焙烧HDS失活催化剂提取钒的动力学

在固定床反应器中 ,用空气焙烧HDS失活催化剂 ,再用碳酸钠水溶液浸取钒和钼。研究了钒焙烧转化率随失活催化剂粒径、焙烧温度及焙烧时间的变化关系 ,结果表明 :实验数据可以用收缩未反应核模型拟合。当催化剂平均粒径小于 6 0 μm ,或在较低反应温度及较低转化率下 ,内扩散阻力可以忽略不计 ,过程受化学反应控制 ;而当平均粒径大于 6 0 μm ,且在较高反应温度及较高转化率下 ,过程同时受化学动力学与内扩散控制。分别导出了 2种情况下焙烧钒的动力学方程式 ,并按方程式计算得到反应温度在 92 3～ 112 3K时的活化能为 5 6 .12kJ·mol-1。     

二硫化钼催化剂的制备与应用

综述了二硫化钼催化剂的物理化学性质以及国内外的几种制备方法,包括工业天然法和化学合成法。简要介绍了载体对催化剂的一些影响;从加氢脱硫、加氢脱氧及催化加氢几个方面对二硫化钼催化剂的应用进行了论述;对二硫化钼的形态,嵌入不同金属的MoS2催化剂在应用中对反应的影响及催化加氢机理进行了简要叙述。     

Synthesis, characterization and hydrotreating performance of supported tungsten phosphide catalysts

Supported tungsten phosphide catalysts were prepared by temperature-programmed reduction of their precursors (supported phospho-tungstate catalysts) in H₂ and characterized by X-ray diffraction (XRD), BET, temperature-programmed desorption of ammonia (NH₃-TPD) and X-ray photoelectron spectroscopy (XPS). The reduction-phosphiding processes of the precursors were investigated by thermogravimetry and differential thermal analysis (TG-DTA) and the suitable phosphiding temperatures were defined. The hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) activities of the catalysts were tested by using thiophene, pyridine, dibenzothiophene, carbazole and diesel oil as the feedstock. The TiO₂, γ-Al₂O₃ supports and the Ni, Co promoters could remarkably increase and stabilize active W species on the catalyst surface. A suitable amount of Ni (3%–5%), Co (5%–7%) and V (1%–3%) could increase dispersivity of the W species and the BET surface area of the WP/γ-Al₂O₃ catalyst. The WP/γ-Al₂O₃ catalyst possesses much higher thiophene HDS and carbazole HDN activities and the WP/TiO₂ catalyst has much higher dibenzothiophene (DBT) HDS and pyridine HDN activities. The Ni, Co and V can obviously promote the HDS activity and inhibit the HDN activity of the WP/γ-Al₂O₃ catalyst. The G-Ni5 catalyst possesses a much higher diesel oil HDS activity than the sulphided industrial NiW/γ-Al₂O₃ catalyst. In general, a support or promoter in the WP/γ-Al₂O₃ catalyst which can increase the amount and dispersivity of the active W species can promote its HDS and HDN activities.     

HDS工艺处理高酸高污染负荷型重金属废水

叙述了某公司采用HDS工艺处理高酸高污染负荷型重金属废水的半工业化实验,经该工艺处理后的废水可达标排放。     

Effect of sintering on the catalytic functionalities of MOS2/Al2O3 catalysts

Effect of sintering on physico-chemical and catalytic properties of Mo, Co-Mo, Ni-Mosupported on -Al₂O₃ is reported. Such effects on hydrodesulfurization (HDS), hydrogenation (HYD) and hydrodeoxygenation (HDO) are investigated as a function of sintering temperature. The results indicated that HDS and HYD have different optimum calcination temperatures and these functionalities originate from different sites. The results are discussed in the light of molybdenum sulfide dispersion, promotional effects and phase transformations of active component, promoters and support.     

The electronic structure of oxide-supported tungsten oxide catalysts as studied by UV spectroscopy

The UV spectra of tungsten oxide catalysts supported on alumina, titania and zirconia, and on titania–alumina and titania–zirconia mixed oxides are reported and discussed. Evidence is provided for the different electronic structure of supports and catalysts, which could affect the behavior of the tungsten oxide centres in the different cases. On alumina, tungsten oxide centres are “isolated” by the insulating support, while on titania-based materials they are likely in electronic contact with each other and with Ti centres through the support conduction band. In the case of WOx2013;ZrO₂, the 5d levels of tungsten ions fall just below of the lower energy limit of the support conduction band. This revised version was published online in July 2006 with corrections to the Cover Date.     

