半再生重整催化剂PRT-C、PRT-D的器内再生

主要介绍了半再生重整催化剂PRT-C、PRT-D器内再生的过程。经过再生,催化剂具有较好的活性、选择性和稳定性,能够满足工业生产需要。     

PRT-C/PRT-D半再生重整催化剂在中国石油独山子石化的长周期工业应用

介绍了中石化石油化工科学研究院有限公司研制的PRT-C/PRT-D半再生催化重整催化剂在中国石油独山子石化公司500 kt·a^-1重整装置上超长周期工业应用的情况。超过12年的工业运行结果表明,在较低的加权平均床层反应温度(WABT,466.5℃)下,重整稳定汽油研究法辛烷值保持在95以上,芳含保持在65%以上,说明PRT-C/PRT-D催化剂抗积炭能力优异,具有较好的活性、稳定性,可以满足半再生催化重整装置长周期稳定运转的需要。     

器外再生重整催化剂3932/3933开工技术的首次应用

介绍了重整催化剂3932/3933器外再生后的工业使用情况,包括各个工序操作指标和过程。最终干燥温度为450 ℃,系统中控制的最终氧含量为16%;还原控制升温速率20～30 ℃·h^－1,还原最高温度480 ℃。硫化以二甲基二硫为硫化剂。半再生重整装置的处理能力为300 kt·a^－1。重整催化剂经过干燥、还原和硫化后投入工业应用,汽油产品质量符合设计要求,通过博士实验,腐蚀等级1a,研究法辛烷值为92。重整装置运行平稳。     

PRT-C PRT-D催化剂首次开工运行总结

本文介绍了陕西延长石油(集团)永坪炼油厂首次工业应用PRT-C、PRT-D重整催化剂性能特点、试车及运行情况,分析运行中存在的问题,总结经验和不足。     

重整催化剂再生质量的改进措施

针对连续重整装置催化剂再生后活性不稳的问题进行分析,找到主要影响因素并采取相应措施,改善了再生后催化剂的活性。提出了进一步优化的建议和技术改造设想。     

重整催化剂硫中毒的工业再生处理

针对中国石化沧州分公司150 kt·a^－1催化重整装置的3932和3933两种重整催化剂两次硫中毒的工业再生处理,阐述了重整催化剂硫中毒工业处理方法。两次再生效果的对比表明,提高热氢除硫操作温度是保证催化剂再生效果的关键。     

连续重整装置催化剂再生系统运行问题分析及对策

催化剂再生系统是连续重整装置的重要组成部分。针对中石化洛阳分公司70万t/a连续重整装置在运行中存在低温部位氯腐蚀、再生器和反应器中心筒跑剂问题、反应器下部料腿堵塞和空料腿现象、重整反应器上部料斗提升氢后路约翰逊网堵塞问题和再生频繁热停问题,分析了这些问题产生的原因并提出具体应对措施。     

重整催化剂再生过程中注氯量的调节

对重整催化剂再生过程氧氯化进行分析，提出了重整催化剂再生时注氯量的调节依据，根据近期内提升时第一反应器床层和出口温度的变化情况，得出了催化剂再生时水氯平衡的调节原则。     

重整装置首次开工关键因素探讨

阐述了做好重整装置首次开工的几个关键因素：做好预处理开工工作,确保重整进料合格;做好重整催化剂的处理工作;把好重整进油后480℃温度关;遵守操作规程,平稳操作。     

固态脱氯技术在重整催化剂再生系统的应用

对持续重整催化剂再生固态脱氯技术进行分析,通过固体脱氯及取代原碱洗与水洗系统,将工艺流程进一步简化,便于操控。通过使用可以看出,固态脱氯技术的使用,降低了再生系统的腐蚀性,令再生运转时间延长,并且减少了再生气体的水含量,提升了催化剂的再生性能,具备良好的经济效益与环保效益。     

分子筛重整催化剂研究进展

催化重整是芳烃的主要来源,但目前所用的重整催化剂存在对直链烷烃选择性差、生产过程中需不断补氯的缺点,国内外纷纷转向分子筛重整催化剂的研究。本文概述了国内外ZSM-5重整催化剂、载铂丝光沸石、β沸石以及L型分子筛重整催化剂的研究进展,详细分析了各种分子筛重整催化剂的优缺点。着重对ZSM-5和L型分子筛重整催化剂的反应性能和芳构化反应机理进行了系统概述,并对分子筛重整催化剂的发展趋势进行了探讨。指出分子筛重整催化剂代替传统重整催化剂是重整领域发展的必然趋势,结合失活机理对分子筛进行合理改性,提高催化剂的稳定性是分子筛重整催化剂发展的关键。另外,还应开发新型分子筛用于重整催化剂中,从而加快分子筛重整催化剂的工业化进程。     

