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.     

炼油废白土在水泥厂燃煤自备电厂中再利用的实践

本项目主要研究和实现了工业废白土在BAYAH燃煤自备电厂中的再利用,实现变废为宝,减少了环境污染,同时为企业创造了一定的经济效益。针对废白土的特性,对燃料输送系统给煤机、皮带机、煤仓、下料溜子和排渣系统进行了改造。通过修改操作规程消除废白土对锅炉运行的影响。     

干熄焦锅炉炉管失效机理分析

通过对干熄焦锅炉炉管及腐蚀产物开展系统研究，提出炉管失效原因为氧化/硫腐蚀＋高温粉尘冲刷。长寿命炉管仅耐磨层发生了较为严重的氧化及硫腐蚀，而近基体层发生了轻微氧化及硫腐蚀，基体只发生了轻微氧化；短寿命炉管耐磨层、近基体层以及基体裂纹内均发生了较为严重的氧化及硫腐蚀，且存在珠光体球化、内表面产生全脱碳层等缺陷。推测短寿命炉管存在超温现象，而超温可加剧氧化及硫腐蚀反应。此外，短寿命炉管遭受了较为严重的高温粉尘冲刷，不仅可造成炉管减薄，还会导致炉管表面温度升高。因此，减少循环气体中粉尘量尤其是大颗粒，可有效减弱冲刷以及控制炉管表面温度，是提高炉管使用寿命的关键。     

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.     

燃煤锅炉除尘专用滤料的开发

介绍机械制造厂燃煤锅炉的烟尘特点,分析滤料失效的原因,提出一套针对该工况的滤料解决方案。介绍针对复杂工况条件所选用的纤维种类以及复合面层原料成分配比的确定,最终选用针刺工艺加工并对该新产品的基本性能进行了测试分析。     

600MW超临界CFB机组深度调峰运行技术

经通过分析超临界CFB机组在深度调峰方面的优势,结合600MW超临界CFB机组的实际运行工况,提出机组在深度调峰前应开展的试验工作。研究600MW超临界CFB机组的深度调峰过程,从汽机、锅炉、电气等方面提出有效的技术措施,解决深度调峰可能带来的锅炉流化不良、环保参数控制困难等问题。通过在600MW超临界CFB机组上应用,机组在30%负荷深度调峰运行,工况稳定,各项参数正常,取得了较好效果。     

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。     

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.