Effect of mass transfer on the deactivation model and GPLE parameters of Co/γ-Al2O3 catalysts in the Fischer Tropsch synthesis

The activity of catalysts with various sizes was compared in a fixed-bed Fischer–Tropsch reactor under similar operating conditions by determining the deactivation model. Catalyst size had no impact on the type of deactivation model. The smaller catalyst showed a smaller deactivation constant of catalyst (k_d) and a lower deactivation rate in the initial stage. The decline in the activities of the catalyst with a mesh size of 40 was lower than the other catalysts, suggesting its higher long-term stability (a_ss). Larger catalyst sizes led to the fouling of carbon and heavy hydrocarbons, decreasing the specific surface of the catalyst, thus increasing the pore diffusion resistance and further decrementing the catalyst activities.     

日产NHR-90W型催化剂失活原因分析

对日产NHR -90W催化剂在抚顺石化分公司石油二厂 6万t/a石蜡加氢装置运行情况进行了研究 ,证明该催化剂活性较高 ,对原料的适应性也较强。同时 ,对造成催化剂短期内失活的原因进行了分析 ,认为原料中铁离子含量过高是造成催化剂失活的主要原因。对相关装置生产控制提出了建议     

Reaction scheme and kinetic modelling for the MTO process over a SAPO-18 catalyst

A kinetic model for simulation of the MTO process over SAPO-18 catalyst in a wide range of operating conditions has been proposed. The kinetic model predicts the experimental evolution of reaction products with time on stream, which follows three consecutive periods: initiation (where olefin production increases), a period of maximum olefin production and a period in which this production decreases. The kinetic scheme takes into account these three steps that evolve with time on stream: formation of active intermediate compounds, an step where olefins are formed by reaction of oxygenates (methanol/DME) with these intermediates and deactivation of intermediates by degradation to coke. The presence of water in the reaction medium attenuates the reaction rate of these steps. Discrimination of kinetic equations and calculation of the parameters of best fit have been carried out by solving the mass conservation equations of the individual components of the kinetic scheme together with the kinetic equation for deactivation and taking into account the effect of water on the kinetics of each step.     

Deactivation of V2O5-WO3-TiO2 SCR catalyst at a biomass-fired combined heat and power plant

The deactivation of a commercial type V₂O₅-WO₃-TiO₂ monolith catalyst under biomass combustion was studied at a full-scale grate-fired power plant burning straw/wood using a slip stream pilot scale reactor. The aerosols in the flue gas consisted of a mixture of potassium chloride and sulphate. Three catalyst elements were exposed at 350 °C, and one element was exposed at 250 °C for comparison. The catalyst activity was measured in the reactor at the exposure temperature by addition of NH₃ and extra NO. The activity, in terms of a first-order rate constant, dropped by 52% after about 1140 h indicating a very fast deactivation compared to coal firing. It was also found that the reactor temperature was not of importance for the deactivation rate. SEM-EDX analysis showed that particle deposition and pore blocking contributed to the deactivation by decreasing the diffusion rate of NO and NH₃ into the catalyst. However, potassium also penetrated into the catalyst wall and the resulting average K/V ratio in the catalyst structure was high enough (about 0.3–0.5) for a significant chemical deactivation. Chemisorption studies carried out in situ showed that the amount of chemisorbed NH₃ on the catalyst decreased as a function of exposure time, which reveals that Brøndsted acid sites had reacted with potassium compounds and thereby rendered inactive. When washed by 0.5 M H₂SO₄ the regenerated catalyst regains a higher activity than that of the fresh catalyst at temperatures higher than 300 °C, but even though reactivation is possible, the deactivation rate appears too high for practical use of the SCR process in straw combustion.     

