Residue catalysts catalytic coke

The structure of the hydrocarbons produced can be modified by the use of catalyst. Catalytic cracking consumes less energy than the noncatalytic process and results in formation of more branch-chain hydrocarbons. On the other hand the addition of the catalyst can be troublesome, and the catalyst accumulates in the residue or coke. There are two ways to contact the melted polymer and catalysts the polymer and catalyst can be mixed first, then melted, or the molten plastics can be fed continuously over a fluidized catalyst bed. The usually employed catalysts are US-Y, and H-ZSM-5. Catalyst activity and product structure have been reported [7-11]. It was found that the H-ZSM-5 and ECC catalysts provided the best possibility to yield hydrocarbons in the boiling range of gasoline. 

Crude residual components (called resid) contain metals such as nickel and vanadium. These metals, especially the nickel, accumulate on the cracking plant zeolite catalyst. The nickel promotes hydrothermal reactions in the FCCU (or "Cat"). Such reactions preferentially produce low-value fuel gas and catalytic coke, consequently reducing the production of more valuable diesel oil and gasoline. Flence, black gas oil downgrades a refinery s ability to produce motor fuels. 

Another approach used to reduce the harmful effects of heavy metals in petroleum residues is metal passivation. In this process an oil-soluble treating agent containing antimony is used that deposits on the catalyst surface in competition with contaminant metals, thus reducing the catalytic activity of these metals in promoting coke and gas formation. Metal passivation is especially important in fluid catalytic cracking (FCC) processes. Additives that improve FCC processes were found to increase catalyst life and improve the yield and quality of products. ... 

Coking is a severe thermal cracking process designed to handle heavy residues with high asphaltene and metal contents. These residues cannot be fed to catalytic cracking units because their impurities deactivate and poison the catalysts. 

Coke is a hydrogen deficient residue left on the catalyst as a by-product of catalytic reactions. 

Stanislaus, A., Absi-Halabi, M., Khan, Z., Influence of Catalyst Pore Size on Asphaltenes Conversion and Coke-Like Sediments Formation During Catalytic Hydrocracking of Kuwait Vacuum Residues, In Catalysts in Petroleum Refining and Petrochemical Industries. Studies in Surface Science and Catalysis. 1996, Elsevier New York, USA. pp. 189-197. 

Petroleum coke is the residue left by the destructive distillation (thermal cracking or coking) of petroleum residua. The coke formed in catalytic cracking operations is usually nonrecoverable because of adherence to the catalyst, as it is often employed as fuel for the process. The composition of coke varies with the source of the crude oil, but in general, is insoluble on organic solvents and has a honeycomb-type appearance. 

The zeolite to matrix surface area ratio can be used for optimization of catalysts for catalytic cracking of atmospheric residues. For North Sea long residues this ratio should be as large as possible, but the ratio should not exceed an upper limit. For the main catalyst type (A) used in this investigation the upper limit of the ZSA/ MSA ratio was around 3.5. There is also a lower limit for the matrix surface area. If the matrix surface area is lower than this limit, the catalyst will not be able to crack all the heavy components in the residue feed, and the coke on the matrix will increase dramatically. This will prevent the catalyst from working properly. Different type of catalysts must be optimized individually, as well as different type of long residues. 

Catalytic activity, assessed by cumene cracking on separated fractions and also by analysis of residual coke on catalyst fractions, shows a sharp decline with increasing density (age). This rapid loss of initial activity coincides with zeolite dealumination which is largely completed as a slow rate of zeolite destruction is established. Subsequent loss of crystallinity has little additional effect on activity. The associated loss of microporosity leads to an apparent increase in skeletal density with increasing age. 

Carbon and metal sulfide deposits are the two main causes of deactivation of residue hydrodemetallization (HDM) catalysts. During a catalytic test, the metals contained in the feed (Ni, V) are slowly deposited on the catalyst surface leading to the build up of large particles of metal sulfides which ultimately plug the catalyst pores. Carbon, on the other hand, is known to accumulate quickly on the catalyst surface within the first days of a run until a steady state is reached (1-20). At the beginning of a run, a strong deactivation of the residue HDM catalyst rapidly occurs to which both types of deposits may contribute. However at the present time it is not clear whether this initial deactivation is mainly due to coke or metal sulfide deposits. 

The deactivation of catalysts, especially zeolites, during cracking, hydrocracking, methanol conversion, etc, is one of the major technological and economic problems of the chemical industry (1). The interest of these materials lies not only in their high catalytic activity and selectivity but also in the possibility of regenerating them several times so that their Lifetime" is compatible with the cost of their production. Consequently, it is necessary to understand the manner and the rate of catalyst deactivation as well as the nature of the carbonaceous residues formed, commonly called coke". 

Coking, widely experienced in the catalysis of hydrocarbon conversion (7), can deactivate both metallic and acid catalytic sites for hydrocarbon reactions (2). Accumulation of such carbonaceous deposits affects selectivity in hydrocarbon conversion (5). Adsorbed ethene even inhibits facile o-p-Hj conversion over Ni or Pt (4 ), the surface of which it appears is very nearly covered at lower temperatures in such deposits. H spillover may enhance hydrocarbonaceous residue formation (6). Accumulated carbonaceous residues can be removed by temperature programmed oxidation, reduction and hydrogenation TPO, TPR, TPH, etc (7) as part of catalyst regeneration. 

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