流化床煤气化炉内脱硫的研究 Ⅱ．脱硫剂焙烧反应动力学与脱硫反应动力学初步研究

钙质脱硫剂的焙烧反应是炉内脱硫的关键过程，本文研究了影响石灰石和白云石焙烧速率的因素。操作温度７５０℃以上时，焙烧速率很快。ＣＯ_２分压显著地影响焙烧过程，Ｐ_（ＣＯ）２高于平衡分压时，石灰几乎不分解。在本实验的粒度范围内，脱硫剂粒度对焙烧速率影响不大。采用未反应核收缩模型模拟焙烧过程的结果和实验结果基本一致。脱硫反应速率对气相Ｈ_２Ｓ浓度呈一级反应，操作温度特别在６００～７００℃的低温时显著地影响反应速率。     

新型Mn-Fe/Al_2O_3高温脱除H_2S的实验研究(Ⅱ)

本文首先研究了粒度dp=07mm脱硫剂的脱硫反应和再生反应性能。研究表明当Mn∶Fe=2∶1(w)、载体在1000℃焙烧后,脱硫剂有较好的脱硫反应性能,其最佳的脱硫反应温度为550℃,且在710℃、O2浓度低于1083%(v)、空速2000～3000h-1再生条件下,可完全对脱硫剂进行再生;H2S浓度影响脱硫剂的初始脱硫反应速率和穿透反应时间,但对脱硫剂的脱除率和穿透硫容影响不大。并研究了粒度dp=3mm脱硫剂的脱硫情况。实验结果表明,小颗粒脱硫剂的脱硫反应主要为化学反应控制,大颗粒脱硫剂主要为扩散控制。为此对大颗粒脱硫剂进行了工程设计,即采用活性组分非均布脱硫剂。研究表明,非均布脱硫剂明显提高了脱硫剂的平均脱硫反应速率和硫容,同均布脱硫剂相比,非均布脱硫剂再生后具有较好的脱硫稳定性能。     

高温煤气中氨的脱除：Ⅰ.氨催化分解催化剂的筛选

制备和筛选了１２ 种氨催化分解催化剂,所选催化剂包括Ｃｕ － Ｍｎ 基脱硫剂,Ｚｎ－ Ｔｉ 基脱硫剂,Ｆｅ 基催化剂及Ｎｉ 基催化剂四大类,其中Ｎｉ－２ 催化剂及Ｎｉ－ ３ 催化剂具有较高的转化率。然后对Ｎｉ－３ 催化剂进行了寿命试验,１００ｈ 内其活性基本维持不变;耐硫性实验表明Ｎｉ－３ 催化剂具有一定的耐硫性能,因而它是所选的最优催化剂     

添加氧化铈对铁锰复合氧化物脱除羰基硫的影响

采用共沉淀法制备铈掺杂铁锰复合氧化物脱硫剂,对掺杂和未掺杂脱硫剂进行XRD、SEM、TG和XPS分析,并对脱硫剂在325℃下进行脱硫实验。实验结果表明,脱硫剂微粒的晶粒尺寸、分散度和表面元素形态随氧化铈的添加有所改变。和未添加氧化铈脱硫剂相比,添加氧化铈脱硫剂晶粒变小,各元素结合能有所增加。掺杂氧化铈后脱硫剂中氧化物分散性增强,表面吸附氧量增加,脱硫剂在还原气氛中易被还原。脱硫实验表明,添加氧化铈增强了脱硫剂脱除羰基硫的活性,羰基硫脱除精度有较大提高。此外,脱硫剂中添加适量氧化铈可以延长脱硫剂的穿透时间,但过量的氧化铈加入会使穿透时间缩短。     

热煤气脱硫工艺基础特性研究

本文介绍了在加压流化床脱硫间歇试验装置上进行的热煤气脱碱工艺基础性研究结果，利用美国ＵＣＩ公司制备的高温钛酸锌脱硫剂研究了反应温度，压力，气体速度等因素对煤气脱硫过程的影响；     

高温煤气脱硫 Ⅱ.锌铁基脱硫剂的化学形态

应用穆斯堡尔谱考察了不同的制备条件对锌铁基脱硫剂相态组成的影响。提高焙烧温度和延长焙煤时间均有利于ZnFe2O4的形成，但焙浇温度过高引起过度烧结从而降低了脱硫剂的活性。原脱硫剂中的ZnFe2O4和α-Fe2O3在脱硫过程中转化成零价铁、碳化铁和硫化铁。此外还形成了一定数量的高自旋Fe^2 含铁相。再生处理后脱硫剂的化学组成基本上可复至起始状态。     

