Structure-dependent activity and stability of Al2O3 supported Rh catalysts for the steam reforming of n-dodecane

Steam reforming of liquid hydrocarbon fuels is an appealing way for the production of hydrogen. In this work, the Rh/Al₂O₃ catalysts with nanorod (NR), nanofiber (NF) and sponge-shaped (SP) alumina supports were successfully designed for the steam reforming of n-dodecane as a surrogate compound for diesel/jet fuels. The catalysts before and after reaction were well characterized by using ICP, XRD, N₂ adsorption, TEM, HAADF-STEM, H₂-TPR, CO chemisorption, NH₃-TPD, CO₂-TPD, XPS, Al²⁷ NMR and TG. The results confirmed that the dispersion and surface structure of Rh species is quite dependent on the enclosed various morphologies. Rh/Al₂O₃-NR possesses highly dispersed, uniform and accessible Rh particles with the highest percentage of surface electron deficient Rh⁰ active species, which due to the unique properties of Al₂O₃ nanorod including high crystallinity, relatively large alumina particle size, thermal stability, and large pore volume and size. As a consequent, Rh/Al₂O₃-NR catalyst exhibited superior catalytic activity towards steam reforming reactions and hydrogen production rate over other two catalysts. Especially, Rh/Al₂O₃-NR catalyst showed the highest hydrogen production rate of 87,600 mmol g_fuel^?1 g_Rh^?1min^?1 among any Rh-based catalysts and other noble metal-based catalysts to date. After long-term reaction, a significant deactivation occurred on Rh/Al₂O₃–NF and Rh/Al₂O₃-SP catalysts, due to aggregation and sintering of Rh metal particles, coke deposition and poor hydrothermal stability of nanofibrous structure. In contrast, the Rh/Al₂O₃-NR catalyst shows excellent reforming stability with negligible coke formation. No significantly sintering and aggregation of the Rh particles is observed after long-term reaction. Such great catalyst stability can be explained by the role of hydrothermal stable nanorod alumina support, which not only provides a unique environment for the stabilization of uniform and small-size Rh particles but also affords strong surface basic sites.     

Economic competitiveness of compact steam methane reforming technology for on-site hydrogen supply: A Foshan case study

On-site hydrogen production through steam-methane reforming (SMR) from city gas or natural gas is believed to be a cost-effective way for hydrogen-based infrastructure due to high cost of hydrogen transportation. In recent years, there have been a lot of on-site hydrogen fueling stations under design or construction in China. This study introduces current developments and technology prospects of skid-mounted SMR hydrogen generator. Also, technical solutions and economic analysis are discussed based on China's first on-site hydrogen fueling station project in Foshan. The cost of hydrogen product from skid-mounted SMR hydrogen generator is about 23 CNY/kg with 3.24 CNY/Nm³ natural gas. If hydrogen price is 60 CNY/kg, IRR of on-site hydrogen fueling station project reaches to 10.8%. While natural gas price fall to 2.3 CNY/Nm³, the hydrogen cost can be reduced to 18 CNY/kg, and IRR can be raised to 13.1%. The conclusion is that skid-mounted SMR technology has matured and is developing towards more compact and intelligent design, and will be a promising way for hydrogen fueling infrastructures in near future.     

Techno-economical evaluations of decarbonized hydrogen production based on direct biogas conversion using thermo-chemical looping cycles

Hydrogen production by biogas conversion represent a promising solution for reduction of fossil CO₂ emissions. In this work, a detailed techno-economic analysis was performed for decarbonized hydrogen production based on biogas conversion using calcium and chemical looping cycles. All evaluated concepts generate 100,000 Nm³/h high purity hydrogen. As reference cases, the biogas steam reforming design without decarbonization and with CO₂ capture by gas-liquid chemical absorption were also considered. The results show that iron-based chemical looping design has higher energy efficiency compared with the gas-liquid absorption case by 2.3 net percentage points as well as a superior carbon capture rate (99% vs. 65%). The calcium looping case shows a lower efficiency than chemical scrubbing, with about 2.5 net percentage points, but the carbon capture rate is higher (95% vs. 65%). The hydrogen production cost increases with decarbonization, the calcium looping shows the most favourable situation (37.14 €/MWh) compared to the non-capture steam reforming case (33 €/MWh) and MDEA and iron looping cases (about 42 €/MWh). The calcium looping case has the lowest CO₂ avoidance cost (10 €/t) followed by iron looping (20 €/t) and MDEA (31 €/t) cases.     

