Abstract:Higher aliphatic alcohols (C
6
–C
18
) are produced in a number of important industrial processes using petroleum‐based raw materials, eg, the Ziegler, oxo, and aldol processes. By far the largest volume synthetic alcohol is 2‐ethylhexanol, C
8
H
18
O, used mainly in production of the poly(vinyl chloride) plasticizer bis(2‐ethylhexyl) phthalate, C
24
H
38
O
… Show more
“…In the detergent manufacturing industry, the separation of C 8 to C 20 1-alcohols and n -alkanes is of interest, as acceptably pure 1-alcohol products are required for further processing . These detergent range 1-alcohols are produced via many different production routes, including the substitution of a hydroxyl group onto n -alkanes or the hydration of olefins, with many processes leading to significant contamination of the resulting product stream with n -alkanes . Separation of mixtures of detergent range alcohols and alkanes by means of conventional separation techniques, such as distillation, are infeasible due to the similarity in the melting and boiling points of the compounds .…”
Section: Introductionmentioning
confidence: 99%
“…1 These detergent range 1-alcohols are produced via many different production routes, including the substitution of a hydroxyl group onto nalkanes or the hydration of olefins, 2 with many processes leading to significant contamination of the resulting product stream with n-alkanes. 3 Separation of mixtures of detergent range alcohols and alkanes by means of conventional separation techniques, such as distillation, are infeasible due to the similarity in the melting and boiling points of the compounds. 4 Azeotropic distillation is currently employed as a means of separating these mixtures, 1 while supercritical fluid fractionation may also be a feasible separation technique.…”
New vapor−liquid equilibrium data for six binary systems of 1alcohols (C m ) + n-alkanes (C m+3 ) were experimentally measured at 40 kPa. The systems that were investigated include 1-pentanol + n-octane, 1-hexanol + nnonane, 1-heptanol + n-decane, 1-octanol + n-undecane, 1-nonanol + ndodecane, and 1-decanol + n-tridecane. All of the data were measured using a commercial, all-glass, dynamic recirculating equilibrium still, and the compositions of the coexisting equilibrium phases were determined using gas chromatography. All systems displayed positive azeotropes, indicative of strong positive deviations. The experimental data were successfully modeled using the PSRK + UNIFAC model, the NRTL model, and the PSRK + NRTL model. The NRTL model outperformed both of the PSRK model variations, with the PSRK + NRTL model performing slightly better than the PSRK + UNIFAC model for the higher homologue combinations.
“…In the detergent manufacturing industry, the separation of C 8 to C 20 1-alcohols and n -alkanes is of interest, as acceptably pure 1-alcohol products are required for further processing . These detergent range 1-alcohols are produced via many different production routes, including the substitution of a hydroxyl group onto n -alkanes or the hydration of olefins, with many processes leading to significant contamination of the resulting product stream with n -alkanes . Separation of mixtures of detergent range alcohols and alkanes by means of conventional separation techniques, such as distillation, are infeasible due to the similarity in the melting and boiling points of the compounds .…”
Section: Introductionmentioning
confidence: 99%
“…1 These detergent range 1-alcohols are produced via many different production routes, including the substitution of a hydroxyl group onto nalkanes or the hydration of olefins, 2 with many processes leading to significant contamination of the resulting product stream with n-alkanes. 3 Separation of mixtures of detergent range alcohols and alkanes by means of conventional separation techniques, such as distillation, are infeasible due to the similarity in the melting and boiling points of the compounds. 4 Azeotropic distillation is currently employed as a means of separating these mixtures, 1 while supercritical fluid fractionation may also be a feasible separation technique.…”
New vapor−liquid equilibrium data for six binary systems of 1alcohols (C m ) + n-alkanes (C m+3 ) were experimentally measured at 40 kPa. The systems that were investigated include 1-pentanol + n-octane, 1-hexanol + nnonane, 1-heptanol + n-decane, 1-octanol + n-undecane, 1-nonanol + ndodecane, and 1-decanol + n-tridecane. All of the data were measured using a commercial, all-glass, dynamic recirculating equilibrium still, and the compositions of the coexisting equilibrium phases were determined using gas chromatography. All systems displayed positive azeotropes, indicative of strong positive deviations. The experimental data were successfully modeled using the PSRK + UNIFAC model, the NRTL model, and the PSRK + NRTL model. The NRTL model outperformed both of the PSRK model variations, with the PSRK + NRTL model performing slightly better than the PSRK + UNIFAC model for the higher homologue combinations.
“…By reducing the pressure to 10 bar and increasing the reaction temperature to 300 °C, the long-chain alkyl groups can be displaced from aluminum as α-olefins, thereby regenerating triethyl aluminum (eq 2) . This chain growth reaction is still commercially exploited today for the synthesis of linear α-olefins (Alfen Process) and primary alcohols from ethylene. , …”
The bis(imino)pyridine iron complex, [[2,6-(MeC=N-2,6-iPr2C6H3)2C5H)N]FeCl2] (1), in combination with MAO and ZnEt2 (> 500 equiv.), is shown to catalyze polyethylene chain growth on zinc. The catalyzed chain growth process is characterized by an exceptionally fast and reversible exchange of the growing polymer chains between the iron and zinc centers. Upon hydrolysis of the resultant ZnR2 product, a Poisson distribution of linear alkanes is obtained; linear alpha-olefins with a Poisson distribution can be generated via a nickel-catalyzed displacement reaction. Other dialkylzinc reagents such as ZnMe2 and ZniPr2 also show catalyzed chain growth; in the case of ZnMe2 a slight broadening of the product distribution is observed. The products obtained from Zn(CH2Ph)2 show evidence for chain transfer but not catalyzed chain growth, whereas ZnPh2 shows no evidence for chain transfer. The Group 13 metal alkyl reagents AlR3 (R = Me, Et, octyl, IBu) and GaR3 (R = Et, nBu) act as highly efficient chain transfer agents, whereas GaMe3 exhibits behavior close to catalyzed chain growth. LinBu, MgnBu2 and BEt3 result in very low activity catalyst systems. SnMe4 and PbEt4 give active catalysts, but with very little chain transfer to Sn or Pb. The remarkably efficient iron catalyzed chain growth reaction for ZnEt2 compared to other metal alkyls can be rationalized on the basis of: (1) relatively low steric hindrance around the zinc center, (2) their monomeric nature in solution, (3) the relatively weak Zn-C bond, and (4) a reasonably close match in Zn-C and Fe-C bond strengths.
“…For instance, the Guerbet selfcondensation of n-butanol produces 2-ethylhexanol (2EH), industrially the most important compound in the group of "plasticizer alcohols". 5,[90][91][92] It is mostly applied in the synthesis of polymer additives, e.g. as a phthalate ester in PVC applications, giving the polymer improved flexibility and durability.…”
The Guerbet condensation reaction is an alcohol coupling reaction that has been known for more than a century. Because of the increasing availability of bio-based alcohol feedstock, this reaction is of growing importance and interest in terms of value chains of renewable chemical and biofuel production. Due to the specific branching pattern of the alcohol products, the Guerbet reaction has many interesting applications. In comparison to their linear isomers, branched-chain Guerbet alcohols have extremely low melting points and excellent fluidity. This review provides thermodynamic insights and unravels the various mechanistic steps involved. A comprehensive overview of the homogeneous, heterogeneous and combined homogeneous and heterogeneous catalytic systems described in published reports and patents is also given. Technological considerations, challenges and perspectives for the Guerbet chemistry are discussed.
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