Linear oxo alcohols

Vincent, R. E, Higher linear Oxo alcohols manufacture", ACS I79th National Meeting. Houston, Texas (25/26 March 1980). 

Catalytic Oligomeri tion. Shell Chemical provides C —C linear internal olefin feedstock for detergent oxo alcohol production from its SHOP... 

These detergent range (C C ) odd and even linear internal olefins are fed to oxo-alcohol plants to produce C22 C2 semilinear alcohols. Most of the alcohols are ethoxylated and sold into detergent markets (8). Shell balances carbon numbers by a combination of the ethylene oligomerization extent. 

A few companies, eg, Enichem in Italy, Mitsubishi in Japan, and a plant under constmction at Eushun in China, separate the olefins from the paraffins to recover high purity (95—96%) linear internal olefins (LIO) for use in the production of oxo-alcohols and, in one case, in the production of polylinear internal olefins (PIO) for use in synthetic lubricants (syn lubes). In contrast, the UOP Olex process is used for the separation of olefins from paraffins in the Hquid phase over a wide carbon range. 

The 0x0 process is employed to produce higher alcohols from linear and branched higher olefins. Using a catalyst that is highly selective for hydroformylation of linear olefins at the terminal carbon atom. Shell converts olefins from the Shell higher olefin process (SHOP) to alcohols. This results in a product that is up to 75—85% linear when a linear feedstock is employed. Other 0x0 processes, such as those employed by ICI, Exxon, and BASE (all in Europe), produce oxo-alcohols from a-olefin feedstocks such alcohols have a linearity of about 60%. Enichem, on the other hand, produces... 

The oxo and modified oxo process involve the reaction of mixed a- and internal olefins with hydrogen and carbon monoxide to give predominantly linear primary alcohols, although both processes yield some branched alcohols. 

He was a Professor of Industrial Chemistry, School of Engineering, Polytechnic Institute of Milan, Milan, Italy since 1937. He became involved with applied research, which led to the production of synthetic rubber in Italy, at the Institute in 1938. He was also interested in the synthesis of petrochemicals such as butadiene and, later, oxo alcohols. At the same time he made important contributions to the understanding of the kinetics of some catalytic processes in both the heterogeneous (methanol synthesis) and homogeneous (oxosynthesis) phase. In 1950, as a result of his interest in petrochemistry, he initiated the research on the use of simple olefins for the synthesis of high polymers. This work led to the discovery, in 1954, of stereospecific polymerization. In this type of polymerization nonsymmetric monomers (e.g., propylene, 1-butene, etc.) produce linear high polymers with a stereoregular structure. 

In summary, it can be said that even-numbered linear oxo phthalates are superior in performance to the corresponding conventional oxo phthalates, and in most respects, closely approach the performance of the completely straight chain alcohol phthalates. Odd-numbered linear alcohols produce phthalates which impart some unique combinations of performance properties to vinyl that were previously available only by using composites of several plasticizers. 

Linear alpha olefins can be copolymerized with polyethylene to form linear low-density polyethylene (LLDPE) and 1-hexene (C6) and 1-octene (C8) are especially useful for this purpose. In addition, linear alpha olefins are used to make detergent alcohols, oxo alcohols for plasticizers, lubricants, lube oil additives, and surfactants are other important products from linear alpha olefins. 

Synthetic fatty alcohols fall into three broad categories and are manufactured from two basic raw materials—ethylene and n-paraffins. One group is secondary alcohols which are prepared by oxidation of n-paraffins in the presence of boric acid. A second group consists of oxo alcohols manufactured by hydroformylation of linear olefins which are derived from either n-paraffins or ethylene. Both of these alcohol types are discussed in separate chapters. The last group is Ziegler alcohols which are prepared from ethylene and are the primary subject of this chapter. 

Linear primary alcohols and alpha olefins in the C6-C 8 range have enjoyed remarkable growth in the last three decades. As esters, the C6—C,0 alcohols are used for plasticizing PVC. In the C 2-C]g range, the alcohols are used to make readily biodegradable surfactants of various types such as ethoxylates (nonionic), alcohol sulfates, and sulfates of ethoxylates (anionic). Alpha olefins are used as polyethylene comonomer (33%) and as raw materials for detergent alcohols (22%), oxo alcohols (10%), and lubricants and lube oil additives (18%). 