Kinetics of steam reforming over a Ni/alumina catalyst

Steam reforming of methane over a commercially available, nickel/alumina catalyst was experimentally studied. The reactor employed for the study was made of 7 mm i.d. quartz tube and catalyst particles were 0.84-1 mm in size. The amount of catalyst charge in the reactor was around 0.3 gram. Experiments were carried out varying the steam to methane ratio in the feed gas from 1 to 10 and reaction temperature from 823 to 1073 K. Nitrogen gas was used to control partial pressure of methane and steam. Using Marquardt method reaction rate derived from the experiments was fitted to $$reaction rate = 1,527 exp( - 14,820/RT) P^{1.014} _{CH_4 } P^{ - 0.9577} _{H_2 0} $$ Thus reaction order was close to one for methane and close to minus one for steam, respectively.     

重整再生气脱氯剂的选择与应用

针对困扰重整装置催化剂再生后活性不稳定的问题,对原装置进行了技改,采用固体脱氯剂代替原来的碱洗来处理重整催化剂再生气,使再生系统达到平稳良好的运行状态。本技改措施的关键是要选择优良的高温脱氯剂。     

Fluidizable catalyst for methane reforming

Fluidizable catalysts are developed in this study for advancing an integral approach towards a new methane reforming process. With this end, catalysts constituted by nickel supported on -alumina, NaY, and USY were developed using the incipient wetness technique producing bulk nickel loadings in the 0–20 wt.% range. These catalysts were also tested under relevant conditions for industrial operation in a novel Riser Simulator. It was found that, for the case of ‘dry’ reforming of methane, nickel deposited in zeolites is a promising catalyst given that it allows for close control of metal dispersion–redispersion process. In fact, when this catalyst was exposed to repeated oxidation and reduction cycles, nickel dispersions remained stable at 25% for NaY zeolite and at 15% for USY zeolite. This catalyst offers, however, limited application for steam reforming of methane given the potential collapse of the zeolite structure under steam atmosphere. As an alternative and for cases where steam reforming of methane is preferred, nickel on -alumina catalyst was considered. In these cases, optimum catalytic activity was achieved with 2.5 wt.% of nickel on -alumina with 3–6% nickel dispersion.     

The catalytic performance of Ni/MgSiO3 catalyst for methane steam reforming in operation of direct internal reforming MCFC

Active and tolerant Ni-based catalyst for methane steam reforming in direct internal reforming molten carbonate fuel cell (DIR-MCFC) was developed. Deactivation of reforming catalysts by alkali metals from electrolyte composed of Li₂CO₃ and K₂CO₃ is one of the major obstacles to be overcome in commercialization of DIR-MCFC. Newly developed Ni/MgSiO₃ reforming catalyst showed activities of ca. 82% methane conversion for 240 min in out-of-cell test. In duration test, the unit cell containing Ni foam impregnated with Ni/MgSiO₃ in anode gas channel did not give performance degradation for more than 2000 h, while the unit cell assembled with Ni/MgSiO₃-coated anode showed a significant performance loss after an operation of 1200 h. Results obtained from X-ray diffraction and Brunauer–Emmett–Teller technique revealed that Ni sintering and support deterioration were decisive factors in decreasing the catalytic activity.     

双金属Ni-Co/HZSM-5催化剂上甲烷二氧化碳重整反应

采用等体积浸渍法制备一系列双金属Ni-Co/HZSM-5催化剂,考察反应温度和Ni与Co质量比对甲烷二氧化碳催化重整性能的影响。采用BET和H2-TPR表征催化剂的孔结构和还原性能,结果表明,负载的活性组分均匀分散在HZSM-5载体孔道内。Ni与Co之间存在协同作用,促进了Ni-Co/HZSM-5催化剂的还原性能。单金属Co催化剂几乎对甲烷没有转化活性,双金属Ni-Co催化剂催化活性明显提高,Ni与Co质量比6∶4时,催化剂甲烷二氧化碳重整反应的催化活性和稳定性优于单金属Ni催化剂。     

优化重整催化剂氯含量的测定方法

催化剂中氯含量的控制对于催化重整过程非常重要。原分析方法存在样品消解不完全,重复性差的缺点,因此更换了还原剂,本文主要阐述对原测定方法进行优化的过程,最终达到操作简便,精密度高,结果准确的目的。