铁掺杂纳米ZnO室温脱硫剂的硫化及再生研究

为降低纳米ZnO脱硫剂的应用成本及避免对环境产生二次污染,本文对均匀沉淀法制备的铁掺杂纳米ZnO脱硫剂(FZ5.0)进行了硫化和再生循环试验研究,并利用XRD、XPS和TEM等表征手段对FZ5.0的硫化及再生前后的结构进行了分析。结果表明,脱硫剂表面存在3种脱硫产物,HS、S形成的吸附配合物和ZnS,370 ℃时可直接通入空气进行连续5次再生。经过第1次再生后纳米脱硫剂结构便趋于稳定,并在后面的循环过程中表现出较稳定的脱硫活性,但与新鲜脱硫剂相比较,其脱硫活性是新鲜脱硫剂的50%左右。再生过程中主要产物为SO₂气体,还有少量的硫酸盐生成,再生后样品的晶粒尺寸、形貌变化不大,但比表面积和孔容变化明显,这也是导致脱硫活性下降的主要原因。     

复合型镍锌纳米线脱硫剂的制备及其脱硫性能研究

采用水热法合成了复合型镍锌纳米线脱硫剂,考察了溶剂中水和乙醇的比例对复合型镍锌纳米线晶体结构和形貌的影响,通过X射线衍射（XRD）、扫描电镜（SEM）、透射电镜（TEM）等方法对脱硫剂进行了表征;以正庚烷-噻吩为模型化合物,在反应温度为350℃、压力1.0 MPa、进料的体积空速6 h^-1及氢油体积比为60的条件下,考察了复合型镍锌纳米线脱硫剂、负载型镍锌纳米线脱硫剂以及纯氧化锌纳米线脱硫剂的脱硫性能。结果表明,由于复合型镍锌纳米线脱硫剂具有良好的纳米线形貌,活性组分金属镍具有更好的分散性、更小的粒径,同时形成了有利于脱硫的NiZn合金,所以其脱硫性能明显高于负载型镍锌纳米线脱硫剂和纯氧化锌纳米线脱硫剂,达到98%;而且复合型镍锌纳米线脱硫剂经过五次再生后,其使用寿命仍能保持90 h,这说明复合型镍锌纳米线脱硫剂具有很好的再生性能。     

钛酸锌脱硫剂硫化过程的动力学分析

利用固定床反应器对钛酸锌高温煤气脱硫剂硫化过程的动力学进行了研究,考察了硫化反应温度、H2S体积分数对脱硫反应过程的影响。结果表明,脱硫剂具有良好的脱硫反应活性,在400 ℃～600 ℃,脱硫剂的硫化反应速率随着硫化反应温度的升高、反应器入口H2S 体积分数的增大而增大。在实验数据的基础上,利用等效粒子模型对其反应动力学进行了分析,发现该脱硫剂的硫化反应主要受固体内扩散控制,固体内扩散活化能为 61.4 kJ/mol,相应的频率因子为 4.4×105 m2/min。硫化反应后脱硫剂比表面积、孔体积显著减小,脱硫剂表面有颗粒聚集物存在,进一步验证了该脱硫剂的硫化反应主要是通过产物层的体相扩散控制的。     

黏结剂对铁酸锌脱硫剂在高温煤气中脱硫性能的影响

以硝酸铁、硝酸锌、氨水及黏结剂为主要原料,用共沉淀法制成六种铁酸锌脱硫剂。研究了各种黏结剂的加入对脱硫剂的尖晶石结构、硫容量和脱硫效果的影响,在固定床上对其进行脱硫试验。并用X射线衍射（XRD）、扫描电子显微镜(SEM)和气体吸附等测试手段,对脱硫剂的物相组成、结构、比表面积和孔容进行了表征。结果表明,用共沉淀法制备的铁酸锌,具有不受黏结剂影响的尖晶石结构,其颗粒属于微米级;添加高岭土黏结剂的脱硫剂的脱硫效果最好,添加硅藻土的脱硫剂的脱硫效果最差;不同黏结剂对脱硫剂的织构的影响不同;脱硫剂的反应活性和硫容量与其孔容的大小有关。     

不同结构氧化锌对CIIR/ENR共混胶的气体阻隔性能和力学性能的影响

以重量比为90∶10的氯化丁基橡胶/环氧天然橡胶共混胶为基体,用密炼法将三种不同结构的氧化锌（普通条状氧化锌、片状氧化锌和纳米结构氧化锌）分散到基体中,研究不同结构的氧化锌对共混胶力学性能和气体阻隔性能的影响.结果表明片状氧化锌和纳米氧化锌复合胶比普通氧化锌复合胶强度下降,伸长率提高.片层氧化锌复合体系硫磺用量提高到2.0份,综合力学性能达到最好,且片状氧化锌能够赋予复合胶最佳的气体阻隔性能,比普通氧化锌体系提高了50％.     

