直馏煤油低压加氢精制生产3号喷气燃料技术开发

拓宽直馏煤油馏分（提高直馏煤油的终馏点）可以增产喷气燃料,但馏分拓宽后会导致原料油的硫、氮含量增加,同时也会导致烟点降低和冰点升高。对馏分拓宽的直馏煤油进行低压加氢工艺试验,研究结果表明较高的反应温度、较低的体积空速有利氮化物的脱除,但在高温情况下会导致产品的色度下降。对低压加氢工艺流程进行优化升级,开发了生产喷气燃料的低压直馏煤油加氢新工艺。与常规工艺相比,该新工艺具有较强的加氢性能,同时还具有改善喷气燃料产品颜色的性能。     

TiO2的加入方法对非负载的磷化镍催化剂加氢脱氮性能促进作用的影响

采用共沉淀法和浸渍法将TiO2引入到非负载的磷化镍催化剂中,并以喹啉作模型化合物考察了其对磷化镍催化剂加氢脱氮(HDN)反应性能的影响。结果表明,两种方法引入的TiO2都对磷化镍催化剂HDN反应活性有很大的促进作用,但是用浸渍法制备的催化剂活性更高。表征结果显示,磷化镍表面的同磷化镍之间存在相互作用的Ti物种是起促进作用的主要原因。浸渍法制备的催化剂表面的Ti含量更高,因此,对磷化镍催化剂HDN反应活性的促进效果更加显著。     

加氢催化剂系列的开发与进展

石油化工科学研究院自1987年将RN-1加氢精制催化剂成功地用于工业装置以来,共开发了11个系列18种催化剂,其中14种催化剂获得工业应用,取得了良好的经济效益和社会效益,其技术水平达到国际先进水平.     

Effect of the zeolite content on the hydrodenitrogenation of 1,2,3,4-tetrahydroquinoline over sulphided NiMo on alumina catalysts

The catalytic hydrodenitrogenation of 1,2,3,4-tetrahydroquinoline was studied on nickel and molybdenum sulphides supported on alumina-zeolite mixtures. Different ratios (number of acid sites)/(number of hydrogenating sites) were obtained by varying the weight of the zeolite in the support. The results obtained indicate the existence of an optimal ratio (number of acid sites)/(number of hydrogenating sites), hence of an optimal distance between both types of sites, for which the decahydroquinoline formed on the hydrogenating sites shifts rapidly on the neighbouring acid sites and cracks into the desired reaction product (propylcyclohexane). The corresponding catalyst exhibits a selectivity for hydrodenitrogenation much higher than classical NiMo on alumina catalysts.     

The activity of transition metal nitrides for hydrotreating quinoline and thiophene

An investigation has been conducted of the activity of AlN, BN, TiN, VN, Mo₂N, and W₂N as catalysts for quinoline hydrodenitrogenation (HDN). The activity of Mo₂N and VN for thiophene hydrodesulfurization (HDS) and the concurrent hydrotreatment of quinoline and thiophene have also been examined. Bulk AlN, BN, and TiN were obtained with low surface areas and found to be inactive for the HDN of quinoline. Bulk Mo₂N, W₂N, and VN could be obtained with high surface area. Each of these nitrides exhibited high activity for quinoline HDN, the turnover frequency for this reaction decreasing in the order Mo₂N>W₂N>VN. Highly dispersed VN supported on SiO₂ was found to have a specific activity for quinoline HDN identical to that of bulk VN. Both bulk Mo₂N and 27% VN/SiO₂ exhibit high activity for the HDS of thiophene. The behavior of these two catalysts for the concurrent hydrotreatment of quinoline and thiophene is also discussed.     

Catalytic upgrading of liquid hydrocarbons derived from coprocessing of heavy oil and coal

Coprocessing of heavy oil and coal under elevated temperature, hydrogen pressure and low space velocity resulted in a product slurry from which the fraction distilling below 430° C was catalytically upgraded over a commercial NiMo/Al₂O₃ catalyst in a flow reactor. At 400° C, 13.3 MPa (H₂) and LHSV of 1.0 h^?1 over 90% of sulfur and nitrogen could be removed, aromaticity reduced to 16% from 26% and the API gravity increased to 36.9 from 23.8. Hydrogen consumption under these conditions was considerably lower than that obtained for upgrading the oil sands coker gas oil. Activation energies for hydrodesulfurization and hydrodenitrogenation reactions were determined to be 59.5 and 120.4 kJ/mol, respectively.     

NiMo/Al2O3加氢精制催化剂上操作变量对HDN和HDS反应性能的影响

Using the JQ-Ⅱ high pressure hydrogenation micro-reactor unit, the reactivity of Athabasca bitumen derived heavy gas oil was studied over commercial and homemade hydrotreating catalysts. The effects of catalyst preparation variables and the influences of operation conditions, such as pressure, temperature, hydrogen/oil ratio and space velocity were also examined. It was shown that the optimal concentrations of the active components were 5% of NiO, 20% of MoO3 and 3.5% of phosphorus (by mass), and the suitable operation conditions were determined experimentally.     

Silica and alumina impregnated with dimethylformamide solutions of molybdophosphoric or tungstophosphoric acids for hydrotreatment reactions

Heteropolyacid (HPA) based catalysts were prepared by impregnation of silica and alumina with dimethylformamide solutions of molybdophosphoric and tungstophosphoric acids. This solvent allows the preservation of the Keggin unit during the impregnation independently of the nature of the support. Ni-promoted catalysts were prepared by impregnation with nickel nitrate solutions of the supported HPA. The stronger interaction of the HPA with alumina than with silica allows a better dispersion of the polyoxometallate species on the former one whereas the formation of bulk oxides is observed on silica. The performance of these HPA–Ni/support catalysts for hydrodenitrogenation and hydrodesulfurization reactions is related to the precursor–support interaction.     

On the continuum approximation of large reaction mixtures

In analyzing a reaction mixture of very many components, treating the mixture as a continuum can produce results of generality. In many practical situations (e.g., hydrodesulfurization), it is highly desirable to predict the overall behavior of the mixture at large times (high conversions) with minimum information on the mixture property. For irreversible first‐order reactions in a plug‐flow reactor, it was previously shown that the continuum approximation cannot be valid at arbitrarily large times. This work is an investigation of the validity of the approximation for mixtures with complex kinetics. It is found that the approximation can be conditionally or universally valid, depending on kinetics, reactor type, pore diffusion, and mixture properties. The validity conditions for a variety of situations, nontrivial as they may seem, take a power‐law form. Backmixing and pore diffusion widen the range of validity. The underlying physics and some dichotomies/subtleties are discussed. The results are applied to catalytic hydroprocessing in petroleum refining. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

负载型磷化钼催化剂的制备及其加氢脱氮活性研究

采用溶胶-凝胶法制备出三元复合载体TiO2-ZrO2-SiO2并负载磷化钼,以其为载体原位还原制备出加氢脱氮催化剂MoP/TiO2-ZrO2-SiO2。以喹啉为模型化合物,考察了三元复合载体TiO2-ZrO2-SiO2中Ti/Zr/Si的不同配比和还原条件对催化剂加氢脱氮性能的影响。结果表明,n(Ti)/n(Zr)/n(Si)为6∶1∶10的复合载体其比表面积和孔结构最为理想,在升温速率为2℃/min,还原H2流速为60 mL/min,还原压力为0.5 MPa,还原终温为600℃的最佳还原条件下,其加氢脱氮率达97.85%。