Inhibiting and deactivating effects of water on the selective catalytic reduction of nitric oxide with ammonia over MnOx/Al2O3

The effect of water on the selective catalytic reduction (SCR) of nitric oxide with ammonia over alumina supported with 2–15 wt.-% manganese oxide was investigated in the temperature range 385–600 K, with the emphasis on the low side of this temperature window. Studies on the effect of 1–5 vol.-% water vapour on the SCR reaction rate and selectivity were combined with TPD experiments to reveal the influence of water on the adsorption of the single SCR reactants. It turned out that the activity decrease due to water addition can be divided into a reversible inhibition and an irreversible deactivation. Inhibition is caused by molecular adsorption of water. TPD studies showed that water can adsorb competitively with both ammonia and nitric oxide. Additional kinetic experiments revealed that adsorbed ammonia is present in excess on the catalyst surface, even in the presence of water. Reduced nitric oxide adsorption is responsible for the observed reversible decrease in the reaction rate; the fractional reaction order changes from 0.79 in the absence of water to 1.07 in its presence. Deactivation is probably due to the dissociative adsorption of water, resulting in the formation of additional surface hydroxyls. As the amount of surface hydroxyls formed is limited to a saturation level, the deactivating effect on the catalyst is limited too. The additional hydroxyls condense and desorb in the temperature range 525–775 K, resulting in a lower degree of deactivation at higher temperature. A high temperature treatment at 775 K results in a complete regeneration. The amount of surface hydroxyls formed per unit surface area decreases at increasing MnO_x-loading. The selectivity to the production of nitrogen is enhanced significantly by the presence of gas phase water.     

Formation of C4 species in the deactivation of a Pd/SiO2 catalyst during the selective hydrogenation of acetylene

The deactivation characteristics of Pd/SiO₂ in the selective hydrogenation of acetylene were correlated with changes in the amount of the C4 species produced. The amounts of butenes produced changed in parallel with the catalyst activity, indicating that the rate limiting step for butene production was the same as that for acetylene hydrogenation. On the other hand, the amount of 1,3-butadiene produced changed, showing a maximum with catalyst deactivation because 1,3-butadiene is an intermediate in the sequential reaction process which involves both the production and consumption of 1,3-butadiene. This was verified by a simultaneous TG/reaction experiment showing that 1,3-butadiene was a precursor of green oil. The catalyst showed a self-regenerative behavior in its activity and the amounts of C4 species produced during the early stage of deactivation because two opposite factors, which contributed to either the lowering or the promotion of activity, were involved in the process. A specific type of polymer species, produced during the initial period of deactivation, is proposed to be responsible for the promotion of catalyst activity.     

裂解汽油加氢一段催化剂失活原因分析

介绍了中国石油辽阳石化分公司烯烃厂裂解汽油加氢装置一段全馏分镍系加氢催化剂失活情况及原因分析。通过对酸性硫来源的分析及酸性硫对催化剂影响的评价，总结了处理酸性硫的对策及方法。     

ZSM-5型沸石催化剂的结焦与失活

本文对ZSM-5型沸石催化剂结焦与失活的关系进行了系统的评述.探讨了ZSM-5沸石的酸度和微孔结构对结焦过程的影响.     

Single and combined deactivating effect of alkali metals and HCl on commercial SCR catalysts

Two commercial SCR catalysts, with a nominal W content of about 9 wt.% and a V nominal content of 0.55 and 1.8 wt.%, respectively, were contacted with different amounts of Na and K and with HCl vapours in order to simulate poisoning by species more specifically contained in exhaust gases from MSW combustion. Catalysts were characterised using XRD analysis, SEM/EDX analysis, BET and pore size distribution measurements, NH₃ TPD, TG analysis. Poisoning agents do not cause loss of surface area nor pore occlusion. A significant loss of surface acidity was observed upon alkali metals poisoning whereas a decreasing of vanadium content was observed for the more concentrated catalysts upon HCl poisoning. Catalysts deactivation is proportional to the number of acid sites neutralised by alkali metals adsorbing ammonia in the temperature range typical of SCR process. HCl promotes the formation of new acid sites showing a lower activity compared to the original one.     

Catalytic wet air oxidation of olive mill wastewater

Au-based catalysts, known for ambient temperature CO oxidation, have to provide stable performance of up to 5000 h in order to be commercially applicable in automotive fuel cells. In this report, the on-line deactivation characteristics of Au/TiO₂ in unconventional PROX conditions are discussed. As opposed to CO removal from air, results in this report suggests that carbonates have a minor effect on deactivation of Au/TiO₂ in dry H₂-rich conditions. Also, no conclusive correlation between surface hydration and deactivation was observed. Rather, deactivation appeared to have occurred as a result of an intrinsic transformation in the oxidation state of the active species in the reducing operating conditions; a process which was reversible in an oxidizing atmosphere.