Olefin fractionation

Crude oil typically contains little to no olefinic compounds. Through refining and processing, however, olefins are produced and become a part of various crude oil fractions. Olefins can be found in thermally cracked and catalytically cracked gasoline fractions as well as in FCC cycle oils and coker gas oils. For this reason, it is not unusual for finished gasoline and distillate blends to contain a high-olefin-content stream. 

Equaticsi (12) takes into account also those molecules that have been subject to diain transfer after the first incorporation of a monomer. Although these ethylene molecules do not contribute to the experimental overall conversion, they are the product of catalytic steps. For practical use it may be more convenient to refer the wei t fraction olefin in a certain range to the amount of ethylene converted to higher homologues. That means to normalize the weight fractions... 

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There are little or no olefins in crude oil or straight run (direct from crude distillation) products but they are found in refining products, particularly in the fractions coming from conversion of heavy fractions whether or not these processes are thermal or catalytic. The first few compounds of this family are very important raw materials for the petrochemical Industry e.g., ethylene, propylene, and butenes. 

This analysis, abbreviated as FIA for Fluorescent Indicator Adsorption, is standardized as ASTM D 1319 and AFNOR M 07-024. It is limited to fractions whose final boiling points are lower than 315°C, i.e., applicable to gasolines and kerosenes. We mention it here because it is still the generally accepted method for the determination of olefins. 

MAV is expressed in mg of anhydride per gram of sample. It is still widely used to evaluate the quantity of conjugated, olefins in a fraction. This type of molecule is highly undesirable in a large number of end products because of its propensity to polymerize spontaneously and to form gums. 

Ethers result from the selective addition of methanol or ethanol to the isobutene contained in C4 olefin fractions. Ethers are used as components in gasoline because of their high octane blending value (RON and MON). 

One can react methanol with the tertiary olefins having five c irbon atoms (isoamylenes). This process increases the octane number of FCC olefinic C5 fractions, in order to reduce the concentration of olefins and to increase gasoline production. 

Products of conversion from catalytic cracking are largely olefinic for light fractions and strongly aromatic for the heavy fractions. 

At high enough concentrations, PAN is a potent eye irritant and phytotoxin. On a smoggy day in the Los Angeles area, PAN concentrations are typically 5 to 10 ppb in the rest of the United States PAN concentrations are generally a fraction of a ppb. An important formation route for formaldehyde [50-00-0] HCHO, is reaction 9. However, o2onolysis of olefinic compounds and some other reactions of VOCs can produce HCHO and other aldehydes. 

Shell Higher Olefin Process) plant (16,17). C -C alcohols are also produced by this process. Ethylene is first oligomerized to linear, even carbon—number alpha olefins using a nickel complex catalyst. After separation of portions of the a-olefins for sale, others, particularly C g and higher, are catalyticaHy isomerized to internal olefins, which are then disproportionated over a catalyst to a broad mixture of linear internal olefins. The desired fraction is... 

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 principal class of reactions in the FCC process converts high boiling, low octane normal paraffins to lower boiling, higher octane olefins, naphthenes (cycloparaffins), and aromatics. FCC naphtha is almost always fractionated into two or three streams. Typical properties are shown in Table 5. Properties of specific streams depend on the catalyst, design and operating conditions of the unit, and the cmde properties. 

Hydrocarbon resin is a broad term that is usually used to describe a low molecular weight thermoplastic polymer synthesized via the thermal or catalytic polymerization of coal-tar fractions, cracked petroleum distillates, terpenes, or pure olefinic monomers. These resins are used extensively as modifiers in the hot melt and pressure sensitive adhesive industries. They are also used in numerous other appHcations such as sealants, printing inks, paints, plastics, road marking, carpet backing, flooring, and oil field appHcations. They are rarely used alone. 

The feedstocks used ia the production of petroleum resias are obtaiaed mainly from the low pressure vapor-phase cracking (steam cracking) and subsequent fractionation of petroleum distillates ranging from light naphthas to gas oil fractions, which typically boil ia the 20—450°C range (16). Obtaiaed from this process are feedstreams composed of atiphatic, aromatic, and cycloatiphatic olefins and diolefins, which are subsequently polymerized to yield resias of various compositioas and physical properties. Typically, feedstocks are divided iato atiphatic, cycloatiphatic, and aromatic streams. Table 2 illustrates the predominant olefinic hydrocarbons obtained from steam cracking processes for petroleum resia synthesis (18). 

Aliphatic C-5—C-6. Aliphatic feedstreams are typically composed of C-5 and C-6 paraffins, olefins, and diolefins, the main reactive components being piperylenes cis-[1574-41 -0] and /n j -l,3-pentadiene [2004-70-8f). Other main compounds iaclude substituted C-5 and C-6 olefins such as cyclopentene [142-29-OJ, 2-methyl-2-butene [513-35-9] and 2-methyl-2-pentene [625-27-4J. Isoprene and cyclopentadiene maybe present ia small to moderate quaatities (2—10%). Most steam cracking operatioas are desigaed to remove and purify isoprene from the C-5—C-6 fraction for applications ia mbbers and thermoplastic elastomers. Cyclopentadiene is typically dimerized to dicyclopentadiene (DCPD) and removed from C-5 olefin—diolefin feedstreams duriag fractionation (19). 

