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31.
An isothermal model for hydrodemetallation (HDM) of crude oils in catalytic fixed-bed reactors is proposed. This model involves a consecutive reaction mechanism, which is capable of accounting for particle deposit profiles with interior maxima. Consistent with the fact that HDM catalysts are conglomerates formed by precipitation, the porous catalyst itself is modeled as randomly overlapping spheres of equal size. The metal is deposited as growing metal sulfide crystallites on the inner surface of the catalyst. These crystallites originate from a certain number of randomly scattered nuclei and increase in size as the deposition proceeds. The random sphere model for the catalyst and the deposit provides the changes in the catalyst pore structure—local porosity and surface area.
The mass transport within the domain of the particle is due to restricted liquid diffusion, since the diameter of the metal bearing compound (porphyrin) and the intermediate are comparable to the pore size. The diffusion restrictions taken into account are the enhanced drag imposed on a molecule by adjacent pore walls and steric partitioning.
Since the deposition process is much slower than diffusion and reaction, the pseudo-steady-state assumption can be justified. The equations of conservation for mass are solved by orthogonal collocation on finite elements. Based on this solution technique a computer simulation program of HDM is designed that allows two modes of operation: constant temperature and constant conversion. The simulation program “SIMULA” is highly flexible with regard to reaction kinetics, catalyst structure, reactor design, and operating conditions. In comparison to a base case with uniform activity, the effect of intraparticle (radial) and bed (axial) activity profiles on the conversion rate is discussed. For the case investigated, a radial distribution of activity higher at the center of the particle than at the edge can increase catalyst life by 25%, but axial distribution was less successful. 相似文献
The mass transport within the domain of the particle is due to restricted liquid diffusion, since the diameter of the metal bearing compound (porphyrin) and the intermediate are comparable to the pore size. The diffusion restrictions taken into account are the enhanced drag imposed on a molecule by adjacent pore walls and steric partitioning.
Since the deposition process is much slower than diffusion and reaction, the pseudo-steady-state assumption can be justified. The equations of conservation for mass are solved by orthogonal collocation on finite elements. Based on this solution technique a computer simulation program of HDM is designed that allows two modes of operation: constant temperature and constant conversion. The simulation program “SIMULA” is highly flexible with regard to reaction kinetics, catalyst structure, reactor design, and operating conditions. In comparison to a base case with uniform activity, the effect of intraparticle (radial) and bed (axial) activity profiles on the conversion rate is discussed. For the case investigated, a radial distribution of activity higher at the center of the particle than at the edge can increase catalyst life by 25%, but axial distribution was less successful. 相似文献
32.
Yu-Hang Yuan Xing-Gui Zhou Wei Wu Yi-Ran Zhang Wei-Kang Yuan Lingai Luo 《Catalysis Today》2005,105(3-4):544-2
Gas phase propylene epoxidation on gold catalysts has attracted wide attention from industry and academia due to its high selectivity. However, it suffers from low propylene conversion and rapid catalyst deactivation. Experiments showed that propylene conversion could be increased by raising H2, O2, or C3H6 concentration in the feed, but the feed compositions were within the explosion limit. It was also shown that the activity of the used catalyst could be fully recovered, but the regeneration temperature was 280 °C, much higher than that for reaction. Therefore a microchannel reactor was devised to suppress explosion and was constructed with Fecralloy, to raise the temperature rapidly for catalyst regeneration by electric heating. In two minutes the temperature of the reactor could be raised from 50 to 300 °C. Catalysts were coated on the alloy belt by dip coating, and the performance of the reactor was evaluated under different operating conditions. Results showed that in the microreactor the overall reaction rate was controlled mainly by the intrinsic reaction rate, and also influenced by film diffusion to a certain extent. The deactivated catalyst was regenerated in the microchannel reactor and the activity was fully recovered. 相似文献
33.