石墨烯掺杂纳米氧化锌用于检测三乙胺的增强气敏性能

通过简单研磨实现固相反应的方法制备了纳米氧化锌材料,并利用石墨烯掺杂对氧化锌进行改性,研究了氧化锌材料的气敏性能。利用X射线衍射仪(XRD)、扫描电镜(SEM)、红外光谱仪(IR)对合成的样品进行了结构和形貌表征,考察了原料比例和石墨烯掺杂量对氧化锌形貌和气敏性能的影响。结果表明:合成的氧化锌均为纳米颗粒,随着柠檬酸量增加,得到许多有气孔的氧化锌;石墨烯掺杂后,均得到纳米颗粒的氧化锌;气体检测表明,石墨烯掺杂后的氧化锌,其最佳工作温度由400℃降为280℃,对三乙胺表现出较高的选择性;掺杂3%石墨烯的氧化锌对浓度为0.1 mmol/L三乙胺的响应值(S=Ra/Rg)达到18,是掺杂前的4倍。石墨烯掺杂纳米ZnO可作为检测三乙胺气体的新型传感材料。     

煤中混入氧化锌高温焦炉煤气脱硫行为的研究

在热力学模拟结果的基础上，利用在练变煤中添加氧化锌进行焦炉煤气均相脱硫的行为的研究。实验结果表明：在炼焦前期，煤中添加氧化锌可以有效抑制煤中硫的释放，实验所用煤样中的最佳的氧化锌添加量是理论计算所需量的1．4倍.顺炼焦后期，由于焦炉煤气中氢气的作用，半焦中硫化锌和氧化锌开始分解，气态锌和H2S随焦炉煤气的温度降低又生成硫化锌，从而实现了焦炉煤气的脱硫，而且对焦炭质量的影响很小，氧化锌的添加量的增加有利于焦炉煤气进一步的脱硫。     

A complementary and synergistic effect of Fe-Zn binary metal oxide in the process of high-temperature fuel gas desulfurization

57Fe Mossbauer spectroscopy was used to investigate the evolution of Fe-Zn binary metal oxide sorbent in the process of high-temperature fuel gas desulfurization. The results of phase analyses show that Fe-Zn binary metal oxide sorbent is rapidly reduced in hot fuel gas and decomposed to new phases of highly dispersed microcrystalline elemental iron and zinc oxide, both of which become the active desulfurization constituents. A complementary and synergistic effect between active iron acting as a high sulfur capacity constituent and active zinc oxide acting as a deep refining desulfurization constituent exists in this type of sorbent for hot fuel gas desulfurization.     

Parameters affecting carbofuran photocatalytic degradation in water using ZnO nanoparticles

Carbofuran photodegradation in water using zinc oxide nanoparticles as a catalyst was examined as well as some parameters influencing its percentage degradation rate such as zinc oxide load, initial concentration of carbofuran, the temperature of the reaction, the initial pH of the solution, and doping of zinc oxide nanoparticles with 5% (w:w) silver. Zinc oxide and Ag-doped zinc oxide nanoparticles were produced using solvothermal and photoreduction methods, respectively, and silver doping effects on the structural, optical, and photocatalytic properties of zinc oxide nanoparticles were investigated using XRD, UV-VIS spectrophotometer, TEM, SEM, SEM/EDX, and FTIR. The average diameter of the synthesized samples was 26.6, 30.55 nm for undoped zinc oxide and Ag-doped zinc oxide, respectively. Zinc oxide doping with silver did not change the shape of the zinc oxide crystal, but decreased the reflection in the visible region, as well as the energy of the bandgap, and increased the zinc oxide photocatalytic activity.     

从氧化锌矿制备高纯超细ZnO粉体

超细ＺｎＯ具有表面效应、体积效应、久保效应以及优良的光活性、电活性、烧结活性和催化活性 ,可用来制造气体传感器、荧光体、紫外线遮蔽材料、变阻器、图像记录材料、压电材料、压敏电阻、高效催化剂、磁性材料、陶瓷材料、化妆品及医药材料。在橡胶工业、染料油墨等领域也有应用前景[1～ 5] 。目前 ,国内外对制备超细ＺｎＯ粉体的研究文章较多 ,但以氧化锌矿为原料直接研制的文章还很少。湿化学法是近二十年来超细ＺｎＯ产品应用开发的主要活跃点之一 ,直接沉淀法是制备超细ＺｎＯ的一种重要湿化学方法 ,它是在含有一种或多种粒子的可溶…     

Comparative Studies on Degradation of Methyl Orange by Nanostructured Zinc and Zinc Oxide Films

