Ultra-deep desulfurization of coker and straight-run gas oils: Effect of lowering feedstock 95% boiling point

Production of diesel fuels with ultra-low-sulfur levels by deep desulfurization of gas oil feeds has received considerable importance in the petroleum refineries in recent years. The type of the gas oil feed and its distillation temperature play a key role in the deep desulfurization process. In the present research project, the effect of lowering the 95% distillation temperature (T₉₅) of two gas oil feeds, namely, straight-run gas oil (SRGO) and coker gas oil (CGO), on deep desulfurization to ultra-low-sulfur levels was investigated. The results showed that for both types of feeds a higher degree of desulfurization was achieved with reduction of T₉₅ from > 360 °C to < 340 °C. The refractory alkyl dibenzothiophenes boiling above 320 °C were present in very low concentrations in the low-boiling cuts and deep HDS to ultra-low-sulfur levels (< 50 ppm) was achieved at low severity operating conditions. Among the two feeds, the CGO that contained high nitrogen content, high concentrations of sterically hindered alkyl DBTs and high aromatics content (low feed saturation) was more difficult to desulfurize than SRGO.     

制备条件对MoO_3/γ-Al_2O_3结构的影响及ZnO改性作用的LRS研究

当MoO_3含量低于单层分散容量时,MoO_3/γ-Al_2O_3喇曼谱图上两个最突出的峰是～950cm~(-1)的宽峰和876cm~(-1)的较尖锐峰。前者代表“二维聚铝酸”(其中的铝主要是八面体配位的),是加氢脱硫(HDS)等活性中心的前身;后者代表孤立的、四面体配位的钿物种,在加氢脱硫反应中没有活性。用定性和定量的方法系统研究了浸渍液的pH值、焙烧温度、时间、MoO_3总含量等因素对MoO_3/γ-Al_2O_3中两种钼物种相对含量的影响。探讨了在制备过程中减少这种四面体配位钼物种相对含量的方法。指出添加ZnO,使γ-Al_2O_3变成缺锌铝酸锌可以在一定程度上抑制此种非活性钼物种的生成,从而达到提高催化剂活性的目的。     

氮化物对柴油加氢脱硫影响的研究进展

分别从催化剂,工艺条件等方面介绍了氮化物对柴油加氢脱硫反应（HDS）影响的机理。介绍了氮化物对柴油HDS反应影响的动力学研究。结果表明：氮化物对柴油HDS反应具有抑制作用;在不同催化剂活性中心上和不同的工艺条件下氮化物对柴油HDS反应的影响存在差异且符合于拟一级反应动力学。氮化物对柴油HDS的影响研究,可以指导高活性催化剂的开发,寻求最优柴油HDS反应工艺。     

Hydrodesulfurization of dibenzothiophene on alumina-supported molybdenum nitride

An alumina-supported molybdenum nitrided catalyst was prepared and tested to determine its activity and selectivity during the hydrodesulfurization of dibenzothiophene. The nitrided catalyst was extremely active for the selective C-S bond breakage of dibenzothiophene to produce biphenyl.     

Genesis of new HDS catalysts through a careful control of the sulfidation of both Co and Mo atoms: Study of their activation under gas phase

Impregnation of oxidic precursor with thioglycolic acid aqueous solution was successfully used to improve the performances of thiophene hydrodesulfurization catalysts. Raman, EXAFS and XPS studies indicate that addition of this chelating agent affects the sulfidation of the supported metals. The higher catalytic performances were attributed to an optimization of the nature and morphology of the active phase obtained by the use of this chelating agent which permits a simultaneous sulfidation of both Co and Mo atoms.     

Synthesis and characterization of cobalt–molybdenum bimetallic carbides catalysts

Co₃Mo₃C, Co₆Mo₆C and MCM41-supported Co₃Mo₃C catalyst are prepared by a simple one-step thermal decomposition method without the conventional temperature-programmed carburization. The resultant carbides are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscope (HRTEM) and BET surface area measurements. The as-prepared Co₃Mo₃C/MCM41 catalyst exhibits good performance in both probe reactions of hydrodesulfurization (HDS) and hydrodenitrogenation (HDN), which proves the one-step decomposition method to be an effective route for the preparation of bimetallic carbide catalyst.     