浅谈国内外钒催化剂的质量差异 总被引:2,自引:0,他引:2
从化学组分、强度、活性、物相结构、孔容积及孔径分布等方面,对国产S101-2H、S108-1H钒催化剂和进口LP120、LP110钒催化剂进行剖析、对比。结果表明,国产催化剂强度比进口催化剂低30%左右;国产催化剂测定活性与进口催化剂相近,但实际使用活性明显劣于进口催化剂;进口催化剂载体中存在方英石、硫酸铝钾相,而国产催化剂没有;进口催化剂孔径分布较宽,主要孔径分布在0.50~1.50μm,而国产催化剂孔径分布较窄,主要孔径分布在0.060~0.30μm,不利于反应气体在催化剂内部的扩散。鉴此,建议采用高温煅烧载体,降低其有机物含量;优化配方,填加无机粘结剂;改进成型设备等措施,提高催化剂的强度和活性。 相似文献
34.
Biodiesel was produced by transesterification of soybean oil with methanol using ZnO loaded with KF as a solid base catalyst.
It was found that the catalyst with 15 wt.% KF loading and calcined at 873 K showed the optimum activity. XRD, IR and Hammett
indicator method were employed for the catalyst characterization. The results showed the activity of the catalysts was correlated
with their basicity. The influence of various reaction variables on the conversion was also discussed. 相似文献
35.
The stereoselective hydrogenation of thymol was studied in liquid phase over several nickel catalysts, modified by coimpregnation of inorganic compounds containing chlorine. The total activity of all catalysts studied was decreased and was on the same order of magnitude, indicating that chlorine even after reduction remains on the surface and is responsible for the poisoning effects. Such blocking of accessible sites results in similar reaction rates for the catalysts studied. Selectivity and stereoselectivity to menthols and menthones changed significantly. The modifiers could influence the rate of keto-enol transformations, which is thought to be the key selectivity and stereoselectivity governing step. 相似文献
36.
The influence has been studied of the partial pressure of hydrogen (0–30 kPa) upon the coking rate of a Cr2O3/Al2O3 commercial catalyst during 1-butene dehydrogenation. Coke deposition has been analysed using a monolayer-multilayer reversible coke growth model (MMRC model). This model provides good fits to the experimental data, within the range of partial pressure of H2 studied, and allows us to estimate the main kinetic parameters involved in the coking-deactivation process. The results obtained reveal a dual effect of hydrogen: competition against 1-butene for the active sites and the removal of coke precursors from the catalyst surface. Bom effects diminish the coking rate as the H2 partial pressure is increased. 相似文献
37.
38.
我国二氧化硫氧化制硫酸的钒催化剂现状和展望 总被引:2,自引:0,他引:2
陈学梅 《硫磷设计与粉体工程》2004,(4):12-16
从钒催化剂的生产、市场、开发、质量等方面分析我国二氧化硫氧化制硫酸催化剂的现状,指出我国钒催化剂与国外产品存在的差距和原因,提出发展钒催化剂的对策。 相似文献
39.
40.
A kinetic study for the one-step conversion of synthesis gas to gasoline on a ZnO–Cr2O3–ZSM-5 catalyst is described. On this catalyst, three reactions are involved in the overall transformation of synthesis gas: the methanol synthesis, the conversion of methanol to hydrocarbons and the water–gas shift reaction. Under the operating conditions selected for the study, it was found that the water–gas shift was at equilibrium and the methanol was completely converted to hydrocarbons. Consequently, it was postulated that the kinetics of the limiting reaction step, the methanol synthesis on the ZnO–Cr2O3 component, was the one that controls the overall reaction rate. Three kinetic model equations describing the rate of synthesis gas conversion on the bifunctional catalyst, were considered to fit the data of the experimental runs performed in a Berty well-mixed reactor. Those equations were derived under very special conditions where the methanol decomposition term could be neglected. It was also observed that in the kinetic equations a term involving the fugacity of CO2 was required to predict the rate properly. The catalyst deactivation was also taken into account in the analysis. 相似文献