Linear internal monoolefins can be oxidized to linear secondary alcohols. The alpha (terminal) olefins from ethylene oligomerization, described earlier in this chapter, can be converted by oxo chemistry to alcohols having one more carbon atom. The higher alcohols from each of these sources are used for preparation of biodegradable, synthetic detergents. The alcohols provide the hydrophobic hydrocarbon group and are linked to a polar, hydrophilic group by ethoxylation, sulfation, phosphorylation, and so forth. 

Knifton has also shown (36 - 38,40) that nitrogen- or phosphorus-ligand modified ruthenium complexes, in a phosphonium salt matrix, can conveniently catalyze the hydroformylation of terminal alkenes with high selec-tivities in linear oxo products. Usually selectivities better than 80% were achieved. In the best case (160°C, 95 bar. CO/H2= 1/2) a linearity in nonanol of 94% was obtained starting from [Ru3(CO),2], 2,2 -bipyridine. and [PBu4]Br. The main products were alcohols and not aldehydes. However, it is often difficult to reduce the isomerization of oct-l-ene as well as its hydrogenation. The [Ru3(CO),2l/2,2 -bipyridine (bipy) system has been extensively explored. Two equilibria have been proposed to account for the infrared data and the effects of the bipy ligand [eqs. (8) and (9)]. 

Bimetallic Cu/Ni colloids stabilized by Ca and Ba stearates were applied in a simple four-neck round-bottomed flask for the amination of linear and branched oxo-alcohols with dimethylamine [16]. 78-92% yields of tertiary amines were achieved within 3-5 h at 210 °C. 

The 13—carbon tridecyl alcohol is usually considered to be a plasticizer range alcohol because of its manufacture by the oxo process and its use in making plasticizers. On the other hand, some types of linear 9- and 11-carbon alcohols find major appHcation in detergents. 

A.luminum Jilkyl Chain Growth. Ethyl, Chevron, and Mitsubishi Chemical manufacture higher, linear alpha olefins from ethylene via chain growth on triethyl aluminum (15). The linear products are then used as oxo feedstock for both plasticizer and detergent range alcohols and because the feedstocks are linear, the linearity of the alcohol product, which has an entirely odd number of carbons, is a function of the oxo process employed. Alcohols are manufactured from this type of olefin by Sterling, Exxon, ICI, BASE, Oxochemie, and Mitsubishi Chemical. 

The spectmm of oxo products ia Japan is far less diverse. Nearly 75% of Japan s total oxo capacity of 733,000 t is dedicated to the hydroformylation of propylene. 2-EH derived from -butyraldehyde is by far the dominant product. Other products iaclude linear alcohols and higher branched alcohols. Additionally, Japan is the world s principal source of branched heptyl alcohol. The three ptincipal Japanese oxo producers having slightly more than 70% of Japan s total oxo capacity are Mitsubishi Kasei, Kyowa Yuka, and Japan Oxocol. 

Linear alcohols used for the production of ethoxylates are produced by the oligomerization of ethylene using Ziegler catalysts or by the Oxo reaction using alpha olefins. 

Linear alcohols (C12-C26) are important chemicals for producing various compounds such as plasticizers, detergents, and solvents. The production of linear alcohols by the hydroformylation (Oxo reaction) of alpha olefins followed by hydrogenation is discussed in Chapter 5. They are also produced by the oligomerization of ethylene using aluminum alkyls (Ziegler catalysts). 

The rheology and phase behavior of sodium linear C16-C18 alcohol sulfate and sodium oxo C14-Cl5 (80% linear) alcohol sulfate was studied by van Zon et al. [75]. The oxoalcohol sulfate can be prepared as a handleable 65-70% concentrate. The linear C16-C18 alcohol sulfate only allows 55-60% as maximum concentration. The hexagonal phase of the oxoalcohol sulfate extends from 38% to 55% active matter whereas the hexagonal band of the linear alcohol sulfate is very narrow, only extending from 35% to 40% and its crystallization line is situated at a higher level than for the oxo derivative. 

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