Study of the catalyst deactivation in an industrial gasoil HDS reactor using a mini-scale laboratory reactor

The activity of a hydrodesulphurization catalyst loaded in an industrial hydrotreater is studied at start up and end of run. Catalyst initial and final activity was determined by performing HDS experiments at industrial conditions in a laboratory mini-scale hydrotreater. The results show that the deactivation of the catalyst samples collected from three different places of the industrial reactor do not vary significantly, the maximum difference among the catalyst samples, being less than ±4%. The experimentally determined deactivation level of the catalyst samples is compared with the deactivation estimated for the same industrial reactor and the same load using a hybrid neural network model trained with operational data of the industrial and the results are in close agreement. Catalyst deactivation appears to be faster for hydrogen consumption reactions than for hydrodesulphurization reactions indicating a decreasing hydrogen consumption trend with time in operation for specific sulphur content in the product.     

Extraction of molybdenum,nickel and aluminium from spent Ni–Mo hydrodesulphurization (HDS) catalyst in oxalic acid solutions

ABSTRACT

Dissolution behaviour of metals in Ni–Mo hydrodesulphurization catalyst waste was investigated in a 1?L jacketed glass reactor. Samples were roasted at 500°C in a tube furnace for the removal of C and S prior to the dissolution experiments. It was determined that roasted samples consisted of mainly 27.692% Al, 20.238% Mo, 5.267% Ni and 4.331% P. Unmilled samples were used for dissolution experiments because dissolution experiments carried out with milled and unmilled samples showed that milling has no significant effect on the dissolution rate. Oxalic acid solutions with 0.25–1 M, reaction temperatures of 25–70°C and solid to liquid ratios of 10–100?g?L^?1 were used as experimental parameters. It was found that the dissolution behaviour of Ni is different from Al, Mo and P. 92% of Mo, 19% of Ni, 28% of Al and 72% of P were dissolved at optimum dissolution conditions.     

新型（不预硫化）Mo—Co／TiO2加氢转化催化剂的反应机理,制备和性能评价

阐述新型（不预硫化）Ｍｏ－Ｃｏ／ＴｉＯ２加氢转化硫（ＨＤＳ）催化剂的反应机理和制备方法;新催化剂具有不需预硫化过程,且初活性及稳定性均高等优点。     

The catalytic activity of Ni/W bimetallic sulfide nanostructured catalysts in the hydrodesulfurization of dibenzothiophene

Two types of catalysts containing NiW bimetallic sulfide nanostructures were prepared by a chemical method employing ammonium thiotungstate and nickel nitrate as metal-sulfide precursors followed by sulfidation in H₂S/H₂ at 400 °C. The nanostructures were grown with excess of Ni, at atomic ratio R = 0.75, 0.85 (R = Ni/Ni + W). High resolution electron microscopy (HRTEM) micrographs revealed the formation of two types of nanostructures, nickel sulfide nanoparticles and long nanorods of tungsten suboxide, both coated by WS₂ layers. The Ni/W catalyst containing mostly nanorods presented twice the catalytic activity (pseudo-zero order constant rate k = 12 × 10⁻⁷ mol/s.g) of the Ni/W catalyst containing nanoparticles (k = 6.3 × 10⁻⁷ mol/s.g) with a low selectivity for tetrahydrodibenzothiophene (THDBT) and high selectivity to cyclohexylbenzene (CHB, 50 mol%). In turn the Ni/W catalyst containing nanoparticles presented a catalytic activity comparable to a Ni/Mo catalyst without inorganic fullerene (IF) nanostructures (k = 7.2 × 10⁻⁷ mol/s.g) but with higher selectivity for hydrogenation to THDBT, (14 mol%) than the sample with nanorods.