Hydrogen explosion incident mitigation in steam reforming units through enhanced inspection and forecasting corrosion tools implementation

Hydrogen (H₂) explosion effects recently examined, are confirming the devastating loss scenarios to humans, environment, assets, and associated business interruption. H₂ production is a core process in refineries used in further process steps. Steam reforming of natural gas or a mix with naphtha or LPG is a common hydrogen production technique, where the latest technologies have adopted enhanced metallurgies to minimize explosion risk and the associated maintenance cost following plant degradation owing to corrosion effects. However, corrosion rates are still high in specific areas of piping and process equipment. The aim of this paper is to present a methodology based on semi-quantitative RBI modeling according to regulations by API and recent EN standards, adopting a family of linear regression forecasting models that depict the yearly corrosion rate (per corrosion loop) of a hydrogen production steam reforming unit; this is done under different operating conditions (e.g., temperature, pressure, and fluid speed), metallurgy and other related physicochemical variables. The model is based on the examination of both ultrasonic wall thinning measurements and the examination of quantitative crosslinking total corrosion effects along with the physicochemical properties prevailing in different plant corrosion loops. The outcome of the regression analysis is an expansive family of multivariable equations describing, with a defined accuracy, the yearly corrosion rate and associated lifespan forecast per corrosion loop, and per examined part. These equations were further utilized in a custom-made database that can be used as an additional loss prevention tool by the hydrogen production unit management team. Evaluation results regarding the tool efficiency are presented in the following of this paper.     

球形氧化铝负载Ni-Co双金属催化剂上沼气重整制氢——操作条件的影响

前期研究开发出了活性、稳定性和抗积碳性能都较好的沼气重整制氢Ni-Co/La2O3-Al2O3催化剂。在此基础上选用商业球形氧化铝作为载体(4~5 mm)并掺杂La2O3,用浸渍法制备了Ni-Co/La2O3-Al2O3球形催化剂,以CH4/CO2体积比为1的混合气模拟沼气,考察了操作条件对工业尺度催化剂沼气重整反应性能的影响。结果表明:负载活性组分的γ-Al2O3球形催化剂的沼气重整活性基本达到小试的水平。反应温度升高有利于提高催化剂的重整活性,850℃以上催化剂的活性趋于稳定。反应温度升高有利于减少催化剂的表面积碳,却加速了金属颗粒的团聚。随着空速的增加,催化剂的活性显著降低。较好的催化剂还原方式为用纯H2在700℃下还原2 h,用该方式还原的催化剂反应后金属粒径较小,平均积碳速率较低。     

Dry reforming of methane over oil palm shell activated carbon and ZSM-5 supported cobalt catalysts

In this study, cobalt supported oil palm shell activated carbon (Co/OPS-AC) and ZSM-5 zeolite (Co/ZSM-5) catalysts have been prepared for dry reforming of methane. Cobalt ratios of 6.0 and 14.0 wt% were deposited via wet impregnation method to the OPS-AC and ZSM-5 catalysts. The catalysts were characterized by XRD, N₂ adsorption--desorption isotherms, BET surface area, SEM, FESEM-EDX, TPR-H₂, and TPD-NH₃. The dry reforming of methane was performed using a micro reactor system under the condition of 10,000 ml/h.g-cat, 3 atm, CH₄/CO₂ ratio of 1.2:1.0 and temperature range from 923 K to 1023 K. The gaseous products were analyzed by gas chromatography (GC) with thermal conductivity detector (TCD) and further quantified to determine the conversions of CH₄ and CO₂, and the yields of CO and H₂. Experimental results revealed both catalysts exhibited lower conversions of CO₂ and CH₄ with the increase in temperature from 923 K to 1023 K. The reduced conversions may be due to the formation of carboneous substance on the catalyst known as coking. Comparatively, Co/OPS-AC gave higher conversions of CO₂ and CH₄ as well as higher yields of H₂ and CO as it has a higher surface area than Co/ZSM-5 which subsequently rendered higher activity for the reforming of methane. With the increasing cobalt loadings and reaction temperature, OPS-AC(14) catalyst exhibited improved activity and H₂/CO ratio. Based on these results, cobalt supported OPS activated carbon catalyst was suggested to be more effective for CO₂ and CH₄ conversions.     

Hydrogen-rich synthesis gas production from waste wood via gasification and reforming technology for fuel cell application

The purpose of this study was to establish a fuel process for an advanced power generation system in which hydrogen-rich synthesis gas, as the fuel for the molten carbonate fuel cell (MCFC), can be extracted from biomass via gasification and reforming technologies. Experiments on waste wood gasification were performed using a bench-scale gasification system. The main factors influencing hydrogen generation in the noncatalytic process and in the catalytic process were investigated, and temperature was identified as the most important factor. At 950°C, without employing a catalyst, hydrogen-rich synthesis gas containing about 54 vol% hydrogen was extracted from feedstock with appropriately designed operation parameters for the steam/carbon ratio and the equivalence ratio. However, by employing a commercial steam reforming catalyst in the reforming process, similar results were obtained at 750°C.     

