Residue catalysts coke distribution

The surface area of the catalyst as well as the pore size distribution can easily be measured, and the zeolite and matrix surface areas of the catalyst can be determined by the t-plot method. The different FCC yields can then be plotted as a function of the ZSA/MSA ratio, zeolite surface area or matrix surface area, and valuable information can be obtained [9], The original recommendation was that a residue catalyst should have a large active matrix surface area and a moderate zeolite surface area [10,11]. This recommendation should be compared with the corresponding recommendation for a VGO catalyst a VGO catalyst should have a low-matrix surface area in order to improve the coke selectivity and allow efficient stripping of the carbons from the catalyst [12], Besides precracking the large molecules in the feed, the matrix also must maintain the metal resistance of the catalyst. 

About 1.2-1.4% Acoke forms on residue catalysts compared with about 0.7- 0.8% on gasoline catalysts. The distribution of Acoke for both types of feed is shown in Table 5.12. Most of the increase is associated with contaminant and feed coke. 

Example 11.15 Coke formation is a major cause of catalyst deactivation. Decoking is accomplished by periodic oxidations in air. Consider a micro-porous catalyst that has its internal surface covered with a uniform layer of coke. Suppose that the decoking reaction is stopped short of completion. What is the distribution of residual coke under the following circumstances ... 

The FCC process is used worldwide in more than 300 installations, of which about 175 are in North America and 70 in Europe. Figure 9.10 shows the principle of an FCC unit. The preheated heavy feed (flash distillate and residue) is injected at the bottom of the riser reactor and mixed with the catalyst, which comes from the regeneration section. Table 9.5 gives a typical product distribution for the FCC process. Cracking occurs in the entrained-flow riser reactor, where hydrocarbons and catalyst have a typical residence time of a few seconds only. This, however, is long enough for the catalyst to become entirely covered by coke. While the products leave the reactor at the top, the catalyst flows into the regeneration section, where the coke is burned off in air at 1000 K. 

S. Stapf, X. Ren, E. Talnishnikh, B. Bliimich 2005, (Spatial distribution of coke residues in porous catalyst pellets analyzed by field-cycling relaxometry and parameter imaging), Magn. Reson. Imag. 23, 383. 

Another coke formed in a FCC unit is occluded or residual coke. In a commercial unit this coke corresponds to coke formed on catalyst porosity and its content depends on textural properties of the catalyst (pore volume and pore size distribution) and the stripping system capacity in the reaction section. Finally on the FCC catalyst rests some high-molecular weight of nonvaporized hydrocarbons. These molecules do not vaporize or react at the reactor conditions and accumulate in the catalyst pores like a soft carbonaceous residue with high hydrogen content. 

Those deactivation models accounting for both coke and metal sulfides are rather simple. Coke and metals foul residue hydrodesulfurization catalysts simultaneously via different processes, and decrease both intrinsic reaction rate and effective diffusivity. They never uniformly distribute in the commercial reactors. We have examined the activity and diffusivity of the aged and regenerated catalysts which were used at the different conditions as well as during the different periods. This paper describes the effects of vacuum residue conversion, reactor position, and time on-stream on the catalyst deactivation. Two mechanisms of the catalyst deactivation, depending on residue conversion level and reactor position, are also proposed. 

Analyzing the self-diffusion behavior of guest molecules in a microporous catalyst by the combined application of pulsed-field gradient NMR selfdiffusion techniques reveals the spatial distribution of transport resistances over the catalyst particles. In the case of coke deposits on ZSM-5, the distribution of carbonaceous residues over the crystal was found to be a function of the crystal morphology, the time onstream, and the chemical nature of the coke-producing reactant. In the case of ZSM-5 modified by H3PO4, the spatial distribution of the P compounds over the ZSM-5 crystals can be determined by self-diffusion measurements. Location of transport hindrances in a zeolite framework is based on self-diffusion measurements, in... 

CFD Model Eulerian-Eulerian approaeh, Two fliiid (emulsion-bubble) model, uses kinetic parameters and effective bubble size as input parameters, reactions ill emulsion phase Flow ami temperature field, Residual coke on catalyst particles. Composition distribution of gas phase =>Re-engineering of gas, distributor, Entry nozzle of spent catalyst... 

All listed TPO spectra show three CO2 peaks (Pi, P2 and P3), while two CO peaks (P4 and P5) are Ccilculated for the spent and cyclohexene coked catalysts, but only P4 is apparent for the 1-hexene coked catalyst. When present, P5 only represents 5 - 10% of the total carbon associated with CO formation and the error in the calculated rate parameters for this peak is large. Care is also required in the interpretation of P3 rate parameters because this is associated with the last 30 - 50 % of the deposited carbon. For this residual coke the structure may have collapsed and a broad distribution of rate parameters are likely. Also at higher heating rates (10 °C/min) this peak becomes very large and oxygen depletion may become rate controlling. 

Effective solutions to the problems of the vacuum residue hydrodesulfurization unit equipped with the fixed bed reactors, such as a hot spot, pressure-drop buildup, and catalyst deactivation by coke fouling, were discussed. Improving liquid distribution can prevent hot spot occurrence. Dispersing inorganic solids throughout the reactors can control a pressure-drop increase in the first bed. For a high conversion operation, controlling the conversion in each bed can minimize the coke deactivation in the fourth bed. 

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