Co-Mo-K催化剂上COS、HCN转化率的热力学分析

利用热力学基础数据和相关软件对Co-Mo-K催化剂上COS、HCN加氢和水解反应进行了热力学计算。在热力学上,COS、HCN加氢和水解反应在耐硫变换条件下均为自发过程。计算结果表明在Co-Mo-K耐硫变换条件下COS、HCN主要发生的是水解反应,该结果与工业经验数据基本一致,可以作为工业实际借鉴。     

结焦抑制剂N-360在乙烷炉上的应用

中国石化扬子石油化工股份有限公司烯烃厂1号乙烯装置两台乙烷炉运行周期一直偏低,辐射段炉管使用寿命较短,并影响急冷油减粘系统的稳定运行。应用结焦抑制剂N-360后,乙烷炉运行周期与辐射段炉管使用寿命大幅延长,并且能耗下降、产品收率提高。     

Mechanistic aspects of the water–gas shift reaction on alumina-supported noble metal catalysts: In situ DRIFTS and SSITKA-mass spectrometry studies

Steady-state isotopic transient kinetic analysis (SSITKA) experiments coupled with mass spectrometry were performed for the first time to study essential mechanistic aspects of the water–gas shift (WGS) reaction over alumina-supported Pt, Pd, and Rh catalysts. In particular, the concentrations (μmol g⁻¹) of active intermediate species found in the carbon-path from CO to the CO₂ product gas (use of ¹³CO), and in the hydrogen-path from H₂O to the H₂ product gas (use of D₂O) of the reaction mechanism were determined. It was found that by increasing the reaction temperature from 350 to 500 °C the concentration of active species in both the carbon-path and hydrogen-path increased significantly. Based on the large concentration of active species present in the hydrogen-path (OH/H located on the alumina support), the latter being larger than six equivalent monolayers based on the exposed noble metal surface area (θ > 6.0), the small concentration of OH groups along the periphery of metal-support interface, and the significantly smaller concentration (μmol g⁻¹) of active species present in the carbon-path (adsorbed CO on the noble metal and COOH species on the alumina support and/or the metal-support interface), it might be suggested that diffusion of OH/H species on the alumina support towards catalytic sites present in the hydrogen-path of reaction mechanism might be considered as a slow reaction step. The formation of labile OH/H species is the result of dissociative chemisorption of water on the alumina support, where the role of noble metal is to activate the CO chemisorption and likely to promote formate decomposition into CO₂ and H₂ products. It was found that there is a good correlation between the surface concentration and binding energy of CO on the noble metal (Pt, Pd or Rh) with the activity of alumina-supported noble metal towards the WGS reaction.     

高温变换催化剂制备条件的神经网络优化

将影响低汽气比条件下LB型节能高温变换催化剂活性的主要因素作为人工神经网络的特征输入向量,将全部实验数据分为训练集和预测集,运用Matlab神经网络工具箱,按改进的Bayes自动归一化算法建立反向传播神经网络模型,不仅可防止网络陷入局部最小,而且提高了网络训练精度和泛化能力。适当拓宽正交实验各因素的水平范围,经过不同因素、不同水平间的组合模拟,预测出LB型节能高温变换催化剂的最佳制备条件为氧化铈质量分数0.76%、氧化铜质量分数5.8%、氧化铬质量分数8.6%、氧化镧质量分数1.0%、铁液浓度92 g/L、中和过程最终pH值9.5。在最佳条件下试制催化剂在低汽气比下的平均活性达77.6%。     

热处理条件对硅酸盐玻璃中原位形成银纳米颗粒的影响

用离子交换结合热处理法制备银(Ag)纳米颗粒-玻璃复合材料.用透射电镜、高分辨透射电子显微镜、Ruthefford背散射谱和紫外-可见光吸收光谱研究了热处理条件对玻璃中原位形成Ag纳米颗粒的影响.结果显示:随着热处理温度升高,玻璃表面的Ag原子逐渐向玻璃内部扩散,其表面摩尔浓度逐渐降低.提高热处理温度和延长热处理时间都有利于提高玻璃中Ag纳米颗粒的体积分数.空气中,高温热处理高掺Ag量的白玻璃样品时发生二次成核,因此,Ag纳米颗粒尺寸呈双峰分布.Ag纳米颗粒尺寸的双峰分布导致其等离子体共振吸收峰出现双峰.在氢气气氛中,在250℃热处理2min,即可在玻璃中形成大量Ag纳米颗粒,颗粒尺寸小于空气中高温热处理样品的尺寸,从而引起表面等离子体共振吸收峰发生蓝移.     

降低全低变工艺阻力的措施

将变换流程改为全低变工艺后,吨氨蒸汽消耗明显下降,但触媒床层阻力迅速上升.通过采取增设焦炭过滤器、更换触媒、改进蒸汽分布器等一系列措施,不仅保证了正常的生产指标,而且还使变换炉的阻力有了明显下降,取得了满意的效果.     

B113-2型低汽气比CO高温变换催化剂的研制

介绍了B113-2型低汽气比CO高温变换催化剂的研制方法及其特点。实验室测试表明,B113-2型催化剂具有堆密度低、运行强度高、选择性好、抗沸水性能优、本体含硫低及低温活性好等优点。     

Identification of the state of palladium in various hydrogenation catalysts by XPS

Various commercial supported palladium hydrogenation catalysts were studied by XPS and treated at ambient pressure with hydrogen and air. Unused catalysts exhibit a significant fraction of divalent Pd (oxide) which is reduced by hydrogen treatment at room temperature. Exposure to air in systems with carbonate, alumina, silica or active carbon as support causes the formation of a solid solution of oxygen in Pd characterized by a Pd 3d chemical shift of ca. + 0.4 eV. The absolute binding energy of Pd depends strongly on the matrix, indicating a significant contribution of extra-atomic screening, which prevents a direct comparison of reference samples and supported catalysts. Using the oxidation of CO to CO₂ at 300 K as in situ chemical probe it was confirmed that Pd supported on carbonate, silica and alumina exists in the same metallic state which could be activated for the test reaction irrespective of the variation in XPS binding energies.     

改良MEA脱碳技术在小氮厂变换气脱碳中的应用

介绍了改良MEA脱碳技术的基本原理、工艺特点以及在工业中的应用情况，实践表明，改良MEA提高了溶液的吸收能力，降低了再生热耗，解决了MEA易降解损耗等问题。     

低压合成甲醇用B119型高温变换催化剂

本文介绍了B119型高温变换催化剂的功能，并与国产某型及进口G-3型催化剂进行了实验室性能对比，其化学组成、结构及活性都与进口G-3型催化剂十分相似。该催化剂已在齐鲁石化公司第二化肥厂使用20余月，运行时的各项指标与进口G-3型催化剂相当。