Although most aromatic modified C-5 resins are typically higher softening point resins, certain appHcations, such as adhesives, require lower softening points. Copolymerization of a C-8—C-10 vinyl aromatic fraction with piperylenes in the presence of a C-4—C-8 mono-olefin chain-transfer stream yields resins with softening points ranging from 0—40°C (44). A particular advantage of these Hquid resins is the fact that they eliminate the need for plasticizers or oils in some pressure sensitive adhesive appHcations. 

Ethylene Stripping. The acetylene absorber bottom product is routed to the ethylene stripper, which operates at low pressure. In the bottom part of this tower the loaded solvent is stripped by heat input according to the purity specifications of the acetylene product. A lean DMF fraction is routed to the top of the upper part for selective absorption of acetylene. This feature reduces the acetylene content in the recycle gas to its minimum (typically 1%). The overhead gas fraction is recycled to the cracked gas compression of the olefin plant for the recovery of the ethylene. 

Molecular sieves have had increasing use in the dehydration of cracked gases in ethylene plants before low temperature fractionation for olefin production. The Type 3A molecular sieve is size-selective for water molecules and does not co-adsorb the olefin molecules. 

The term naphthenic acid, as commonly used in the petroleum industry, refers collectively to all of the carboxyUc acids present in cmde oil. Naphthenic acids [1338-24-5] are classified as monobasic carboxyUc acids of the general formula RCOOH, where R represents the naphthene moiety consisting of cyclopentane and cyclohexane derivatives. Naphthenic acids are composed predorninandy of aLkyl-substituted cycloaUphatic carboxyUc acids, with smaller amounts of acycHc aUphatic (paraffinic or fatty) acids. Aromatic, olefinic, hydroxy, and dibasic acids are considered to be minor components. Commercial naphthenic acids also contain varying amounts of unsaponifiable hydrocarbons, phenoHc compounds, sulfur compounds, and water. The complex mixture of acids is derived from straight-mn distillates of petroleum, mosdy from kerosene and diesel fractions (see Petroleum). 

Temperature and Product Yields. Most oil shale retorting processes are carried out at ca 480°C to maximize liquid product yield. The effect of increasing retort temperature on product type from 480 to 870°C has been studied using an entrained bed retort (17). The oil yield decreased and the retort gas increased with increased retorting temperature the oil became more aromatic as temperature increased, and maximum yields of olefinic gases occurred at about 760°C. Effects of retorting temperatures on a distillate fraction (to 300°C) are given in Table 6. 

Linear a-olefins were produced by wax cracking from about 1962 to about 1985, and were first commercially produced from ethylene in 1965. More recent developments have been the recovery of pentene and hexene from gasoline fractions (1994) and a revival of an older technology, the production of higher carbon-number olefins from fatty alcohols. 

Olefin distribution in the Albemarle stoichiometric process tends to foUow the Poisson equation, where is the mole fraction of alkyl groups in whichp ethylene units have been added, and n is the average number of ethylene units added for an equal amount of aluminum. 

The solvent is 28 CC-olefins recycled from the fractionation section. Effluent from the reactors includes product a-olefins, unreacted ethylene, aluminum alkyls of the same carbon number distribution as the product olefins, and polymer. The effluent is flashed to remove ethylene, filtered to remove polyethylene, and treated to reduce the aluminum alkyls in the stream. In the original plant operation, these aluminum alkyls were not removed, resulting in the formation of paraffins (- 1.4%) when the reactor effluent was treated with caustic to kill the catalyst. In the new plant, however, it is likely that these aluminum alkyls are transalkylated with ethylene by adding a catalyst such as 60 ppm of a nickel compound, eg, nickel octanoate (6). The new plant contains a caustic wash section and the product olefins still contain some paraffins ( 0.5%). After treatment with caustic, cmde olefins are sent to a water wash to remove sodium and aluminum salts. 

Ethylene is recycled, some of which is purged, to eliminate the accumulation of ethane. The olefins are distilled into even-carbon-number fractions... 

The reactor outlet is flashed to remove ethylene which is then compressed and recycled a-olefins are separated from the solvent that contains the catalyst, treated to remove catalyst, and then distilled into commercial fractions. Most of the catalyst in the solvent is recycled but a portion is purged. The catalyst in the purge stream is recovered by reducing the oxidized nickel with boron hydride. 

Propjiene (qv) [115-07-1] is the predominant 0x0 process olefin feedstock. Ethylene (qv) [74-85-1J, as well as a wide variety of terminal, internal, and mixed olefin streams, are also hydroformylated commercially. Branched-chain olefins include octenes, nonenes, and dodecenes from fractionation of oligomers of C —C olefins as well as octenes from dimerization and codimerization of isobutylene and 1- and 2-butenes (see Butylenes). 

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