Industrial steam cracking

The complexity of the steam-cracking plant is largely coimected with the type of feedstock treated. Among the various altemati es, how ever, the choice of naphtha oSers the most complete, and hence the most representative case study. This is because this petroleum cut constitutes one of the most wklelv used raw materials for the manufacture of ethylene, and also because its treatment includes that of ethane, by recycling in special furnaces. 

On the whole, a steam-cracking facility ccunprises two main sections a so-called hot section, where the feedstock is pyrolysed and the effluent conditioned, and a so-called cold section, w here the products fonned are separated and purified. 

The effluents are then transferred (part 6) to a primary fractionatioa column ipart SX which separates a heavy residue at the bottom (part ) and a fraction of pyrolysis gasoline and water on sidesntams. while the tight pyrolysis products leave at the cop in gaseous form. 

After compression (part 9X caustic scrubbing and drying, these light effluents enter the cold section of the unit, which can be designed in various ways, and which perfonns the following separations  

Pyrolysis furnaces are designed to proride a rapid lerr.peraturc rise of the feedstock, a hi exit temperature, and very short residence time, in solving these problems, the design of the pyrolysis tubes and furnaces are of decisive importance. 

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Figure 2Z0 summarizes the complete arrangements of the different units of the hot and cold sections of an industrial steam cracking plant... 

The status and fiitine trends in the development and application of novel reactors equipped with solid electrolyte based membrane materials was analyzed in a review article [105]. BaCo Fe Zr Oj perovskite hollow-fiber membrane reactor was used with permeable and passivated surface segments to enable controlled oxygen insertion into the reactor. The reduced oxygen concentration offered higher ethene selectivity. At low and moderate ethane conversion, the performance of the membrane reactor was on par with the best catalysts used in cofeed mode. The ethene yield was comparable with that of the industrial steam cracking process. However, the reaction temperature was 100°C lower [106],... 

Gyclopentadiene/Dicyclopentadiene-Based Petroleum Resins. 1,3-Cyclopentadiene (CPD) is just one of the numerous compounds produced by the steam cracking of petroleum distillates. Due to the fact that DCPD is polymerized relatively easily under thermal conditions without added catalyst, resins produced from cycloaHphatic dienes have become a significant focus of the hydrocarbon resin industry. 

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. 

Raw materials for obtaining benzene, which is needed for the production of alkylbenzenes, are pyrolysis gasoline, a byproduct of the ethylene production in the steam cracking process, and coke oven gas. Reforming gasoline contains only small amounts of benzene. Large amounts of benzene are further produced by hydrodealkylation of toluene, a surplus product in industry. 

Small olefins, notably ethylene (ethene), propene, and butene, form the building blocks of the petrochemical industry. These molecules originate among others from the FCC process, but they are also manufactured by the steam cracking of naphtha. A wealth of reactions is based on olefins. As examples, we discuss here the epoxida-tion of ethylene and the partial oxidation of propylene, as well as the polymerization of ethylene and propylene. 

Propylene is manufactured by steam cracking of hydrocarbons as discussed under ethylene. The best feedstocks are propane, naphtha, or gas oil, depending on price and availability. About 50-75% of the propylene is consumed by the petroleum refining industry for alkylation and polymerization of propylene to oligomers that are added to gasoline. A smaller amount is made by steam cracking to give pure propylene for chemical manufacture. 

Olefins are hydrocarbon compounds with at least two carbon atoms and having a double bond. Their unstable nature and tendency to polymerize makes them one of the very important building blocks for the chemical and petrochemical industry (Gary and Handwerk, 1994). Although olefins are produced by fluid catalytic cracking in refineries, the main production source is through steam cracking of liquefied petroleum gas (LPG), naphtha or gas oils. 

