRD谱图与通过晶体数据拟合的HKUST-1图出峰位置基本一致.SEM结果表明,合成电压对样品形貌的影响很大.HKUST-1-E15主要呈长棒状结构,长约为15μm.随着电压的增大,HKUST-1-E20的形貌逐渐转变为较短的四棱柱体.当电压为25 V时,所得HKUST-1-E25呈八面体状.进一步提高合成电压,HKUST-1-E30颗粒变小,没有特殊形貌,并出现明显的团聚.COS水解测试结果显示,不同电压下合成样品的活性差异大,这主要是由于样品的形貌及比表面积差异引起的.其中,HKUST-1-E25样品的活性较好.在150°C下,该样品对COS的转化率接近100%,比水热法合成的HKUST-1-Hy的活性更高.在此基础上,进一步对活性测试过程的条件进行优化,发现当原料气流速为30 mL/min,水温为40°C时,催化剂的COS水解性能最优.此外,样品的活性稳定性测试结果显示,相比传统的氧化铜材料,HKUST-1是一类较稳定的COS水解催化剂.     

汽车尾气中NO的脱除方法

对汽车尾气中NO的脱除方法进行了介绍。对于选择性催化还原,目前的方法主要有以NH3作为还原剂选择还原NO、以碳氢化合物作为还原剂选择还原NO和三效催化剂法。非选择性催化还原方法主要包括CO催化还原NO和H2催化还原NO等。NO的直接催化分解和贫燃条件下NO的催化还原也得到了广泛研究。低温等离子体技术、改性碳纤维以及TiO2光催化法等是近几年新发展的脱除方法。     

Al_(2)O_(3)-Zn-K催化水解COS和CS_(2)的研究北大核心CSCD

以活性氧化铝为载体,浸渍负载Zn、K活性组分,制备优选Al_(2)O_(3)-Zn-K催化剂.考察了反应工艺条件对COS、CS_(2)脱除精度的影响,并对失活的催化剂进行表征,分析催化剂的失活原因.结果表明,负载Zn、K活性组分后,催化剂的弱碱性中心显著提高,负载量为4%时催化剂具有最优的水解活性.在180℃催化水解过程中,工艺条件对CS_(2)脱除精度的影响较COS更为明显.无氧条件下,反应过程中生成的硫酸盐和表面活性物质发生迁移导致催化剂碱性中心减少是催化剂失活的主要原因.     

Using of Dithiooxamide Alkali Solution in Potentiometric Titration

Ditiooxamid is sulfur-containing organic reagent, which forms stable chelate complexes with many sulfide forming metal ions. This reagent is widely using, in spectrophotometric methods of analysis.     

Lead Sulfide Nanocrystal-Polymer Composites for Optoelectronic Applications

Summary: Nanocomposite films were prepared by two methods in which lead sulfide (PbS) nanocrystals were contained in an organic matrix. One method used a wet chemical synthesis of the nanocrystals in the direct presence of a polymer, where the polymer controlled nanocrystal growth. The second method was gaseous deposition of nanocrystals into the organic phase. The two methods were similar in that the nanocrystals in the composites were free from surfactant capping layers that otherwise would add an interfacial region between the nanocrystal and the organic matrix. The gaseous deposition technique had several advantages over the wet chemical synthesis in that it allowed direct control over nanocrystal size and density, improved flexibility in the choice of organic phase, and was compatible with lithographic methods.     

锂硫二次电池正极研究进展

综述了锂硫电池中硫基正极材料的制备方法、结构特征以及电化学性能. 简述了单质硫正极材料, 重点探讨了有机硫化物、碳/硫复合材料、聚合物/硫复合材料的结构设计、材料制备、反应机理以及充放电特性, 并对其中存在的问题进行了分析, 还介绍了硫化锂正极材料. 最后对硫基正极的进一步发展, 以及锂硫电池的商业化应用进行了展望.     

