Hydroprocessing catalysts based on Ni, Co, Mo and W are used in various refinery processing applications where several deactivation mechanisms become of importance (coke formation, active phase sintering, metals deposition, poisoning) in the catalyst's life cycle. The life cycle of commercial hydroprocessing catalysts is very complex and includes the catalyst production, sulfidation, use, oxidative regeneration followed by re-sulfidation and reuse or, if reuse is not possible, recycling or disposal. To understand the changes in catalyst properties taking place during a life cycle, the catalyst quality in the different stages can be best monitored by using advanced analytical techniques. The catalyst's life cycle is further complicated by numerous technical, environmental and organizational issues involved. In principle, different companies can be involved in each of the life cycle steps. Leading catalyst manufacturers, together with specialized firms, offer refineries a total catalyst management concept, starting with the purchase of the fresh catalyst and ending with its final recycling or disposal. Total catalyst management includes a broad range of services, ensuring optimal timing during the change-out process, reliable, smooth and safe operations, minimal downtime and maximum catalyst and unit performance. 相似文献
Catalytic hydrolysis of NaBH4 and NH3BH3 has been studied. It was shown that the nature of the support and the active component of the catalyst affect the H2 generation rate. Despite similar sizes of rhodium particles formed on the surface of different supports (γ-Al2O3, TiO2, carbon), their reactivity is different. Rh/TiO2 with low rhodium concentration (1 wt.%) is the most active catalyst both in the hydrolysis of NaBH4 and NH3BH3. The obtained results show that the rhodium chloride interaction with titania determines the reactivity of rhodium particles formed under action of NaBH4 medium. TEM, DRS UV–vis and XPS were used to characterize the catalysts. 相似文献
Carbon black composites (CBCs) have been prepared by pyrolyzing mixture of a carbon black with polyfurfuryl alcohol and then pretreated by oxidation with nitric acid, gasification with water steam or ammoxidation. The effects of the chemical character of the carrier surface, nature of the active metal phase and pH value of the impregnation solution on the catalytic activity towards the hydrodesulfurization (HDS) of thiophene of the CBC supported Mo (Co) catalysts were determined. It was stated that the catalytic properties of the CBC supported sulfides of Mo or Co and of Mo carbides are affected by the chemical character of the carrier surface. Generally, catalysts supported over basic surface CBC exhibit higher activity than those ones supported over CBC possessing acidic surface character. Co catalysts supported on acidic surface show lower activity (per mol of active metal) than Mo based ones supported on the same carrier. In the case of catalysts supported on basic CBC, Co exhibits distinctly higher activity than Mo. At the experimental conditions adopted for this study, CBC surface properties, active phase nature, and catalyst impregnation pH were found to exert a relatively small influence on both HDS and hydrogenation activities. 相似文献
The liquid-phase hydrodechlorination of 3-chloropyridine and chlorobenzene has been studied over alkali-modified zirconia-supported palladium catalysts. The modification of the ZrO2 with alkali metal carbonates improves the catalytic activity of the final palladium catalyst. Therefore, the larger the ionic radii (Li+ < Na+ < K+), the greater the catalytic activity (TOF) of the palladium catalyst. For 3-chloropyridine, hydrodechlorination proceeds without catalyst deactivation. This is explained as the result of the interaction of reaction products (pyridine and HCl) forming pyridinium chloride, thus avoiding the detrimental effect of HCl on the palladium particles. Catalytic hydrodechlorination of chlorobenzene over Pd catalysts exhibits an initial catalytic activity (TOF) much lower than that of 3-chloropyridine and the Pd catalysts deactivate as the reaction proceeds. Finally, chlorobenzene hydrodehalogenation has also been carried out in the presence of an equimolecular amount of pyridine resulting in a decrease in the initial reaction rate on the one hand, but also in an increase in final conversion on the other. 相似文献
In the design process of the photocatalytic oxidation (PCO) reactor using TiO2-coated foam nickels, the optimum of catalyst film thickness, light intensity and flow velocity were considered. A model was developed to study the effect of catalyst film thickness on photocatalytic degradation of formaldehyde by a TiO2-coated foam nickel at continuous flow mode. In this model, external mass transfer and internal molecule diffusion-reaction were considered. A first-order kinetics equation was used to account for the photocatalytic reaction. Two exponential equations were employed to describe the distribution of light intensities in foam nickels and catalyst films, respectively. Validated with experimental data, the model can be used to predict the optimal thickness of catalyst films. A method for determining appropriate light intensities was proposed and discussed. The appropriate light intensity can be obtained by giving a margin, regarded as an excess coefficient, to the light intensity calculated based on the assumption of complete use of excited electron–hole pairs. The excess coefficient needs to be determined experimentally. In addition, the optimal flow velocity of PCO reactors could be consistent with the required one by changing the windward area of foam nickels. Based on the theoretical analyses, a novel PCO reactor containing 15 parallel-connected cells was designed. Each reaction cell was composed of an UV lamp and a TiO2-coated tubular foam nickel. The performance of the reactor was tested by degrading gaseous formaldehyde at an indoor concentration level. The results showed that the reactor had low pressure loss and good degradation capability. 相似文献
A promising catalytic system for the low temperature oxidation of methane to a methanol derivative has been investigated under both batch and semi-continuous operation in two different reactor types. The system comprises of a bimetallic palladium and copper(II) chloride catalyst contained in a trifluoroacetic acid (TFA) and an aqueous phase. Methane, oxygen and a co-reductant carbon monoxide constitute the gas phase. Typical operating conditions were a temperature of 85 °C and a pressure of 83 bar.
The yields of the methyl trifluoroacetate product observed in this present work were less than those obtained in other batch autoclave works, which employed only 4 ml of liquid phase, compared with 50 ml in this study. Furthermore, an encouraging initial product formation rate of ca. 40 mol/m3 h, quickly decreased after the first hour, and came to an apparent end after only 2 h. This observation had not been reported previously.
Work performed in a semi-continuous porous tube reactor (300 ml of re-circulating liquid phase) also showed the same reaction characteristics as in the batch reactor. Thus, the deteriorating product formation rate cannot be attributed to gaseous reactant depletion (batch operation). The results suggest problems associated with catalyst instabilities, e.g. with the previously elucidated Wacker chemistry. 相似文献
The paper reports the results of on-site regeneration catalytic bed of the natural gas reformer in a 5 kW PEM fuel cell system. The Ni catalyst previously poisoned by sulphur from the available natural gas, could be re-activated by injection of pure water steam, following the method developed for industrial reformers using the same metal catalyst: this method was shown to be perfectly efficient, provided no natural gas was fed during the operation. Results of the tests conducted are presented and discussed in relation to published data on S-sorption on Ni surfaces. 相似文献