Propylene is a colorless, flammable gas that follows ethylene as the second simplest alkene hydrocarbon. It has an odor similar to garlic and has wide use in the chemical industry as an intermediate in the synthesis of other derivatives such as polypropylene, propylene oxide, isopropyl alcohol, acetone, and acrylonitrile. The production of propylene is similar to ethylene and is obtained through steam cracking of hydrocarbon feedstocks. Steam cracking is a process used to break molecules into smaller molecules by injecting the catalysts with steam. 

The major industrial source of ethylene and propylene is the pyrolysis (thermal cracking) of hydrocarbons.137-139 Since there is an increase in the number of moles during cracking, low partial pressure favors alkene formation. Pyrolysis, therefore, is carried out in the presence of steam (steam cracking), which also reduces coke formation. Cracking temperature and residence time are used to control product distribution. 

Selective hydrogenation of diolefins and alkenylaromatics in steam-cracked gasoline is of industrial importance. Specific refining by selective hydrogenation of these polymerizable hydrocarbons without hydrogenating other unsaturated compounds (alkenes, aromatics) is required to increase the stability of gasoline (see Section 11.6.1). 

Natural gas liquids represent a significant source of feedstocks for the production of important chemical building blocks that form the basis for many commercial and industrial products. Ethylene (qv) is produced by steam-cracking the ethane and propane fractions obtained from natural gas, and the butane fraction can be catalytically dehydrogenated to yield 1,3-butadiene, a compound used in the preparation of many polymers (see Butadiene). The -butane fraction can also be used as a feedstock in the manufacture of MTBE. 

Pyrolysis gasoline is a by-product of steam cracking of hydrocarbon feeds in ethylene. Coke over light oil is a by product of the manufacture of coke for the steel industry. 

Chapter 7 is the climax of the book Here the educated student is asked to apply all that he/she has learned thus far to deal with many common practical industrial units. In Chapter 7 we start with a simple illustrative example in Section 7.1 and introduce five important industrial processes, namely fluid catalytic cracking in FCC units in Section 7.2, the UNIPOL process in Section 7.3, industrial steam reformers and methanators in Section 7.4, the production of styrene in Section 7.5, and the production of bioethanol in Section 7.6. 

The olefins ethylene and propylene are highly important synthetic chemicals in the petrochemical industry. Large quantities of such chemicals are used as feedstock in the production of polyethylene, polypropylene, and so on [31]. The prime source of lower olefins is the olefin-paraffin mixtures from steam cracking or fluid catalytic cracking in the refining process [32]. Such mixtures are intrinsically difficult to... 

Both of these reactions have very important industrial uses (Section 14.3.9). In order to obtain alkene streams of sufficient purity for further use, the products of steam-cracking or catalytic cracking of naphtha fractions must be treated to lower the concentration of alkynes and alkadienes to very low levels (<5ppm). For example, residual alkynes and dienes can reduce the effectiveness of alkene polymerisation catalysts, but the desired levels of impurities can be achieved by their selective hydrogenation (Scheme 9.4) with palladium catalysts, typically Pd/A Os with a low palladium content. A great deal of literature exists,13,37 particularly on the problem of hydrogenating ethyne in the presence of a large excess of... 

In industrial practice, however, the most widespread technique consists in passmg a mixture of hydrocarbons and steam through tubes placed in a furnace. The hydrocarbons, which are raised to high temperature, are pyrolysed and the resulting products are separated after a rapid quench. Coke deposits are periodically removed by controlled combustion. This is the technology of steam cracking, which is the main focus of this chapter. 

Based on the foregoing considerations, it can therefore be infen that a decrease in the tube diameter, which causes a reduction in residence ime, results in a higher ethylene yield (diagram a in Fig. 2.12) in industrial naphtha steam cracking conditions. Simultaneously, a drop in the propylene yield (diagram b in Fig. 2.12) is observed in the normal... 

The synthesis of ethylene by the dehydration of fennemation ethanol was formerly practised in the industrial countries before the development of steam cracking. This... 

Industrial separation of butadiene from steam-cracked cuts... 

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