Alcohol from syngas

Zhang, H., Dong, X., Lin, G., Liang, X. L., and Li, H. Y. 2005. Carbon nanotube-promoted Co-Cu catalyst for highly efficient synthesis of higher alcohols from syngas. Chemical Communications 40 5094—96. 

Dobanol A process for making linear fatty alcohols from syngas. Developed by Deutsche Shell Chemie. 

Considerable attention has been paid to the application of CNTs as the catalyst support for Fischer Tropsch synthesis (FTS), mainly driven by utilization of the confinement effect (Section 15.2.3). In general, this process is a potential alternative to synthesize fuel (alkanes) or basic chemicals like alkenes or alcohols from syngas, which can be derived from coal or biomass. The broad product spectrum, which can be controlled only to a limited extent by the catalyst, prohibited its industrial realization so far, however, it is considered an important building block for future energy and chemical resource management based on renewables. 

Methanol Production and Higher Alcohols from Syngas... 

While entry 5 (CYPHOS IL 163) may be considered a borderline ionic, to date, of all the phosphonium-based ILs, it has received the most attention. Garayt et al. have patented a process to fluorinate aromatics [20]. Previously, Knifton, lin et al. have published and patented an enormous number of petrochemical applications using entry 5 as the solvent-alcohols from syngas [21-29], synthesis of acetaldehyde and acetic acid from syngas [40-45], synthesis of esters from syngas [46, 47], and synthesis of formamides and amines [48, 49],... 

Ethanol and Higher Alcohols from Syngas. Direct synthesis of ethanol from syngas is intensely investigated especially in North America. Another approach in this context is the homologjzation of methanol, i.e. the reaction of methanol with syngas to yield ethanol. Higher alcohols can also be formed. The reactions are summarized in equations (8.3) and (8.4). 

For the production of higher alcohols from syngas, two kinds of perovskites have been reported in the literature. First, perovskites with noble metals, like LaRhOs, have been studied in the past [23,24] for the ethanol synthesis with a CO/H2 mixture. More recently, LaCoi Cu 03 perovskites have been investigated to explore the opportunity of the Ci-C alcohols synthesis following an Anderson-Schulz-Flory (ASF) distribution [25-32] similar to that obtained by the so-called Co-Cu IFP catalyst [33]. 

Liu, G., Niu, T., Pan, D., Liu, F., and Liu, Y. (2014) Preparation of bimetal Cu-Co nanoparticles supported on meso-macroporous SiOa and their application to higher alcohols from syngas. Appl Catal A, 483, 10-18. 

Y. Zhang, Y. Sun and B. Zhong. Synthesis of higher alcohols from syngas over ultrafine Mo-Co-K catalysts. Catal. Lett. 76, 2001, 249-253. 

Oxalic acid produced from syngas can be esteiified (eq. 20) and reduced with hydrogen to form ethylene glycol with recovery of the esterification alcohol (eq. 21). Hydrogenation requires a copper catalyst giving 100% conversion with selectivities to ethylene glycol of 95% (15). 

Skeletal catalysts are usually employed in slurry-phase reactors or fixed-bed reactors. Hydrogenation of cottonseed oil, oxidative dehydrogenation of alcohols, and several other reactions are performed in sluny phase, where the catalysts are charged into the liquid and optionally stirred (often by action of the gases involved) to achieve intimate mixing. Fixed-bed designs suit methanol synthesis from syngas and catalysis of the water gas shift reaction, and are usually preferred because they obviate the need to separate product from catalyst and are simple in terms of a continuous process. 

Before 1920s, methanol was obtained from wood as a co-product of charcoal production, hence the name wood alcohol. Methanol is currently manufactured worldwide from syngas, which is derived from natural gas, refinery off-gas, coal or petroleum, as ... 

One shortcoming of the Fischer-Tropsch synthesis is its lack of selectivity in giving complex product mixtures. In an attempt to improve the selectivity of syngas-based hydrocarbon synthesis, Mobil researchers developed a process consisting of converting methyl alcohol (itself, however, produced from syngas) to gasoline (or other hydrocarbons) over a shape-selective intermediate-pore-size zeolite catalyst (H-ZSM-5) 22 78... 

This alcohol can be reacted with methanol in the presence of a catalyst to produce methyl-r-butyl ether. Although it is currently cheaper to make Ao-butyl alcohol from Ao-butcne (Ao-butylene), it can be synthesized from syngas with alkali-promoted zinc oxide catalysts at temperatures above 400°C (750°F). 

Recent study found that Pd sulfide prepared by sulfiding PdCU (structure detennined with XRD was Pd S ) yielded methanol with a selectivity above 95-mol% (70). This result is notable because, so far, only Mo and W sulfides have been known to show weak activities for the synthesis of gaseous hydrocarbons from syngas (77). This type of sulfides had some attentions because Mo sulfide modified with alkali metal additives showed a constant activity for alcohol synthesis even in die presence of H2S (77). This is in marked contrast with the... 

Another possible way to separate they catalyst from the fatty products was found by Davis [52-54] and further investigated by Fell [55]. This new method is supported aqueous-phase catalysis (SAPC cf. Section 4.7). On a hydrophilic support, e.g., silicon oxide with a high surface area, a thin aqueous film is applied which contains the water-soluble rhodium catalyst, for instance HRh(CO)L3 with sodium TPPTS ligands. Oleyl alcohol and syngas react at the organic/aqueous interface and form the formylstearyl alcohol in a yield of 97%. The catalyst can be separated from the product by simple filtration without loss of activity. 

The oldest patents concerning polyhydric alcohols mention Mn, Cr, and Co catalysts which were applied at very high pressures but nevertheless were still of poor activity and selectivity. Substantial progress in selectivity has been achieved with Rh catalysts by, e.g.. Union Carbide. With proper co-catalysts e.g., firmly co-ordinated Cs) up to 75% of ethylene glycol can be made from syngas mixtures. Keim et al. reported that solvents are also important for the resulting activity and selectivity. For example, the order of activity in oxygenates formation of various metal complexes (mostly carbonyls) dissolved in A -methyl pyrrolidone is ... 

Methanol and higher alcohol production from syngas. 

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