Olefinic hydrocarbons from cracking ethane

More than 90% of today s petrochemicals are produced from refineiy products. Most are based on the use of C2-C4 olefins and aromatics finm hydrocarbon steam cracking units, which are even more closely linked to refineries. In North America, the feedstock for steam cracker units have generally been ethane, propane, or LPG. As a result, most of the propylene and aromatics have been provided by FCC units and catalytic reformers. In maity other parts of the world where naphtha feed has been more readily available, suppUes of propylene and aromatics have been produced directly by steam cracking. When necessary, the catalytic dehydrogenation of paraffins or dealkylation of toluene can balance the supply of olefins or benzene. In Table 7.2 some of the catalytic processes that convert olefins and benzene from a steam cracker into basic petrochemicals for the modem chemical industry are shown. 

Olefins are produced primarily by thermal cracking of a hydrocarbon feedstock which takes place at low residence time in the presence of steam in the tubes of a furnace. In the United States, natural gas Hquids derived from natural gas processing, primarily ethane [74-84-0] and propane [74-98-6] have been the dominant feedstock for olefins plants, accounting for about 50 to 70% of ethylene production. Most of the remainder has been based on cracking naphtha or gas oil hydrocarbon streams which are derived from cmde oil. Naphtha is a hydrocarbon fraction boiling between 40 and 170°C, whereas the gas oil fraction bods between about 310 and 490°C. These feedstocks, which have been used primarily by producers with refinery affiliations, account for most of the remainder of olefins production. In addition a substantial amount of propylene and a small amount of ethylene ate recovered from waste gases produced in petroleum refineries. 

Fired reactors contain tubes or coils in which an endothermic reaction within a stream of reac tants occurs. Examples include steam/ hydrocarbon reformers, catalvst-filled tubes in a combustion chamber pyrolyzers, coils in which alkanes (from ethane to gas oil) are cracked to olefins in both types of reac tor the temperature is maintained up to 1172 K (1650°F). 

Natural gas and crude oils are the main sources for hydrocarbon intermediates or secondary raw materials for the production of petrochemicals. From natural gas, ethane and LPG are recovered for use as intermediates in the production of olefins and diolefms. Important chemicals such as methanol and ammonia are also based on methane via synthesis gas. On the other hand, refinery gases from different crude oil processing schemes are important sources for olefins and LPG. Crude oil distillates and residues are precursors for olefins and aromatics via cracking and reforming processes. This chapter reviews the properties of the different hydrocarbon intermediates—paraffins, olefins, diolefms, and aromatics. Petroleum fractions and residues as mixtures of different hydrocarbon classes and hydrocarbon derivatives are discussed separately at the end of the chapter. 

The techniques of preparation and of separation of hydrocarbons were improved. New construction materials led to cracking being conducted under more severe conditions, to increase the amount of olefins produced.. This also permitted a change from propane to ethane as the raw material for ethylene synthesis. Aromatics became available from petroleum naphthenes. Diolefins and acetylene were also manufactured from petroleum sources. 

Today, the majority of ethylene is produced by thermal cracking of hydrocarbon feedstocks ranging fi-om ethane to heavy vacuum gas oils. Over 60% of the world s propylene is produced as a by-product of thermal cracking, with the balance being supplied from refinery sources and others. Raw materials are mosdy natural gas condensate components (principally ethane and propane) in the US and Mideast and naphtha in Europe and Asia. Alkanes/olefins are broken apart at high temperatures, often in the presence of a zeolite catalyst, to produce a mixture of primarily aliphatic alkenes and lower molecular weight alkanes. The mixture is feedstock and temperature dependent and separated by fractional distillation. 

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