Cracking of hydrocarbon

The original method for the manufacture of ethyne, the action of water on calcium carbide, is still of very great importance, but newer methods include the pyrolysis of the lower paraffins in the presence of steam, the partial oxidation of natural gas (methane) and the cracking of hydrocarbons in an electric arc. 

The superacid-catalyzed cracking of hydrocarbons (a significant practical application) involves not only formation of trivalent carbo-cationic sites leading to subsequent /3-cleavage but also direct C-C bond protolysis. 

Pyrolysis gasoline is a by-product of the steam cracking of hydrocarbon feeds in ethylene crackers (see Ethylene). Pyrolysis gasoline typically contains about 50—70 wt % aromatics, of which roughly 50% is benzene, 30% is toluene, and 20% is mixed xylenes (which includes EB). 

The pattern of commercial production of 1,3-butadiene parallels the overall development of the petrochemical industry. Since its discovery via pyrolysis of various organic materials, butadiene has been manufactured from acetylene as weU as ethanol, both via butanediols (1,3- and 1,4-) as intermediates (see Acetylene-DERIVED chemicals). On a global basis, the importance of these processes has decreased substantially because of the increasing production of butadiene from petroleum sources. China and India stiU convert ethanol to butadiene using the two-step process while Poland and the former USSR use a one-step process (229,230). In the past butadiene also was produced by the dehydrogenation of / -butane and oxydehydrogenation of / -butenes. However, butadiene is now primarily produced as a by-product in the steam cracking of hydrocarbon streams to produce ethylene. Except under market dislocation situations, butadiene is almost exclusively manufactured by this process in the United States, Western Europe, and Japan. 

Although ethylene is produced by various methods as follows, only a few are commercially proven thermal cracking of hydrocarbons, catalytic pyrolysis, membrane dehydrogenation of ethane, oxydehydrogenation of ethane, oxidative coupling of methane, methanol to ethylene, dehydration of ethanol, ethylene from coal, disproportionation of propylene, and ethylene as a by-product. 

Mechanism. The thermal cracking of hydrocarbons proceeds via a free-radical mechanism (20). Siace that discovery, many reaction schemes have been proposed for various hydrocarbon feeds (21—24). Siace radicals are neutral species with a short life, their concentrations under reaction conditions are extremely small. Therefore, the iategration of continuity equations involving radical and molecular species requires special iategration algorithms (25). An approximate method known as pseudo steady-state approximation has been used ia chemical kinetics for many years (26,27). The errors associated with various approximations ia predicting the product distribution have been given (28). 

In chemical laboratories, small flasks and beakers are used for liquid phase reactions. Here, a charge of reactants is added and brought to reaction temperature. The reaction may be held at this condition for a predetermined time before the product is discharged. This batch reactor is characterized by the varying extent of reaction and properties of the reaction mixture with time. In contrast to the flasks are large cylindrical tubes used in the petrochemical industry for the cracking of hydrocarbons. This process is continuous with reactants in the tubes and the products obtained from the exit. The extent of reaction and properties, such as composition and temperature, depend on the position along the tube and does not depend on the time. 

Polymerization of alkenes and the isomerization of alkanes and alkenes occur in the presence of a cocatalyst such as H2O, whereas the cracking of hydrocarbons is best performed with HF as cocatalyst. These latter reactions are of major commercial importance in the petrochemicals industry. 

Ethylene is a constituent of refinery gases, especially those produced from catalytic cracking units. The main source for ethylene is the steam cracking of hydrocarbons (Chapter 3). Table 2-2 shows the world ethylene production by source until the year 2000. U.S. production of ethylene was approximately 51 billion lbs in 1997. ... 

Like ethylene, propylene (propene) is a reactive alkene that can be obtained from refinery gas streams, especially those from cracking processes. The main source of propylene, however, is steam cracking of hydrocarbons, where it is coproduced with ethylene. There is no special process for propylene production except the dehydrogenation of propane. 

The main route for producing light olefins, especially ethylene, is the steam cracking of hydrocarbons. The feedstocks for steam cracking units range from light paraffinic hydrocarbon gases to various petroleum fractions and residues. The properties of these feedstocks are discussed in Chapter 2. 

Butadiene is mainly obtained as a byproduct from the steam cracking of hydrocarbons and from catalytic cracking. These two sources account for over 90% of butadiene demand. The remainder comes from dehydrogenation of n-butane or n-butene streams (Chapter 3). The 1998 U.S. production of butadiene was approximately 4 billion pounds, and it was the 36th highest-volume chemical. Worldwide butadiene capacity was nearly 20 billion pounds. 

Riser-cyclone separator attached to another separation device to minimize re-cracking of hydrocarbon vapors. External or internal. 

For a monomolecular reaction, such as the cracking of hydrocarbons by protonic zeolites, the rate expression is very similar to the one in Eq. (1.5). The rate of the reaction is now proportional to the concentration of molecules at the reaction center, the proton of the zeolite, Eq. (1.22a). 

The process is conducted at 700 °C. It yields semicoke, which is popular as a smokeless domestic fuel. It can at times be used in boiler also to avoid smoke. Yield of coke oven gas is less, of tar high, and of ammonia less. Calorific value of coke oven gas generated is more. The process produces aliphatic natured tar. Following carbonization the coke discharging process is difficult as it swells extensively but does not shrink much upon carbonization. Free carbon in tar (produced from the cracking of hydrocarbons) is less Coke produced is weaker. Volatile matter in the coke produced is more. Hydrogen content in the coke oven gas is less. 

H2, hydrogen, is a colorless, odorless, tasteless, nonpolar, diamagnetic, diatomic gas with the lowest atomic weight and density of any known substance. It has low solubility in water and is very flammable. Hydrogen is prepared by reactions of metals with water, steam or various acids, electrolysis of water, the water gas reaction and thermal cracking of hydrocarbons. It combines with metals and nonmetals to form hydrides. 

Rice has shown that the cracking of hydrocarbons at high temperatures gives free radicals.48 Only the methyl and ethyl radicals survive long enough to react with mercury to give dialkylmercury. Presumably the others decomposes by a beta cleavage process. 

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