Detection of volatile organic sulfur compounds in water by headspace gas chromatography and membrane inlet mass spectrometry

Two gas chromatographic methods, GC-FID (flame ionization detection) and GC-ELCD (electrolytic conductivity detector) are compared in tlie analysis of volatile organic sulfur compounds (VOSCs) in water samples with a membrane inlet mass spectrometry (MIMS) technique. Carbon disulfide, ethanethiol, dimethyl sulfide, ethyl-methyl sulfide, thiophene, and dimethyl disulfide were used as test compounds. Linear dynamic ranges were found to be two decades with the GC-ELCD method and four decades with the GC-FID and MIMS methods. Detection limits were at low (μg/1 levels with the two gas chromatographic methods and clearly below μg/1 level with the MIMS method. Analysis of one sample takes 40 min with the gas chromatographic methods and five minutes with the MIMS method. The selectivity was good, especially with the GC-ELCD and the MIMS method. In addition, quantitative results obtained with spiked water samples by the three methods are compared.     

氧化与还原条件下伊通河长春区段沉积物重金属形态特征的对比研究

利用改进的Tessier连续萃取法研究了伊通河长春市自由大桥处不同深度沉积物样品在氧化及还原条件下Cu,Pb,Zn和Ni的形态变化规律,同时分析了沉积物样品中酸可挥发性硫(Acid volatile sulfide,AVS)和同时提取重金属(Simultaneous extract metals,SEM)的含量. 实验结果表明，样品经干燥、研磨处理后,Cu有机/硫化物结合态比例减少40%,锰氧化物结合态的比例显著增加; Pb,Zn和Ni 3种元素有机/硫化物结合态比例均略有下降,变化幅度小于Cu,并重新分配到不同的化学相中. 通过SEM中各金属含量与有机/硫化物结合态中金属含量的对比可知,还原性沉积物中Cu除了与硫化物结合外,很大一部分是以有机物形态存在的,Pb,Zn,Ni,Fe和Mn则主要以硫化物形态存在,各元素形态分析均不同程度地受到萃取剂的影响.     

哈密煤温和液化固体产物热解过程中硫的变迁规律

利用固定床反应器研究了哈密煤温和液化固体产物（MLS）在热解过程中含硫气体的释放规律以及不同形态硫的变迁规律，并分析了矿物质对硫变迁规律的影响。结果表明，在实验考察的条件范围内，MLS热解过程中大部分的硫残留在半焦中，仅有不到10%的硫迁移到焦油中或转化为含硫气体逸出。热解生成的含硫气体以H₂S为主，当热解温度为400℃时H₂S的逸出速率达到最大。通过改进方法测定了MLS及其热解半焦中各种形态硫的含量，发现MLS热解过程中以硫化物硫和有机硫的分解和转化为主。随着热解温度的升高，MLS中有机硫逐渐分解并以含硫气体的形式逸出；当热解温度低于600℃时，MLS中硫化物硫逐渐转化为含硫气体、有机硫和少量的黄铁矿硫；当热解温度高于600℃时，MLS中碱性矿物质吸收气相中的H₂S转化为硫化物硫，硫化物硫缓慢增加。醋酸酸洗可以保留MLS中大部分的硫化物硫，且酸洗后MLS热解生成的H₂S逸出速率增大，峰温向低温方向移动；当热解温度高于600℃时，有机硫和硫化物硫的脱硫反应速率降低，并且MLS中的碱性矿物质与H₂S反应生成金属硫化物，导致H₂S逸出速率明显降低。     

Binary system organic base-anode in the oxidative activation of hydrogen sulfide

Initiation of the reaction between hydrogen sulfide and aliphatic, aromatic, and heteroaromatic hydrocarbons in acetonitrile using the binary system organic base-anode is described. The reaction of hydrogen sulfide with nitrogen-containing organic bases is studied by means of cyclic voltammetry. The reaction of hydrogen sulfide with triethylamine leads to the formation of thiolate anion. The next step o reaction is electrochemical oxidation of the thiolate anion that to lead thiyl radical formation in situ thiyl radicals. In the presence of binary system on the basis of hydrogen sulfide aliphatic, aromatic, and heteroaromatic thiols and sulfides are formed at room temperature.     