生物质废物热解过程中气相产物的生成及等离子体重整研究

针对松木屑的热解以及产物的等离子体重整进行研究。热解温度分别为400,500,600,700,800℃时,在加热30 min的条件下,主要气体产物是H2、CO、CH4和CO2,热解气的总生成量的摩尔分数由46.11%(400℃)增至80.12%(800℃)。介质阻挡放电等离子体重整结果显示,随着放电功率的增加,CH4和CO2的转化率以及H2/CO的摩尔比都呈现增长趋势,控制等离子体重整条件有助于获得高品位能源。     

工业废气在循环流化床锅炉中的掺烧应用

介绍了东方化工厂两台循环流化床锅炉掺烧工业废气改造的背景及原则,叙述了火炬气回收及供气系统、燃气燃烧器、PLC控制三个主要系统的布置、选择、设计等情况,论述了锅炉掺烧火炬气后的安全、掺烧比例的确定、掺烧位置的选择等三个需要重点关注的问题,分析了项目实施后所取得的节能效益、环保效益,是同行业回收利用工业废气,实现节能降耗的一种有效方式,具有很好的参考价值和推广意义。     

水碳比变化对汽油氧化重整制氢影响的研究

本文用正辛烷代替汽油从理论和实验两方面研究了水碳比变化对汽油氧化重整制氢反应的影响。理论研究表明 ,在绝热反应条件下 ,对应确定的反应温度存在一个最佳的氧油比及水碳比 ;实验研究表明 ,在非绝热反应体系中 ,在一定的氧油比及反应温度条件下 ,反应体系的转化率及生成氢的选择性均随水碳比的增加而增加 ,为实现燃料电池汽油制氢自热反应 ,反应体系应在一定水碳比条件下进行 ,实验条件下最佳的水碳比范围是 1.5— 2 .5之间。     

PEMFC制氢技术现状

本文系统地论述了目前国内外离子交换膜燃料电池（ＰＥＭＦＣ）制氢技术现状,较全面的分析了ＰＥＭＦＣ汽油重整制氢技术存在的问题,并对开发适合于ＰＥＭＦＣ汽油重整制氢工作提出了几点建议。     

Biogas from the organic fraction of municipal solid waste: Dealing with contaminants for a solid oxide fuel cell energy generator

The present work investigates electricity production using a high efficiency electrochemical generator that employs as fuel a biogas from the dry anaerobic digestion of the organic fraction of municipal solid waste (OFMSW).The as-produced biogas contains several contaminants (sulfur, halogen, organic silicon and aromatic compounds) that can be harmful for the fuel cell: these were monitored via an innovative mass spectrometry technique that enables for in-line and real-time quantification.A cleaning trap with activated carbons for the removal of sulfur and other VOCs contained in the biogas was also tested and monitored by observing the different breakthrough times of studied contaminants.The electrochemical generator was a commercial Ni anode-supported planar Solid Oxide Fuel Cell (SOFC), tested for more than 300 h with a simulated biogas mixture (CH₄ 60 vol.%, CO₂ 40 vol.%), directly fed to the anode electrode. Air was added to promote the direct internal conversion of CH₄ to H₂ and CO via partial oxidation (POx).The initial breakthrough of H₂S from the cleaning section was also simulated and tested by adding ～1 ppm(v) of sulfur in the anode feed; a full recovery of the fuel cell performance after 24 h of sulfur exposure (～1 ppm(v)) was observed upon its removal, indicating the reliable time of anode exposure to sulfur in case of exhausted guard bed.     

载体结构对Co/MgO-Al2O3催化剂催化C2H6/CO2反应性能的影响

采用共沉淀-浸渍法制备了不同载体结构的Co/Al₂O₃、Co/MgO_（25）-Al₂O_3（75） （Co/M₁A₃-Spinel）、Co/MgO_（75）-Al₂O_3（25） （Co/M₃A₁-Solid）和Co/MgO催化剂,用于CO₂氧化乙烷脱氢（ODEC）和乙烷干重整（DRE）反应.XRD、Raman、H₂-TPR、XPS表征结果表明,载体结构显著影响催化剂上Co物种的落位、结构和还原性能.Co³⁺和Co²⁺在C₂H₆/CO₂反应气氛中可相互转化,促进C₂H₆和CO₂活化;尖晶石结构中的Co物种比固溶体中的Co物种可还原性强,在高温ODEC反应条件下,催化剂表面的Co物种会被还原成Co⁰,协同Co³⁺/Co²⁺导致C—C键和/或CC键断裂,使得反应路径向DRE转变.MgO基固溶体结构中Co物种与载体相互作用更强,在高温ODEC反应中避免了被大量还原为低价态的Co⁰,ODEC反应可稳定进行.