Nanostructured zinc and zinc oxide films were prepared by magnetron sputtering processes and succeeded air annealing treatments. Comparison of reductive degradation rate of methyl orange (MO) by zinc films and photocatalytic degradation rate of MO by zinc oxide films was carried out. Both reductive degradation and photocatalytic degradation process of MO by zinc and zinc oxide films can be described by first order kinetic model. It was found that although MO liquid was most quickly decolorized by metallic zinc films, the mineraliza-tion of MO was not thorough. Observation of extra ultraviolet absorption peaks indicated the formation of aromatic intermediates. On the other hand, although the photocatalytic degradation rate of MO liquid by ZnO films was only as about 1/4 large as the reductive degradation rate by zinc films, no signs of aromatic intermediates were found. Moreover, it was found that partially oxidized zinc oxide film showed higher photocatalytic efficiency than the totally oxidized ZnO films. Synergy effect between zinc and zinc oxide phase in the partially oxidized films was considered to be responsible for the higher photocatalytic efficiency.     

Interaction of Zinc Oxide and Copper Oxide Nanoparticles with Chlorophyll: A Fluorescence Quenching Study

The present study aims to investigate the interactions of zinc oxide nanoparticles and copper oxide nanoparticles with the major photosynthetic pigment chlorophyll using ultraviolet-visible, steady state, and time resolved laser induced fluorescence spectroscopy. The steady state fluorescence measurements show that zinc oxide and copper oxide nanoparticles quench the fluorescence of chlorophyll in concentration-dependent manner. The Stern-Volmer plot for the chlorophyll-zinc oxide nanoparticles is linear, and the value of quenching constant has been observed to increase with temperature indicating the possibility of dynamic quenching. A decrease in the lifetime of chlorophyll with increase in the concentration of zinc oxide nanoparticles confirms the involvement of dynamic quenching in the chlorophyll–zinc oxide nanoparticle interaction. In the case of copper oxide nanoparticles, the Stern-Volmer plot deviates from linearity observed in the form of upward curvature depicting the presence of both static and dynamic quenching. In addition, the lifetime of chlorophyll decreases with increase in the concentration of copper oxide nanoparticles displaying the dominance of dynamic quenching in the chlorophyll-copper oxide nanoparticle interaction. The decrease observed in the value of binding constant with increasing temperature and negative values of change in enthalpy, entropy, and Gibb’s free energy indicates that van der Waal and hydrogen bonding are the prominent forces during the interaction of chlorophyll with both zinc oxide and copper oxide nanoparticles and that the process is spontaneous and exothermic. The interaction of zinc oxide and copper oxide nanoparticles with chlorophyll occurs through electron transfer mechanism. The obtained results are useful in understanding the sensitization processes involving chlorophyll and zinc oxide and copper oxide nanoparticles.     

Colloidal and Chemical Processes during the Interaction between Polyacrylic Acid and Zinc Oxide Dispersion

The kinetics of the accumulation of zinc ions in a solution during the interaction between polyacrylic acid and an aqueous dispersion of zinc oxide is investigated. It is shown that the concentration of zinc ions in solution reaches its maximum within 1.5–5 min after the onset of the process, depending on the concentration of the acid and zinc oxide. The initial rate of a process and the maximum concentration of zinc ions in the solution depend on the initial concentration of reagents in the system. The dissolution rate of zinc oxide is affected by the flocculation of dispersion particles and the concentration of zinc ions in the solution. The adsorption isotherm of polyacrylic acid on zinc oxide particles is of a step-wise type.     

便携式X射线荧光光谱法同时测定氧化锌富集物中锌铁氯镉砷

氧化锌富集物的进口能弥补我国锌矿资源的不足,但要求ZnO>50%、Fe<10%、Cl<8%、Cd<0.25%、As<0.6%。目前常采用YS/T 1171.1～10-2017《再生锌原料化学分析方法》检测氧化锌富集物中锌铁氯镉砷含量,该系列检测方法均需要繁琐的湿法样品前处理,测量过程较为冗长,不能满足氧化锌富集物大量进口时快速通关的需求。故实验建立了采用便携式X射线荧光光谱法(PXRF)同时测定氧化锌富集物中锌铁氯镉砷的方法。采用YS/T 1171.3-2017和YS/T 1171.5-2017方法对氧化锌富集物样品进行定值,然后选取21个含量具有梯度的氧化锌富集物样品作为校准样品,建立起各元素X射线荧光强度值与含量的校准曲线。各曲线相关系数在0.8164～0.9999,方法检出限为0.013%～1.95%,各元素的相对标准偏差(RSD,n=11)均小于0.05%。采用本方法和化学方法分别检测氧化锌富集物样品,各元素的本方法检测值与化学分析方法检测值的相对误差均小于20%。本方法能应用到口岸现场进口氧化锌富集物快速筛查,检测一个样品仅需1分钟测量时间,极大地加快了进口氧化锌富集物通关速度。