Formation of coke

The visbreaking process thermally cracks atmospheric or vacuum residues. Conversion is limited by specifications for marine or Industrial fuel-oil stability and by the formation of coke deposits in equipment such as heaters and exchangers. 

Metal oxides, sulfides, and hydrides form a transition between acid/base and metal catalysts. They catalyze hydrogenation/dehydro-genation as well as many of the reactions catalyzed by acids, such as cracking and isomerization. Their oxidation activity is related to the possibility of two valence states which allow oxygen to be released and reabsorbed alternately. Common examples are oxides of cobalt, iron, zinc, and chromium and hydrides of precious metals that can release hydrogen readily. Sulfide catalysts are more resistant than metals to the formation of coke deposits and to poisoning by sulfur compounds their main application is in hydrodesulfurization. 

The operating conditions of the unit, particularly during startups and feed interruptions, will have a large influence on the formation of coke. Coke normally grows wherever there is a cold spot in the reactor system. When the temperature of the metal surfaces in the reactor... 

Some deactivation processes are reversible. Deactivation by physical adsorption occurs whenever there is a gas-phase impurity that is below its critical point. It can be reversed by eliminating the impurity from the feed stream. This form of deactivation is better modeled using a site-competition model that includes the impurities—e.g., any of Equations (10.18)-(10.21)— rather than using the effectiveness factor. Water may be included in the reaction mixture so that the water-gas shift reaction will minimize the formation of coke. Off-line decoking can be... 

The stability of catalyst is one of the most important criteria to evaluate its quality. The influence of time on stream on the conversion of n-heptane at SSO C is shown in Fig. 5. The conversion of n-heptane decreases faster on HYl than on FIYs with time, so the question is Could the formation of coke on the catalyst inhibit diffusion of reactant into the caves and pores of zeolite and decrease the conversion According to Hollander [8], coke was mainly formed at the beginning of the reaction, and the reaction time did not affect the yield of coke. Hence, this decrease might be caused by some impurities introduced during the catalyst synthesis. These impurities could be sintered and cover active sites to make the conversion of n-heptane on HYl decrease faster. 

To probe the formation of coke we conducted TPO measurements on samples previously used in the butene TPD experiments. The TPO profiles corresponding to catalyst INiSZ(s) are shown in Fig. 6. Significant evolution of CO2 was detected, indicating the formation of coke during the adsorption/desorption of 1-butene. The INiSZ(s) catalyst exhibited almost twice as much CO2 as the unpromoted SZ sample. 

The two limiting cases for the distribution of deactivated catalyst sites are representative of some of the situations that can be encountered in industrial practice. The formation of coke deposits on some relatively inactive cracking catalysts would be expected to occur uniformly throughout the catalyst pore structure. In other situations the coke may deposit as a peripheral shell that thickens with time on-stream. Poisoning by trace constituents of the feed stream often falls in the pore-mouth category. 

Extensive catalyst poisoning results from the deposition of carbon in or on the catalyst surface. In technological parlance, this is usually referred to as the formation of coke. At temperatures in excess of those normally used for catalysis, hydrocarbon decomposition at metal surfaces is known... 

Pore size optimization is one area where developmental efforts have been focused. Unimodal pore (NiMo) catalysts were found highly active for asphaltene conversion from resids but a large formation of coke-like sediments. Meanwhile, a macroporous catalyst showed lower activity but almost no sediments. The decrease of pore size increases the molecular weight of the asphaltenes in the hydrocracked product. An effective catalyst for VR is that for which average pores size and pore size distribution, and active phase distribution have been optimized. Therefore, the pore size distribution must be wide and contain predominantly meso-pores, but along with some micro- and macro-pores. However, the asphaltene conversion phase has to be localized in the larger pores to avoid sediment formation [134],... 

Effect of time on stream on oxime conversion and product selectivity was studied over CeMAPO-36 at 200 °C and 4.4 h"1 WHSV. The results are depicted in Fig. 5. Although the conversion decreased with increase of time on stream, the decrease was only 7% for 6 h time on stream. This observation elucidates that the reaction occurs over Lewis acid sites particularly the formation of coke. In addition, higher WHSV (4.4 h 1) is also the main cause for suppression of coke formation. The yield of caprolactum decreased with increase in time on stream. The selectivity of caprolactum did not show... 

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. 

A naphthene is used for this illustration as we believe that the relative amounts of naphthene cracking versus hydrogen transfer control product distributions and qualities in octane catalyst systems. Gasoline selective catalysts favor hydrogen transfer reactions with these molecules with consequent formation of coke. 

The addition of oxygen as air leads to an increase in the H2 yield through an increase in the conversion of glycerol to gaseous products. Moreover, it inhibits the formation of coke precursor. 