Hydrogen Production from Catalytic Steam Reforming of Bio-Oils: A Critical Review

In the future, hydrogen will be an important energy carrier and industrial raw material. Catalytic steam reforming of bio-oils is a promising and economically viable technology for hydrogen production. However, during the reforming process, the catalysts are rapidly deactivated due to coke formation and sintering. Thus, maintaining the activity and stability of catalysts is the key issue in this process. Optimized operation conditions could extend the catalyst lifetime by affecting the coke morphology or promoting coke gasification. This article summarizes the recent developments in the field of catalytic steam reforming of bio-oils, focusing on the operation conditions, the properties of the catalysts, and the effects of the catalyst supports. The expected insights into the catalytic steam reforming of bio-oils will provide further guidance for hydrogen production from bio-oils.     

综合高速效应的凝析气藏流入动态

当井底压力低于露点压力时,凝析液在近井地带开始析出并不断聚集产生凝析油堵塞现象。因此,在制定凝析气井工作制度时,通常以控制生产压差为指导思想,往往忽略高速流动下凝析气液相变的非平衡特征。对于凝析气体系,当外界温压变化速度超过凝析气液的相平衡速度时,凝析气体系相变滞后,开始呈现非平衡特征,即凝析液的析出量随着压降速度的增加而减小。凝析气在向井筒流动的过程中,近井区高速流动使凝析气产生非平衡相变,凝析气在比较高的压降速度下流入井筒,使得凝析液来不及析出。在分析非平衡相变规律与近井地带凝析气渗流参数分布的基础上,评价凝析气液流动过程中的非平衡特征,给出了考虑非平衡相变的凝析液饱和度分布计算公式,并进行了产能预测结果对比。实例分析表明,可以通过适当放大生产压差,增加凝析气液相变非平衡特征,减小井筒附近的凝析液饱和度,提高气井产能与气藏开发效果。     

聚丙烯装置聚合区设备布置及管廊的配管设计

结合工程特点及工艺流程,阐述了300 kt/a聚丙烯装置的布置原则,管道、管架设计要点和方法,以及需要注意的问题。     

反凝析现象对雅克拉凝析气处理工艺的影响

雅克拉凝析气田位于塔里木盆地北部，地处新疆维吾尔自治区阿克苏地区境内，它是中国石化集团公司西北分公司探明并投入开发的最大凝析气田，采用衰竭式开采。通过对井口物流的相态研究，认识了凝析气的反凝析规律，采取了提高凝析气中C^＋₃收率的方法，以确保外输干气的烃露点达到管输要求，并提高该气田开发的经济效益。在工艺方案设计过程中，通过多种工艺方案比选，确定选用膨胀机进口压力为6.0 MPa的膨胀机制冷工艺， C^＋₃收率达到92％以上，外输干气烃露点满足管输要求。     

Dealumination–aging pattern of REUSY zeolites contained in fluid cracking catalysts

The evolution of the properties of a REUSY zeolite contained in a fluid cracking catalyst was investigated under laboratory steam deactivation procedures and in age fractions of the corresponding equilibrium catalyst (Ecat). The aging pattern, defined by the evolution of the zeolite surface area (ZSA) related to the decrease of the unit cell size (UCS), was similar between lab-steamed zeolites and Ecat fractions. A sharp drop in ZSA occurred at ca. 2.430 nm UCS. A study done by FT-IR spectroscopy suggested that zeolite dealumination initially took place more extensively on the sodalite cages and double six-member rings (D6R) of the structure and that the final collapse of the zeolite framework occurred through destruction of the 12-member rings (12M). This can be explained by a crystal fracture and break down process and disassembling of the sodalite cages in the faujasite structure. NH₃ microcalorimetry showed that strong acid sites in faujasites are destroyed by steam aging, but this effect does not lead to a reduction in the cracking activity of the Ecat form. The microactivity test (MAT) showed that the specific activity declined sharply at 2.430 nm UCS. Differences in product selectivity were related to the extent of damage of the zeolite, extra-framework alumina and mesoporosity. While further aging canceled the effect attributed to extra-framework alumina differences attributed to mesoporosity increased.     

椰子油甲酯化法合成烷基醇酰胺

以国产椰子油为原料,在碱性催化剂作用下先甲酯化再缩合制备烷基醇酰胺,通过多次平行实验,确立了最佳反应条件:甲酯化反应的油醇比(mol)为1:5,催化剂氢氧化钾用量为剂油比(w)0.07:1,反应时间1小时;缩合反应的酯胺比(mol)为1:1.15,催化剂氢氧化钾用量为剂酯比(w)0.01:1,反应温度100～110℃,反应压力40～50mmHg,反应时间3.5小时.     

适用于微机的核蒸汽发生器热工水力分析程序—SGTH—2

本程序用于计算核蒸汽发生器的热工水力分布参数以及一次侧流动压降、二次侧自然循环和稳态特性,将本程序的计算结果与法国对同型号蒸汽发生器的实测数据以及用 ATHOS 程序的相应计算结果进行比较,表明主要热工水力参数能令人满意地吻合。