Linear a-olefin

Ziegler found that adding certain metals or their compounds to the reaction mixture led to the formation of ethylene oligomers with 6-18 carbons but others promoted the for matron of very long carbon chains giving polyethylene Both were major discoveries The 6-18 carbon ethylene oligomers constitute a class of industrial organic chemicals known as linear a olefins that are produced at a rate of 3 X 10 pounds/year m the... 

One of the mam uses of the linear a olefins prepared by oligomerization of ethylene is in the preparation of linear low density polyethylene Linear low density polyethylene is a copoly mer produced when ethylene is polymerized in the presence of a linear a olefin such as 1 decene [H2C=CH(CH2)7CH3] 1 Decene replaces ethylene at random points in the growing polymer chain Can you deduce how the structure of linear low density polyethylene differs from a linear chain of CH2 units ... 

The linear a olefins described m Section 14 15 are starting materials for the preparation of a variety of aldehydes by reaction with carbon monoxide The process is called hydroformylation... 

Fig. 2. Dependence of olefin reactivity on its carbon atom number when linear a-olefins are copolymerized with ethylene.

Butene. Commercial production of 1-butene, as well as the manufacture of other linear a-olefins with even carbon atom numbers, is based on the ethylene oligomerization reaction. The reaction can be catalyzed by triethyl aluminum at 180—280°C and 15—30 MPa ( 150 300 atm) pressure (6) or by nickel-based catalysts at 80—120°C and 7—15 MPa pressure (7—9). Another commercially developed method includes ethylene dimerization with the Ziegler dimerization catalysts, (OR) —AIR, where R represents small alkyl groups (10). In addition, several processes are used to manufacture 1-butene from mixed butylene streams in refineries (11) (see BuTYLENEs). 

Other Higher Oleiins. Linear a-olefins, such as 1-hexene and 1-octene, are produced by catalytic oligomerization of ethylene with triethyl aluminum (6) or with nickel-based catalysts (7—9) (see Olefins, higher). Olefins with branched alkyl groups are usually produced by catalytic dehydration of corresponding alcohols. For example, 3-methyl-1-butene is produced from isoamyl alcohol using base-treated alumina (15). 

The Cg—0 2 branched, odd and even, linear and internal olefins are used to produce improved flexible poly(vinyl chloride) plastics. Demand for these branched olefins, which are produced from propylene and butylene, is estimated to be increasing at a rate of 2% per year. However, the growth of the linear a-olefins is expected to slow down to a rate of 5% per year from 1992 to 1997 (3), as opposed to growth rates of 7—10% in the 1980s. 

Olig omerization and Polymerization. Siace an aHyl radical is stable, linear a-olefins are not readily polymerized by free-radical processes such as those employed ia the polymerization of styrene. However, ia the presence of Ziegler-Natta catalysts, these a-olefins can be smoothly converted to copolymers of various descriptions. Addition of higher olefins during polymerization of ethylene is commonly practiced to yield finished polymers with improved physical characteristics. 

Most linear a-olefins are produced from ethylene. Ethylene-based capacity in 1993 was 2,196,000 t, compared to only 30,000 t for fatty alcohol-based manufacture. 

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. 

Idemitsu Process. Idemitsu built a 50 t x 10 per year plant at Chiba, Japan, which was commissioned in Febmary of 1989. In the Idemitsu process, ethylene is oligomerised at 120°C and 3.3 MPa (33 atm) for about one hour in the presence of a large amount of cyclohexane and a three-component catalyst. The cyclohexane comprises about 120% of the product olefin. The catalyst includes sirconium tetrachloride, an aluminum alkyl such as a mixture of ethylalurninumsesquichloride and triethyl aluminum, and a Lewis base such as thiophene or an alcohol such as methanol (qv). This catalyst combination appears to produce more polymer (- 2%) than catalysts used in other a-olefin processes. The catalyst content of the cmde product is about 0.1 wt %. The catalyst is killed by using weak ammonium hydroxide followed by a water wash. Ethylene and cyclohexane are recycled. Idemitsu s basic a-olefin process patent (9) indicates that linear a-olefin levels are as high as 96% at C g and close to 100% at and Cg. This is somewhat higher than those produced by other processes. 

Linear terminal olefins are the most reactive in conventional cobalt hydroformylation. Linear internal olefins react at less than one-third that rate. A single methyl branch at the olefinic carbon of a terminal olefin reduces its reaction rate by a factor of 10 (2). For rhodium hydroformylation, linear a-olefins are again the most reactive. For example, 1-butene is about 20—40 times as reactive as the 2-butenes (3) and about 100 times as reactive as isobutylene. 

Coordination-catalyzed ethylene oligomerization into n-a-olefins. The synthesis of homologous, even-numbered, linear a-olefins can also be performed by oligomerization of ethylene with the aid of homogeneous transition metal complex catalysts [26]. Such a soluble complex catalyst is formed by reaction of, say, a zero-valent nickel compound with a tertiary phosphine ligand. A typical Ni catalyst for the ethylene oligomerization is manufactured from cyclo-octadienyl nickel(O) and diphenylphosphinoacetic ester ... 

Production of chemicals became increasingly important. The recovery of oxygenates from the Fischer-Tropsch aqueous product was expanded to include niche chemicals, such as 1-propanol.45 Ethylene and propylene extraction was increased and even supplemented by the addition of a high-temperature catalytic cracker.46 Linear a-olefin extraction units for the recovery of 1-pentene, 1-hexene, and 1-octene were added to the refinery,45-47 and a new facility for the extraction of 1-heptene and its... 

The design intent was to produce transportation fuels, and the design did not specifically make provision for chemicals co-production. It is in principle possible to extract chemicals from the HTFT syncrude, such as the alcohols that are being recovered from the Fischer-Tropsch aqueous product. Extraction of linear a-olefins may also be considered, which has indeed been investigated,57 and many other opportunities exist. However, it should be noted that the Mossgas facility is much smaller than the Sasol Synfuels facility, and recovery of valuable products in HTFT syncrude may not have economy of scale. 

Most commercial Fischer-Tropsch refinery designs (Figures 18.1 to 18.9) included the co-production of chemicals with transportation fuels. The chemicals potential of Fischer-Tropsch syncrude has been pointed out repeatedly.38,47,65 66 This is a natural consequence of the properties of Fischer-Tropsch syncrude, that is, richness in linear hydrocarbons, olefins (especially linear a-olefins), and oxygenates. Furthermore, it is sulfur-free and nitrogen-free, which enables access to synthetic routes sensitive to such compounds. 

Linear a-olefins, 20 414. See also Linear higher a-olefins manufacture of, 17 713-724 world producers of, 17 710t Linear blending value (LBV), 12 412—413 Linear burning rate, 10 720 Linear collider, 23 862... 

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