Carbonaceous intermediates hydrocarbons

As a starting point, the book reviews the general properties of the raw materials. This is followed by the different techniques used to convert these raw materials to the intermediates, which are further reacted to produce the petrochemicals. The first chapter deals with the composition and the treatment techniques of natural gas. It also reviews the properties, composition, and classification of various crude oils. Properties of some naturally occurring carbonaceous substances such as coal and tar sand are briefly noted at the end of the chapter. These materials are targeted as future energy and chemical sources when oil and natural gas are depleted. Chapter 2 summarizes the important properties of hydrocarbon intermediates and petroleum fractions obtained from natural gas and crude oils. 

Carbonaceous species on metal surfaces can be formed as a result of interaction of metals with carbon monoxide or hydrocarbons. In the FTS, where CO and H2 are converted to various hydrocarbons, it is generally accepted that an elementary step in the reaction is the dissociation of CO to form surface carbidic carbon and oxygen.1 The latter is removed from the surface through the formation of gaseous H20 and C02 (mostly in the case of Fe catalysts). The surface carbon, if it remains in its carbidic form, is an intermediate in the FTS and can be hydrogenated to form hydrocarbons. However, the surface carbidic carbon may also be converted to other less reactive forms of carbon, which may build up over time and influence the activity of the catalyst.15... 

The formation of hydrocarbons from methanol catalyzed by zeolite H-MFI has been investigated extensively 60,61). As with many hydrocarbon conversions, the catalytic activity of the methanol-to-hydrocarbons reaction decreases over time as a result of the buildup of high-molecular-weight carbonaceous deposits (coke). UV Raman spectroscopy was employed to characterize the accumulation and chemical nature of deposited hydrocarbons as a function of time and reaction temperature with both methanol and dimethyl ether as reactants and with zeolite MFI of various Si/Al atomic ratios as catalysts the first account of this work reported results for a zeolite MFI with low acid content (Si/Al = 90) (62). Both polyolefin and a cyclopentadienyl species were observed as intermediates during the formation of polyaromatic retained hydrocarbons. These observations strongly confirm the mechanism of coke formation proposed by Schulz and Wei (63) involving aromatic formation via a five-membered ring... 

The relatively slow rate of hydrocarbon fuel cell oxidations prompted an intensive examination of the adsorption characteristics of organic reactants in the 1960s. Because of the low potential for the development of hydrocarbon fuel cells, such studies have largely subsided today and no modern surface analysis techniques have been applied to characterize intermediates. Conventional adsorption studies of carbonaceous species have been reviewed repeatedly (7, 9-12, 100 -, therefore, we summarize here only some essential adsorption features for fuel cell and selective electrocatalytic oxidations. 

Selective surface poisoning may involve impurities or reaction intermediates, such as carbonaceous layers formed during hydrocarbon reactions. The order or disorder of this carbonaceous layer appears to affect selectivity, with demanding reactions favored by an ordered layer (575). Although alkene hydrogenation is assumed to occur on this layer (575), further characterization of its significance for catalyst selectivity is necessary. 

The model of deactivation describes the transformations of two boundary forms of the carbonaceous deposits during the catalytic hydrogenation of CO2. These are the hydrocarbon-formed active deposit (CH) and the graphitic inactive one (C)n. Thus deactivation is based on dehydrogenation of the active deposit into the inactive one that blocks active centers for hydrogenation. The active deposit, a product of polymerization of surface methane precursors (CH ), is simultaneously their consumer and producer. The mass balance of the active intermediates derived from the model assumptions gave the kinetic equation which quantitatively describes the deactivation. 

The MgyAlOx activity declines in the acetone oligomerization reaction due to a blockage of both basic and acid active sites by a carbonaceous residue formed by secondary aldol condensation reactions. The key intermediate species for coke formation are highly unsaturated linear trimers that are formed by aldol condensation of mesityl oxide with acetone and remain strongly bound to the catalyst surface. The catalyst surface acid-base properties determine the preferential formation of a given trimeric intermediate, which in turn defines the chemical nature of the carbon deposit. Aromatic hydrocarbons are the main component of coke formed on acidic Al-rich MgyAlOx samples whereas heavy a,P-unsaturated ketones preferentially form on basic Mg-rich catalysts. 

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