Zeolite catalyst deactivation

Modeling Zeolite Catalyst Deactivation by Coking and Nitrogen Compound Poisoning... 

The zeolite catalysts deactivate very fast during the isobutane alkylation with C4 olefins due to coke deposition. This coke requires very high temperature and long times to be fully eliminated in air. However, the regeneration in ozone can be carried out at low temperatures. 

Guillemot M, Mijoin J, Mignard S, Magnoux P. Mode of Zeolite Catalysts Deactivation Dnring Chlorinated VOCs Oxidation. A/ / / Catal A Gen 2007 327 211-217. 

A good catalyst is also stable. It must not deactivate at the high temperature levels (1300 to 1400°F) experienced in regenerators. It must also be resistant to contamination. While all catalysts are subject to contamination by certain metals, such as nickel, vanadium, and iron in extremely minute amounts, some are affected much more than others. While metal contaminants deactivate the catalyst slightly, this is not serious. The really important effect of the metals is that they destroy a catalyst s selectivity. The hydrogen and coke yields go up very rapidly, and the gasoline yield goes down. While Zeolite catalysts are not as sensitive to metals as 3A catalysts, they are more sensitive to the carbon level on the catalyst than 3A. Since all commercial catalysts are contaminated to some extent, it has been necessary to set up a measure that will reflect just how badly they are contaminated. 

Deactivation of zeolite catalysts occurs due to coke formation and to poisoning by heavy metals. In general, there are two types of catalyst deactivation that occur in a FCC system, reversible and irreversible. Reversible deactivation occurs due to coke deposition. This is reversed by burning coke in the regenerator. Irreversible deactivation results as a combination of four separate but interrelated mechanisms zeolite dealu-mination, zeolite decomposition, matrix surface collapse, and contamination by metals such as vanadium and sodium. 

Figure 1 shows tire relationship betweai CHO conversion, CL selectivity and process time (time on str m) over TS-ls with different Si/11 ratio and SSZ-41, The result over ZSM-5 (Si/Al ratio=90) is also represented in Figure 1. The CHO conversion decreases with process time, whereas the CL selectivity is almost constant during the process time. The deactivation of SSZ-31 is largest among toe zeolites. The CL selectivity over SSZ-31 is lowest among the zeolites. The catalyst dractivation of TS-1(45) is larpr than fliat of TS-1(200). These results suggest that the acidity and micro pesre size of the zeolite siraultaiKously affected the catalyst deactivation.

The desulfurization process reported by the authors was a hybrid process, with a biooxidation step followed by a FCC step. The desulfurization apparently occurs in the second step. Thus, the process seems of no value, since it does not remove sulfur prior to the FCC step, but only oxidizes it to sulfoxides, sulfones, or sulfonic acids. The benefit of such an approach is not clearly outlined. The benefit of sulfur conversion can be realized only after its removal, and not via a partial oxidation. Most of the hydrotreatment is carried out prior to the FCC units, partially due to the detrimental effect that sulfur compounds exert on the cracking catalyst. It is widely accepted that the presence of sulfur, during the regeneration stage of the FCC units, causes catalyst deactivation associated with zeolite decay. In general terms, the subject matter of this document has apparent drawbacks. 

Catalytic oxidative dehydrogenation of propane by N20 (ODHP) over Fe-zeolite catalysts represents a potential process for simultaneous functionalization of propane and utilization of N20 waste as an environmentally harmful gas. The assumed structure of highly active Fe-species is presented by iron ions balanced by negative framework charge, mostly populated at low Fe loadings. These isolated Fe sites are able to stabilize the atomic oxygen and prevent its recombination to a molecular form, and facilitate its transfer to a paraffin molecule [1], A major drawback of iron zeolites in ODHP with N20 is their deactivation by accumulated coke, leading to a rapid decrease of the propylene yield. 

Initial activity (TOF) was measured on fresh catalysts and EB conversion was also followed with time on stream (table 1). ZSM-5 zeolite catalyst is respectively 40, 25 and 2 times initially more active for the EB conversion than the Ferrierite, ZSM-22 and EU-1 catalysts (table 1). Except for ZSM-5, high deactivation occurs on zeolite catalysts as shown by EB conversion drop at different contact time (table 1). 

On ferrierite, ZSM-22 and EU-1 zeolite catalysts, 10MR monodimensional zeolite structures (ID), the main reaction is the isomerization of ethylbenzene (figure la). ZSM-5, 10MR three-dimensional structure (3D) zeolite is very selective in dealkylation (90%) (figure lb) and no deactivation was observed within 8 hours of reaction. This particular selectivity of the zeolite ZSM-5 can be partly explained by the presence of strong acid sites and its porous structure that on one hand promotes the containment of molecules in the pores (presence of 8-9A cages at the intersection of channels) and on the other hand prevents the formation of coke and therefore pore blockage. 

Home, P.A., Williams, P.T., The effect of zeolite ZSM-5 catalyst deactivation during the upgrading of biomass-derived pyrolysis vapours, J. Anal. Appl. Pyrolysis, 1995, 34, 65. 

Gayubo, A.G., Aguayo, A.T., Atutxa, A., Prieto, R., Bilbao, J., Deactivation of a HZSM-5 zeolite catalyst in the transformation of the aqueous fraction of biomass pyrolysis oil into hydrocarbons, Energy Fuels, 2004, 18, 1640. 

Moreover, the catalyst deactivation must also be considered in order to use these solid materials in industrial processes. Figure 13.8 shows the variation of catal54ic activity (2-butene conversion) with the time on stream obtained under the same reaction conditions on different solid-acid catalysts. It can be seen how all the solid-acids catalysts studied generally suffer a relatively rapid catalyst deactivation, although both beta zeolite and nafion-sihca presented the lower catalyst decays. Since the regeneration of beta zeolite is more easy than of nafion, beta zeolite was considered to be an interesting alternative. ... 

For a zeohtic catalyst where Pt, Pd or other transition metal might be present to provide metal activity, STEM can be used to determine whether the metal is agglomerated and to what extent, whether the metal is in the zeolite or present on the geometric exterior or whether the metal is associated with the zeolite or binder. As an example of the utility of the technique. Figure 4.15 shows the growth of Pt clusters for fresh and spent faujasite zeolite catalyst. After time under reaction conditions, the Pt clusters have grown from Inm to 2nm. The clusters have remained in the channels of the faujasite. Pt agglomeration can be concluded as the deactivation mechanism. 

D.Y. (2006) Isomerization of n-butane to isobutane over Pt-modified beta and ZSM-5 zeolite catalyst catalyst deactivation and regeneration. Chem. Eng. ]., 120, 83-89. 

ECC catalyst is subject to hydrothermal deactivation. This occurs when the A1 atom in the zeolitic cage is removed in the presence of water vapor and temperature. The result is a loss of activity and unit conversion. The effect of temperature on this process is nonlinear. The deactivation rate increases exponentially with temperature. Units that experience high afterburn have attributed high rates of catalyst deactivation on the higher dilute phase temperatures. This phenomenon is more apparent on units with high combustion air superficial velocities. The high velocity not only increases afterburn, but also increases catalyst entrainment to the cyclones and dilute area. COP is used to decrease afterburn and minimize catalyst deactivation. 

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