Oxo-alcohols

Fig. 5. Flow diagram for oxo alcohol manufactured by the two-stage process. Courtesy of the Ethyl Corporation.

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 demand for amyl alcohols is expected to remain unchanged until 1993. Competition from other alcohols and limited appHcations limit growth in markets for amyl alcohols. U.S. demand was predicted to grow from 29 x 10 t in 1983 to 32 x Kf t by 1990 (152). In Europe, amyl alcohols account for over 80% of the demand for valeraldehyde (17,000 t in 1984). BASE and Hoechst AG produce both / -valeraldehyde and 2-methylbutyraldehyde from butenes by the oxo process (149). The demand for C-5 in Europe is also predicted not to grow substantially (150). Amyl alcohols are growing at a much lower rate than other oxo alcohols as shown in Table 7. 

Xanthates have been synthesized from C -Cg oxo alcohols ia a reactor with iatensive stirring at 25°C. The water and unreacted alcohol are removed from the product at 40—50°C under vacuum to give a friable powder of 80% purity ia 77% yield (79) (see Oxo process Alcohols, higher aliphatic). 

All lation. CPD can be multiply alkylated in high yields using alkyl haUdes, oxo alcohols, and Guerbet alcohols (35—36). After hydrogenation of the diene products, these so-called multiply alkylated cyclopentanes (6), where R = C Hg -C20 and m = 2-6, have been demonstrated to be useful as synthetic lubricants. 

Most of the propylene polymerized by this process is used in motor gasoline ("Polymer Gasoline"). However, an appreciable portion of the C7, C, and C,2 olefins find use as feedstocks for production of Oxo alcohols. 

As a constituent of synthesis gas, hydrogen is a precursor for ammonia, methanol, Oxo alcohols, and hydrocarbons from Fischer Tropsch processes. The direct use of hydrogen as a clean fuel for automobiles and buses is currently being evaluated compared to fuel cell vehicles that use hydrocarbon fuels which are converted through on-board reformers to a hydrogen-rich gas. Direct use of H2 provides greater efficiency and environmental benefits. ... 

The 1997 U.S. propylene demand ws 31 billion pounds and most of it was used to produce polypropylene polymers and copolymers (about 46%). Other large volume uses are acrylonitrile for synthetic fibers (Ca 13%), propylene oxide (Ca 10%), cumene (Ca 8%) and oxo alcohols (Ca 7%). ... 

Potential sources of carbon monoxide hazards include metal-refining processes, in which it is formed as a byproduct and used as a fuel (LEL 12.5%), and running vehicle engines (particularly petrol-driven) or gas-fired heaters in poorly ventilated confined spaces. It is also a feedstock in the manufacture of a variety of chemicals, e.g. methanol, acetic acid, phosgene and oxo-alcohols. 

Synthesis H2 or Refinery Ammonia Methanol Fischer-Tropsch Oxo Alcohols... 

A method has been developed which is designed to remove nucleotide residues singly from a polynucleotide chain, and it is anticipated that more precise information will shortly be forthcoming regarding the order in which the nucleotides are linked.220 The method is based on the fact that esters of 3-oxo alcohols are unstable toward alkali. In agreement with this, it is found that the products of the action of periodate on adenosine 5-phosphate (XXX) or adenosine 5-(benzyl hydrogen phosphate) are hydrolyzed under very mild conditions. Thus, after removal of terminal, singly-esterified phosphoryl residues from a polynucleotide chain, it is anticipated that periodate oxidation and hydrolysis will result in the removal of the... 

Enhanced surfactant flooding, 23 532 Enhancement factor, gas absorption with reaction, 1 47-48 Enhancement programs, aquatic organisms, 3 183, 198 Enhancement reagents, 12 102 Enhancer, 10 688 Enichem oxo-alcohols, 17 725 Enkaid, molecular formula and structure, 5 92t... 

Surfactants can be produced from both petrochemical resources and/or renewable, mostly oleochemical, feedstocks. Crude oil and natural gas make up the first class while palm oil (+kernel oil), tallow and coconut oil are the most relevant representatives of the group of renewable resources. Though the worldwide supplies of crude oil and natural gas are limited—estimated in 1996 at 131 X 1091 and 77 X 109 m3, respectively [28]—it is not expected that this will cause concern in the coming decades or even until the next century. In this respect it should be stressed that surfactant products only represent 1.5% of all petrochemical uses. Regarding the petrochemically derived raw materials, the main starting products comprise ethylene, n-paraffins and benzene obtained from crude oil by industrial processes such as distillation, cracking and adsorption/desorption. The primary products are subsequently converted to a series of intermediates like a-olefins, oxo-alcohols, primary alcohols, ethylene oxide and alkyl benzenes, which are then further modified to yield the desired surfactants. 

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. 

The Oxo alcohols contain one more carbon atom chan the original olefin used. They differ in two respects from the natural alcohols. First the Oxo alcohols contain either even or odd numbers of carbon atoms, the natural alcohols only even. Second, the Oxo alcohols all have some branched molecules—originally about 40% but with recent process improvements, as low as 5%. See Figure 15—4.)... 

Genapol UD030 C11 oxo alcohol ethoxylate with 3 moles ED Hoechs... 

Diisononyl Phthalate and DiisodecylPhthalate. These primary plasticizers are produced by esterification of oxo alcohols of carbon chain length nine and ten. The oxo alcohols are produced through the carbonylation of alkenes (olefins). The carbonylation process (eq. 3) adds a carbon unit to an alkene chain by reaction with carbon monoxide and hydrogen with heat, pressure, and catalyst. In this way a C, alkene is carbonylated to yield a C9 alcohol a C9 alkene is carbonylated to produce a C10 alcohol. Due to the distribution of the C=C double bond in the alkene and the varying effectiveness of certain catalysts, the position of the added carbon atom can vary and an isomer distribution is generally created in such a reaction the nature of this distribution depends on the reaction conditions. Consequendy these alcohols are termed iso-alcohols and the subsequent phthalates iso-phthalates, an unfortunate designation in view of possible confusion with esters of isophthalic acid. 

Under mild conditions, hydroformylation of olefins with rhodium carbonyl complexes selectively produces aldehydes. A one-step synthesis of oxo alcohols is possible using monomeric or polymeric amines, such as dimethylbenzylamine or anion exchange resin analog to hydrogenate the aldehyde. The rate of aldehyde hydrogenation passes through a maximum as amine basicity and concentration increase. IR data of the reaction reveal that anionic rhodium carbonyl clusters, normally absent, are formed on addition of amine. Aldehyde hydrogenation is attributed to enhanced hydridic character of a Rh-H intermediate via amine coordination to rhodium. 

T T ydroformylation of olefins to aldehydes over cobalt carbonyl catalysts is the first step in the industrial synthesis of oxo alcohols (1, 2). Reaction conditions require temperatures above 150 °C and pressures up to 3000 psig. Subsequent aldehyde hydrogenation occurs over supported cobalt or molybdenum disulfide catalysts. 

In contrast to cobalt, rhodium permits a one-step oxo alcohol synthesis in the presence of certain monomeric and polymeric amines (8, 9, 10). Included in this group are triethylamine, N-alkylpiperidines, N-methylpyrrolidine, and N,N-dimethylbenzylamine (DMBA). Initial kinetic data on this amine-promoted alcohol synthesis (under severe reaction conditions) have been reported by B. Fell and coworkers (II), but no attempt has been made to characterize the catalytic species in the reaction cycle. 

Denney, R. G., Oxo Alcohols, Stanford Research Inst., Report No. 21,... 

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