Analysis of polysulfides in drinking water distribution systems using headspace solid-phase microextraction and gas chromatography–mass spectrometry

Sulfide and polysulfides are strong nucleophiles and reducing agents that participate in many environmentally significant processes such as the formation of sulfide minerals and volatile organic sulfur compounds. Their presence in drinking water distribution systems are of particular concern and need to be assessed, since these species consume disinfectants and dissolved oxygen, react with metal ions to produce insoluble metal sulfides, and cause taste and odour problems. The analysis of sulfide and polysulfides in drinking water distribution systems is challenging due to their low concentrations, thermal instability and their susceptibility to undergo oxidation and disproportionation reactions. This paper reports on the development and optimisation of a rapid, simple, and sensitive method for the determination of sulfide and polysulfides in drinking water distribution systems. The method uses methyl iodide to derivatise sulfide and polysulfides into their corresponding dimethyl(poly)sulfides, which are then extracted using solid-phase microextraction in the headspace mode and analysed by gas chromatography–mass spectrometry. Good sensitivity was achieved for the analysis of dimethyl(poly)sulfides, with detection limits ranging from 50 to 240 ng L⁻¹. The method also demonstrated good precision (repeatability: 3–7%) and good linearity over two orders of magnitude. Matrix effects from raw drinking water containing organic carbon (3.8 mg L⁻¹) and from sediment material from a drinking water distribution system were shown to have no interferences in the analysis of dimethyl(poly)sulfides. The method provides a rapid, robust, and reliable mean to analyse trace levels of sulfides and polysulfides in aqueous systems. The new method described here is more accessible and user-friendly than methods based on closed-loop stripping analysis, which have been traditionally used for the analysis of these compounds. The optimised method was used to analyse samples collected from various locations in a drinking water distribution system. Some of the samples were shown to contain inorganic polysulfides, and their presence was associated with high sediment density in the system and the absence of disinfectant residual in the bulk water.     

Combined adsorption and oxidation mechanisms of hydrogen sulfide on granulated coal ash

Hydrogen sulfide is highly toxic to benthic organisms and may cause blue tide with depletion of dissolved oxygen in water column due to its oxidation. The purpose of this study is to reveal the combined adsorption and oxidation mechanisms of hydrogen sulfide on granulated coal ash that is a byproduct from coal electric power stations to apply the material as an adsorbent for hydrogen sulfide in natural fields. Sulfur species were identified in both liquid and solid phases to discuss removal mechanisms of the hydrogen sulfide with the granulated coal ash. Batch experiments revealed that hydrogen sulfide decreased significantly by addition of the granulated coal ash and simultaneously the sulfate ion concentration increased. X-ray absorption fine structure analyses showed hydrogen sulfide was adsorbed onto the granulated coal ash and successively oxidized by manganese oxide (III) contained in the material. The oxidation reaction of hydrogen sulfide was coupling with reduction of manganese oxide. On the other hand, iron containing in the granulated coal ash was not involved in hydrogen sulfide oxidation, because the major species of iron in the granulated coal ash was ferrous iron that is not easily reduced by hydrogen sulfide.     

Lanthanide-centered covalently bonded hybrids through sulfide linkage: molecular assembly, physical characterization, and photoluminescence

A series of novel photoactive lanthanide (europium, terbium, dysprosium, samarium) hybrid materials with organic parts covalently bonded to inorganic parts via sulfide linkage have been assembled by the sol-gel process. The organic parts as molecular bridge are obtained from the functionalized thiosalicylic acids by five silane crosslinking reagents, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-(triethoxysilyl)propylisocyanate. The intramolecular energy transfer process between lanthanide ions and the molecular bridges took place within these molecular-based hybrids and especially the quantum efficiency of europium hybrids were determined, suggesting that the hybrid material systems derived from different molecular bridges present different luminescence efficiencies.