Coke, catalyst support

The MTO process employs a turbulent fluid-bed reactor system and typical conversions exceed 99.9%. The coked catalyst is continuously withdrawn from the reactor and burned in a regenerator. Coke yield and catalyst circulation are an order of magnitude lower than in fluid catalytic cracking (FCC). The MTO process was first scaled up in a 0.64 m /d (4 bbl/d) pilot plant and a successfiil 15.9 m /d (100 bbl/d) demonstration plant was operated in Germany with U.S. and German government support. 

Early workers viewed carriers or catalyst supports as inert substances that provided a means of spreading out an expensive material like platinum or else improved the mechanical strength of an inherently weak material. The primary factors in the early selection of catalyst supports were their physical properties and their cheapness hence pumice, ground brick, charcoal, coke, and similar substances were used. No attention was paid to the possible influence of the support on catalyst behavior differences in behavior were attributed to variations in the distribution of the catalyst itself. 

The enormous importance of carbon in such diverse fields as inorganic and organic chemistry and biology is well known however, only the aspects of carbon relevant to catalysis will be described here. The main topics we are concerned with are porous activated carbons, carbon black as catalyst supports and forms of coking. Carbon is also currently used as storage for natural gas and to clean up radioactive contamination. Carbon is available at low cost and a vast literature exists on its uses. Coal-derived carbon is made from biomass, wood or fossil plants and its microstructure differs from carbon made from industrial coke. Activated carbons are synthesized by thermal activation or by chemical activation to provide desirable properties like high surface area. 

Catalysts for coal liquefaction require specific properties. Catalysts of higher hydrogenation activity, supported on nonpolar supports, such as tita-nia, carbon, and Ca-modified alumina, are reasonable for the second stage of upgrading, because crude coal liquids contain heavy polar and/or basic polyaromatics, which tend to adsorb strongly on the catalyst surface, leading to coke formation and catalyst deactivation. High dispersion of the catalytic species on the support is very essential in this instance. The catalyst/support interactions need to be better understood. It has been reported that such interactions lead to chemical activation of the substrate 127). This is discussed in more detail in Section XIII. 

The HYSEC Process was developed by Mitsubishi Kakoki K. Ltd. and The Kansai Coke Chemicals Company. It has basically the same PSA unit as the UCC Process. It has prefilter beds with activated carbon that remove dirty components. After the main PSA beds, trace amounts of remaining oxygen are removed by a deoxo catalytic converter followed by a zeolitic dehumidifier. A Ni-LaaOj-Rh catalyst, supported on silica, could lower the reaction temperature to about 30°( a. 

There have been attempts to use catalysts in order to reduce the maximum temperature of thermal decomposition of methane. In the 1960s, Universal Oil Products Co. developed the HYPROd process for continuous production of hydrogen by catalytic decomposition of a gaseous hydrocarbon streams.15 Methane decomposition was carried out in a fluidized bed catalytic reactor from 815 to 1093°C. Supported Ni, Fe and Co catalysts (preferably Ni/Al203) were used in the process. The coked catalyst was continuously removed from the reactor to the regeneration section where carbon was burned off by air, and the regenerated catalyst returned to the reactor. Unfortunately, the system with two fluidized beds and the solids-circulation system was too complex and expensive and could not compete with the SR process. 

In the second step, the dioxanes are vaporized, superheated, and then cracked on a solid catalyst (supported phosphoric acid) in the presence of steam. The endothermic reaction takes place a about 200 to 2S0°C and 0.1 to OJ. 10 Pa absolute. The heat required is supplied by the introduction of superheated steam, or by heating the support of the catalyst, which operates in a moving, fluidized or fixed bed, and, in this case, implies cyclic operation to remove the coke deposits formed. Isoprene selectivity is about SO to 90 mole per cent with once-through conversion of 50 to 60 per cent The 4-4 DMD produces the isoprene. The other dioxanes present are decomposed into isomers of isoprene (piperylene etc.), while the r-butyl alcohol, also present in small amounts, yields isobutene. A separation train, consisting of scrubbers, extractors and distillation columns, serves to recycle the unconverted DMD, isobutene and fonnol, and to produce isoprene to commercial specifications. 

The structure and activity of coked catalysts exposed for a short time to aromatic feedstocks has been studied (26). It was concluded that coke is primarily located on the bare alumina support, and that the Ni(Co)Mo sulfides have a selfcleaning capability with increasing coke content, coke gradually approaches the (active) edges of the NiMoS function. At a coke level of 10%, catalyst activity decreased by some 75%. It has been shown (27) that the nature of the coke not only depends on conditions but also on the type of catalyst. 

The Conversion of Ethylene to Coke on Supported Platinum Catalysts invesiigated by NMR... 

After panial oxidation of a coked catalyst, the first peak of the TPO profile disappears, and the activity for n-buiane dehydrogenation is completely recovered. A signiricaiu amount of graphitic carbon is detected by TEM and SAED examination of the residual carbon on Pt-Sn catalysts after partial oxidation. This implies that the first peak of the 1 PO profile corresponds to carbon deposits located mainly on the metal surface, wbile the second one derives from the more graphitC Iikc carbon located on the support. 

A further complication that can detract from the validity of quantitative XPS for the characterization of coke deposits Is the mobility of coke components. After Introduction into ultra-high vacuum this mobile fraction may migrate from the inside of catalyst powder grains to their boundary as analysed by XPS. For certain catalyst systems this phenomenon has been observed. It can be easily identified however since the signal intensity ratio for the coke versus support increases with time the catalyst spent in the spectrometer. For the catalysts in this study no change of the signal ratio with time in the measurement chamber was observed. 

Coronene adsorbs on catalyst sites present on both the alumina support and on the active NiMo sulfide phase 3). It has been found that adsorption decreases with coke content to a very Jow value at high coke levels (4), Therefore, it appears that coronene adsorption on the coke is nil. On this basis, it is assiimmed that the loss in adsorption with increasing coke is proportional to the loss in pore surface area due to coverage by coke. The results of coronene adsorption measurements on the VGO-coked catalysts show an initial drop for the 2% C sample, but little change thereafter for higher coked catalysts (Fig. lA) This implies that the coke Is concentrated near the mouth of the pores, On the other hand, catalyst dlffusivity measurements show a continual and sig-... 

Studies of catalysts deactivation by coke are abundant in the literature most of them are usually conducted at high temperatures (around 500°C) using metal catalysts supported on oxides with low surface area such as silica, aluminas or silica-alumina [2 and references therein]. The deactivation by coke of zeolite catalysts has also been studied and such studies have mostly been done for high temperature reactions such as the conversion of n-hexane or the isomerization of xylenes [2,4]. However, low temperature coke formation (20-25°C) combining the effect of high acidity and size specificity for a high coking component such as nickel, has not yet been considered from the point of view of the presence of compounded effects of crystalline structure and location of metal particles. 

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