Although the stoichiometry for reaction (9.1) suggests that one only needs 1 mol of water per mole of methane, excess steam must be used to favor the chemical equilibrium and reduce the formation of coke. Steam-to-carbon ratios of 2.5-3 are typical for natural gas feed. Carbon and soot formation in the combustion zone is an undesired reaction which leads to coke deposition on downstream tubes, causing equipment damage, pressure losses and heat transfer problems [21]. 

The first reaction is the isomerization from a zero-octane molecule to an alkane with 100 octane the second is the dehydrocyclization of heptane to toluene with 120 octane, while the third is the rmdesired formation of coke. To reduce the rate of cracking and coke formation, the reactor is run with a high partial pressure of H2 that promotes the reverse reactions, especially the coke removal reaction. Modem catalytic reforming reactors operate at 500 to 550°C in typically a 20 1 mole excess of H2 at pressures of 20-50 atm. These reactions are fairly endothermic, and interstage heating between fixed-bed reactors or periodic withdrawal and heating of feed are used to maintain the desired temperatures as reaction proceeds. These reactors are sketched in Figure 2-16. 

In additional experiments, HZSM-5 was precoked by converting methanol alone (into hydrocarbons) at 400 °C. Afterwards the zeolite was exposed to the 2-methylnaphtha-lene/methanol mixture, under the usual reaction conditions. The initial yield of 1-methylnaphthalene was significantly reduced (1.5 % compared to 4 % for the fresh catalyst, cf. Fig. 4). Furthermore, the initial content of 2,6- + 2,7-dimethylnaphthalene in the dimethyl-naphthalene fraction was 84 % instead of 70 % for the fresh catalyst. In another run, HZSM-5 was loaded with 0.5 wt.-% of Pt, and H2 was used as carrier gas instead of N2. Under these conditions, the formation of coke was avoided or at least drastically diminished. In-line with our model, no changes in the product yields and in the distribution of the dimethylnaphthalene isomers were observed with time on stream. 

Thermodynamics. Formation of coke is thermodynamically favorable even at POX conditions. Consider the formation of two compounds that approximate the structure of coke, anthracene (C14H10, a 3-ring polycyclic aromatic compound) and naphthacene (CigHi2, a 4-ring polycyclic aromatic). These compounds can be formed from n-Cie by the following two reactions ... 

Effect of Aromatics on Formation of Coke and Carbon. Conventional liquid fuels contain widely differing levels of aromatics gasoline usually contains more than diesel. The studies show that these compounds cause more rapid deactivation than linear alkanes alone. A related result is that the steady state conversion of diesel fractions is also reduced in the presence of aromatics—i.e., these compounds act as kinetic inhibitors, limiting the production of H2. 

Catalyst deactivation is primarily caused by the blockage of active sites due to the coke formed from these olefinic intermediates. Higher hydrogen pressures suppress the diolefin formation, making the selectivity between olefinic intermediates and liquid products (in contrast to coke products) more favorable. However, higher pressures reduce selectivity to aromatics in the desired liquid product. Thus, a rigorous model must accurately predict not only the rates of product formation, but also the formation of coke precursors... 

Thus, the number of ring isomerization sites available for reaction is the total number of active sites minus those sites blocked by the formation of coke. Since the metal and acid sites can be used for reactions other than isomerization, intermediates from these other reactants adsorbed on the site also affect the ring isomerization reaction by reducing the number of active sites for the ring isomerization reaction. Since isomerization involves both metal and acid sites in a unique way, all intermediates from other reactions that utilize metal and acid sites in this manner have the potential to block these active sites. This is illustrated in Fig. 13. 

Assuming that all steps in the formation of coke precursors are in equilibrium and that the final coke formation step is irreversible, the coke buildup rate [from Eq. (32)] can be expressed as... 

The constant a is a function of the operating conditions and its use should be limited within the range of conditions for which it has been estimated. For estimating the reaction rate, the relation of Cc with time has to be determined. If the formation of coke occurs in par allel with the main reaction, the following equation is applicable ... 

Clays are a family of crystalline aluminosilicate solids that interact with a variety of organic compounds (Theng, 1974). Acid treatment develops acidic sites by removing aluminum from the structure and often enhances the reactivity of the clay with specific families of organic compounds. The acid sites also catalyze the formation of coke, and Houdry developed a moving bed process that continuously removed the coked beads from the reactor for regeneration by oxidation with air (McEvoy, 1996). 

Coke formation is considered, with just cause, to be a malignant side reaction of normal carbonium ions. However, while chain reactions dominate events occurring on the surface, and produce the majority of products, certain less desirable bimolecular events have a finite chance of involving the same carbonium ions in a bimolecular interaction with one another. Of these reactions, most will produce a paraffin and leave carbene/carboid-type species on the surface. This carbene/carboid-type species can produce other products but the most damaging product will be one which remains on the catalyst surface and cannot be desorbed and results in the formation of coke, or remains in a noncoke form but effectively blocks the active sites of the catalyst. 

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