Ethylene from steam cracking process

Chemicals directly based on propane are few, although as mentioned, propane and LPG are important feedstocks for the production of olefins. Chapter 6 discusses a new process recently developed for the dehydrogenation of propane to propylene for petrochemical use. Propylene has always been obtained as a coproduct with ethylene from steam cracking processes. Chapter 6 also discusses the production of aromatics from LPG through the Cyclar process. ... 

IFP Process for 1-Butene from Ethylene. 1-Butene is widely used as a comonomer in the production of polyethylene, accounting for over 107,000 t in 1992 and 40% of the total comonomer used. About 60% of the 1-butene produced comes from steam cracking and fluid catalytic cracker effluents (10). This 1-butene is typically produced from by-product raffinate from methyl tert-huty ether production. The recovery of 1-butene from these streams is typically expensive and requires the use of large plants to be economical. Institut Francais du Petrole (IFP) has developed and patented the Alphabutol process which produces 1-butene by selectively dimerizing ethylene. 

The principal sources of feedstocks in the United States are the decant oils from petroleum refining operations. These are clarified heavy distillates from the catalytic cracking of gas oils. About 95% of U.S. feedstock use is decant oil. Another source of feedstock is ethylene process tars obtained as the heavy byproducts from the production of ethylene by steam cracking of alkanes, naphthas, and gas oils. There is a wide use of these feedstocks in European production. European and Asian operations also use significant quantities of coal tars, creosote oils, and anthracene oils, the distillates from the high temperature coking of coal. European feedstock sources are 50% decant oils and 50% ethylene tars and creosote oils. 

The most important olefins and diolefins used to manufacture petrochemicals are ethylene, propylene, butylenes, and hutadiene. Butadiene, a conjugated diolefin, is normally coproduced with C2-C4 olefins from different cracking processes. Separation of these olefins from catalytic and thermal cracking gas streams could he achieved using physical and chemical separation methods. However, the petrochemical demand for olefins is much greater than the amounts these operations produce. Most olefins and hutadienes are produced hy steam cracking hydrocarbons. 

The three isomers constituting n-hutenes are 1-hutene, cis-2-hutene, and trans-2-hutene. This gas mixture is usually obtained from the olefinic C4 fraction of catalytic cracking and steam cracking processes after separation of isobutene (Chapter 2). The mixture of isomers may be used directly for reactions that are common for the three isomers and produce the same intermediates and hence the same products. Alternatively, the mixture may be separated into two streams, one constituted of 1-butene and the other of cis-and trans-2-butene mixture. Each stream produces specific chemicals. Approximately 70% of 1-butene is used as a comonomer with ethylene to produce linear low-density polyethylene (LLDPE). Another use of 1-butene is for the synthesis of butylene oxide. The rest is used with the 2-butenes to produce other chemicals. n-Butene could also be isomerized to isobutene. ... 

D. Netzer, Process for the coproduction of benzene from refinery sources and ethylene by steam cracking, US Patent 6 677 496, January 13, 2004. 

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... 

As previously discussed, alkyl radicals decomposition reactions constitute an important fate and reaction path of alkyl radicals. Due to the very short lifetimes of alkyl radicals, Rice and Herzfeld (1933, 1934) suggested a complete decomposition mechanism where all the radicals larger than methyl were considered instantaneously decomposed into alkenes and H and CH3 radicals. In this mechanism, all the intermediate alkyl radicals decompose to directly form alkenes and smaller alkyl radicals. This would mean that the final ethylene production from a steam cracking process would be significantly overestimated when compared with the experimental measurements. For instance, the net and final result of the successive decomposition mechanism of 1-decyl radical would be 5 moles of ethylene and one H radical. 

On the other hand, from an environmental point of view, very high CO2 emissions are associated with the production processes of oIefins, either the ones inherent to chemical reactions themselves or those derived from the high energy consnmption. In this way, CO2 emissions associated with ethylene production in a steam cracking process are of ca. 1,200 gco2/kgoiefm This means that in 2004, global CO2 emissions associated with ethylene production was 180-200 million tons, and it is estimated to have been abont 250 million tons in 2008. ... 

The removal of acetylenes and dienes from steam-cracked olefins is a critical step in purification. Selective hydrogenation processes and catalysts have become more important as worldwide olefin production has increased in 1999 to more than 90 million tormes of ethylene and almost 50 million tonnes of propylene. Demand for better catalysts with improved selectivity and longer operating cycles has grown as larger plants are built. Tighter product specifications have also been imposed now that more of the olefins produced are being converted to polyolefins. 

Properly speaking, steam cracking is not a refining process. A key petrochemical process, it has the purpose of producing ethylene, propylene, butadiene, butenes and aromatics (BTX) mainly from light fractions of crude oil (LPG, naphthas), but also from heavy fractions hydrotreated or not (paraffinic vacuum distillates, residue from hydrocracking HOC). 

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. 

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. 

Steam Cracking. Steam cracking is a nonselective process that produces many products from a variety of feedstocks by free-radical reactions. An excellent treatise on the fundamentals of manufacturing ethylene has been given (44). Eeedstocks range from ethane on the light end to heavy vacuum gas oil on the heavy end. All produce the same product slate but in different amounts depending on the feedstock. 

Higher molecular weight hydrocarbons present in natural gases are important fuels as well as chemical feedstocks and are normally recovered as natural gas liquids. For example, ethane may be separated for use as a feedstock for steam cracking for the production of ethylene. Propane and butane are recovered from natural gas and sold as liquefied petroleum gas (LPG). Before natural gas is used it must be processed or treated to remove the impurities and to recover the heavier hydrocarbons (heavier than methane). The 1998 U.S. gas consumption was approximately 22.5 trillion ft. ... 

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. 

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. 

Table 8.1 shows the stochastic model solution for the petrochemical system. The solution indicated the selection of 22 processes with a slightly different configuration and production capacities from the deterministic case, Table 4.2 in Chapter 4. For example, acetic acid was produced by direct oxidation of n-butylenes instead of the air oxidation of acetaldehyde. Furthermore, ethylene was produced by pyrolysis of ethane instead of steam cracking of ethane-propane (50-50 wt%). These changes, as well as the different production capacities obtained, illustrate the effect of the uncertainty in process yield, raw material and product prices, and lower product... 

Propylene is a coproduct of steam cracking, the yield of which accounts for nearly half of the ethylene yield. Currently, propylene demand exceeds ethylene demand and steam cracking cannot keep up with the required propylene/ethylene balance. To close the gap, an increase in propylene production from the FCC process is needed. 

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