FF-18 FCC原料预处理催化剂反应性能的研究

考察了反应温度、空速、氢油比和不同原料对FF-18催化剂反应性能的影响,并进行了催化剂稳定性试验,结果表明:FF-18催化剂显示出好的加氢脱硫性能及原料适应性,活性稳定性较好.     

加氢裂化预处理催化剂的开发及其性能评价

以拟薄水铝石为主要载体原料,以W—Ni为加氢成分,进行了加氢裂化预处理催化剂的开发。通过添加改性助剂,调节了催化剂的表面酸性和金属分散性,提高了催化剂活性。在200mL固定床加氢装置上评价结果表明。以大庆CGO与VGO混合油为原料,在压力15MPa、空速1．0h-1、氢油比760：1的操作条件下,所研制的催化剂加氢脱氮率为99．47％、加氢脱硫率为99．74％、加氢脱芳率为66．12％,显示了较好的催化活性。2000h活性稳定性试验表明催化剂活性稳定,能满足加氢裂化装置长周期运转要求。     

桦甸页岩油柴油馏分中氮化物的加氢反应性能

采用硫化态NiMoW/Al2O3催化剂、在微型固定床加氢反应装置上,考察了反应温度、反应压力、停留时间和氢油体积比对桦甸页岩油柴油馏分中氮化物脱除率的影响,计算了加氢脱氮反应的表观动力学常数。实验结果表明,升高反应温度和反应压力或延长停留时间都能使碱性氮、非碱性氮及总氮的脱除率增加,但三者的增幅不同;增大氢油体积比使碱性氮、非碱性氮及总氮的脱除率先显著增加后略有减小。碱性氮、非碱性氮及总氮的加氢反应均符合拟一级反应动力学方程,在较低温度(340℃)下,总氮的脱除速率由碱性氮的脱除速率决定;而在较高温度(380℃)下,总氮的脱除速率由非碱性氮的脱除速率决定。NiMoW/Al2O3催化剂可有效降低加氢脱氮反应的表观活化能,具有较高的加氢脱氮活性。     

Hydrodesulfurization, Hydrodenitrogenation, Hydrodemetallization, and Hydrodeasphaltenization of Maya Crude over NiMo/Al2O3 Modified with Ti and P

The effect of adding Ti (4.5 wt%) and P (∼1.0 wt%) by several routes to a NiMo/ab Al₂O₃ catalyst on the hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrodemetallization (HDM), and hydrodeasphaltenization (HDAs) of heavy Maya crude was investigated. The results show that not all the catalyst functionalities respond equally well to the addition of Ti and P to the catalyst formulation. There is not a single catalyst formulation that can achieve optimum performance in all the catalyst functionalities. For HDS, Ti incorporation increases activity but the route by which P is added afterwards can improve or be detrimental to HDS activity. For HDN, the incorporation of P to the catalyst can lead to significant improvements in catalytic activity and catalyst stability. Ti increases HDM activity but the addition of P to the catalyst is detrimental to this functionality. For the elimination of asphaltenes, the catalyst supported on pure alumina is the best. So for HDAs, no benefit is obtained by the addition of Ti or P to the catalyst. Textural properties are important and HDM and HDAs increase with catalyst average pore diameter. Hydrodemetallization activity increases with the acidity of the catalyst.     

Mechanism of carbon–nitrogen bond scission in the presence of H2S on Pt Supported catalysts

The reactivity of a series of amines with various structures and different numbers of hydrogen atoms on the carbon atoms in the and position was used to evidence the C–N bond scission mechanism in the presence of H₂S on Pt based catalysts (deposited on alumina, zirconia and silica–alumina) and compare it with the mechanism on a NiMoP on alumina sulfide catalyst. The effect of the H₂S partial pressure was also checked. Catalytic activities (amine overall conversion, C₅ hydrocarbon formation, and amine disproportionation) deeply depend on the structure of the N-containing molecule. Tert-pentylamine is the most reactive molecule for sulfide catalysts whereas, in the case of n-pentylamine, Pt on zirconia was found to be the most efficient for C–N bond breaking. Such properties cannot be related to the acidic properties of the support but to a unique support–metal interaction, since alumina or silica–alumina supported platinum catalysts do not present this behaviour.     