柠檬酸对WP催化剂噻吩加氢脱硫性能影响

以柠檬酸(CA)为助剂,采用共浸渍和程序升温还原的方法制备了不同n(CA)/n(WP)的WP催化剂。并用X射线衍射(XRD)、比表面积测定(BET)、扫描电镜(SEM)、热重(TG)分析等方法对催化剂进行了表征,通过高压微反评价了催化剂的噻吩加氢脱硫(HDS)性能。结果表明,柠檬酸并没有改变WP的本体结构,但具有阻止WP晶相颗粒生长的作用,并提高了WP催化剂的BET比表面积。加入柠檬酸改变了硝酸根的分解过程,降低了催化剂的起始磷化还原温度和磷化还原过程终结温度,有利于活性组分在催化剂表面的分散。柠檬酸对WP催化剂噻吩HDS反应有利。Cat-5催化剂具有相对最好的HDS活性,与不加柠檬酸的催化剂相比,其噻吩转化率提高近20.4%。     

Upgrading Siberian (Russia) crude oil by hydrodesulfurization in a slurry reactor: A kinetic study

Hydrodesulfurization (HDS) of sour crude oil is an effective way to address the corrosion problems in refineries, and is an economic way to process sour crude oil in an existing refinery built for sweet oil. In the current study, the HDS of Siberian crude oil was carried out in a slurry reactor. The Co–Mo, Ni–Mo, and Ni–W catalysts supported on γ-Al₂O₃ were compared at the temperature of 340 °C and the pressure of 4.5 MPa. The HDS activity follows the order of Co–Mo > Ni–Mo > Ni–W at a high concentration of H₂S, and the difference between Co–Mo and Ni–Mo becomes insignificant at a low concentration of H₂S. The influence of reaction temperature 320–360 °C and reaction pressure 3–5.5 MPa was investigated, and both play a positive role in the HDS reaction. A kinetic model over Ni–Mo/Al₂O₃ in the slurry reactor was established. The activation energy is estimated as 60.34 kJ·mol⁻¹; the orders of sulfur components and hydrogen partial pressure are 1.43 and 1.30, respectively. The kinetic parameters are compared with those in a trickle-bed reactor, implying that the mass transfer is greatly enhanced in the slurry reactor. The back mixing effect is present in the slurry reactor and can be reduced by a multi-stage design, which would lead to higher reactor efficiency in industrial application.     

New approach to unsupported ReS2 nanorod catalyst for upgrading of heavy crude oil using methane as hydrogen source

Highly active ReS₂ nanocatalysts were prepared by CVD method and characterized by XRD, BET -BJH, Raman spectroscopy, XPS, TPR, NH₃-TPD, SEM, and HRTEM techniques. Catalytic activities were used in upgrading heavy crude oil using methane as hydrogen source. The results showed a significant increase in API and decrease in sulfur and nitrogen content of crude oil. RSM technique was used to investigate the interactive effects of temperature (200–400 °C), pressure (20–40 bar) and dosage of nanocatalyst (0.5–2 wt. %) on the performance of HDS reaction. The results represent that the maximum predicted HDS activity (74.375%) was estimated under the optimal conditions (400 °C, 20 bars, and 2 wt % of nanocatalyst). Also, the effect of reaction temperature, pressure and dosage of ReS₂ nanorods catalyst on HDN of heavy crude oil was investigated and highest efficiency in the HDN process (93%) occurred at 400 °C and 40 bar using 2 wt % ReS₂.     

Nanometric bimetallic sulfides prepared via thermal decomposition of Ni and Fe heteropolymolybdate emulsions

NiMo and FeMo nanometric particles were prepared by thermal decomposition of water in oil emulsions, where the aqueous phase was a solution of iron or nickel heteropolymolybdates. Decomposition experiments were carried out at 573 K and 70 Bar of hydrogen, with carbon disulfide added to the emulsions. Solids were characterized by X ray diffraction, confocal microscopy and BET surface area. Thiophene hydrodesulfurization was performed in a continuous flow microreactor at 553 K and 1.0 Bar. Particles with diameters between 370 and 560 nm were obtained, and thiophene HDS was in the order NiMoS > MoS ≈ FeMoS > NiS > FeS. The feasibility of using thermal decomposition of emulsions to obtain nanometric bimetallic sulfides particles was shown.