ＦＨ-５Ａ型加氢精制催化剂在缓和反应条件下的性能考察

在大型柴油加氢装置上对ＦＨ-５Ａ型精制催化剂的性能进行了考察。结果表明,由不同比例的重油催化柴油、焦化柴油和高含硫直馏柴油组成的多种混合原料,在缓和的反应条件下,采用ＦＨ-５Ａ加氢精制催化剂都能生产出符合环保要求的低硫优质柴油。     

A comprehensive study of indole catalytic hydrodenitrogenation under hydrothermal conditions

This article focuses on the catalytic hydrodenitrogenation (HDN) mechanism of indole under hydrothermal conditions. Formic acid (FA), which is a donor of both gaseous hydrogen and liquid hydrogen, can improve indole conversion and total yield of denitrogenated products. Ru/C showed the highest activity among the catalysts in this study for indole conversion at all temperature conditions with the existence of H₂, and 91.17% indole was converted at 400°C and 60 min. Based on reaction kinetic experiments, a kinetic model was developed mathematically to describe the hydrothermal HDN reaction of indole over the home-made Ni₈₀Ru₂₀/γ-Al₂O₃ catalyst, which clearly captured all data trends and fitted the temporal variation of all major liquid products. High activation energy for the formation of the O-containing substance o-cresol from both mathematical fitting and density functional theory (DFT) calculation indicated the rare occurrence of a reaction between the pyrrole ring-opening product methyl aniline and H₂O, consistent with the experimental observation that only a trace of o-cresol was detected.     

EDTA对NiW／Al2O3催化剂表面金属分散性、形貌及HDN性能的影响

为提高负载催化剂中金属的分散性,以含EDTA螫合剂的浸渍液浸渍制备了NiW／Al2O3加氢处理脱氮催化剂,其中络合剂与Ni的摩尔比为1：1,考察了EDTA对活性金属分散性及加氢脱氮性能的影响。通过BET、XRD、XPS和HRTEM表征发现,EDTA的引人,可以提高M和W在氧化铝载体表面的分散性,W／A1原子比从0．096提高到0．127。EDTA的引入,同时减弱了活性金属与氧化铝载体间的相互作用,有利于形成堆积程度较高的WS：相。EDTA的引入,可以大幅提高催化剂对喹啉的加氢脱氮活性,相对于传统方法制备的催化剂,其加氢脱氮活性可提高27％。     

离子淌度飞行时间质谱表征减压蜡油加氢脱氮过程中氮化物的变化

用配备了电喷雾电离源(ESI)的离子淌度飞行时间质谱(IMS-TOF MS),对不同温度下加氢的大庆减三线蜡油(VGO)中的碱性氮化物和中性氮化物进行了表征,探讨了加氢脱氮过程中氮化物的转化机理。氮元素分析结果表明,反应温度更高的加氢产物脱氮程度更深,大庆VGO的中性氮含量高于碱性氮,经过轻度脱氮处理后会出现中性氮含量低于碱性氮的情况,但深度脱氮后2种氮化物的含量相当。质谱表征结果显示：加氢前大庆VGO的中性氮化物以苯并咔唑和二苯并咔唑类化合物为主,碱性氮化物以吡啶类化合物为主。在脱氮程度较浅的大庆VGO样品里,中性氮化物的含量有所下降,还出现了环胺类碱性氮化物,这部分环胺类化合物在深度脱氮的大庆VGO样品中明显减少,说明中性氮化物经加氢后先生成了环胺类碱性氮化物,再进一步被加氢去除。研究结果表明,无论是中性氮化物还是碱性氮化物,不饱和度更高以及侧链更短、更少的氮化物都更容易被加氢去除。