Butanol butyraldehyde

Manufacture of thiophene on the commercial scale involves reactions of the two component method type wherein a 4-carbon chain molecule reacts with a source of sulfur over a catalyst which also effects cyclization and aromatization. A range of suitable feedstocks has included butane, / -butanol, -butyraldehyde, crotonaldehyde, and furan the source of sulfur has included sulfur itself, hydrogen sulfide, and carbon disulfide (29—32). 

Uses Preparation of 1-butanol, butyraldehyde, 2-ethylhexanol, quinaldine chemical warfare insecticides leather tanning alcohol denaturant solvent warning agent in fuel gases purification of lubricating oils organic synthesis. 

Petal, J., and Ollis, D., 1992, Heterogeneous photocatalytic oxidation of gas-phase organics for air purification acetone, 1-butanol, butyraldehyde, formaldehyde, and rn-xylene oxidation . J. of Catalysis 136 554-565. 

Figure 2. Mol of liquid products in dry basis per mol of converted butanol ( butyraldehyde, butyl butyrate, conversion) at steady state and 673 K.

The highest volume oxo chemical ia the United States, -butyraldehyde, is converted mainly iato / -butanol, employed chiefly to produce butyl... 

The principal commercial source of 1-butanol is -butyraldehyde [123-72-8] obtained from the Oxo reaction of propylene. A mixture of n- and isobutyraldehyde [78-84-2] is obtained in this process this mixture is either separated initially and the individual aldehyde isomers hydrogenated, or the mixture of isomeric aldehydes is hydrogenated direcdy and the n- and isobutyl alcohol product mix separated by distillation. Typically, the hydrogenation is carried out in the vapor phase over a heterogeneous catalyst. For example, passing a mixture of n- and isobutyraldehyde with 60 40 H2 N2 over a CuO—ZnO—NiO catalyst at 25—196°C and 0.7 MPa proceeds in 99.95% efficiency to the corresponding alcohols at 98.6% conversion (7,8) (see Butyraldehydes Oxo process). 

Several species of bacteria under suitable conditions cause / -butyraldehyde to undergo the Canni22aro reaction (simultaneous oxidation and reduction to butyric acid and butanol, respectively) this reaction can also be cataly2ed by Raney nickel (7). The direct formation of butyl butyrate [109-21 -7] or isobutyl isobutyrate [97-85-8](Vish.ch.erik.o reaction) from the corresponding aldehyde takes place rapidly with aluminum ethylate or aluminum butyrate as catalyst (8). An essentially quantitative yield of butyl butyrate, CgH2 02, from butyraldehyde has been reported usiag a mthenium catalyst, RuH,[P(C,H,)3], (9). 

The majority (92% in 1988) of the butyraldehyde produced in the United States is converted into 1-butanol and 2-ethyIhexanol (2-EH). 2-EH is most widely used as the di(2-ethylhexyl) phthalate [117-81-7] ester for the plasticisation of flexible PVC. Other uses for 2-EH include production of intermediates for acryflc surface coatings, diesel fuel, and lube oil additives (24). 

The overall growth for -butyraldehyde depends primarily on / -butanol and 2-ethyIhexanol. 2-EthyIhexanol is expected to face competition from other alcohols, eg, isodecyl alcohol [25339-17-7] as well as from newer production sources. 

Butanol is the highest volume derivative of -butyraldehyde in the United States with nearly twice the production of 2-EH (56% vs. 36.5%). In sharp contrast, in Western Europe, Japan, and all other countries producing butyraldehydes, 2-EH is dominant. 

Ethanol s use as a chemical iatemiediate (Table 8) suffered considerably from its replacement ia the production of acetaldehyde, butyraldehyde, acetic acid, and ethyUiexanol. The switch from the ethanol route to those products has depressed demand for ethanol by more than 300 x 10 L (80 x 10 gal) siace 1970. This decrease reflects newer technologies for the manufacture of acetaldehyde and acetic acid, which is the largest use for acetaldehyde, by direct routes usiag ethylene, butane (173), and methanol. Oxo processes (qv) such as Union Carbide s Low Pressure Oxo process for the production of butanol and ethyUiexanol have totaUy replaced the processes based on acetaldehyde. For example, U.S. consumption of ethanol for acetaldehyde manufacture declined steadily from 50% ia 1962 to 37% ia 1964 and none ia 1990. Butadiene was made from ethanol on a large scale duriag World War II, but this route is no longer competitive with butadiene derived from petroleum operations. 

However, the 0x0 reaction starting frompropylene and proceeding via the hydrogenation of butyraldehyde, has become the more widely employed commercial route for preparing / -butanol (see BuTYL ALCOHOLS Oxo PROCESS). 

The largest commercial process is the hydroformylation of propene, which yields n-butyraldehyde and isobutyraldehyde. n-Butyraldehyde (n-butanal) is either hydrogenated to n-butanol or transformed to 2-ethyl-hexanol via aldol condensation and subsequent hydrogenation. 2-Ethylhexanol is an important plasticizer for polyvinyl chloride. This reaction is noted in Chapter 8. 

As an example of the system in which parallel and consecutive reactions occur simultaneously, we have chosen the hydrogenation of crotonaldehyde, which may lead through two two-stage paths (via butyraldehyde and via crotyl alcohol) to the same final product, butanol... 

Fig. 9. Dependence of relative molar concentrations Wj/nA0 of reaction components on reciprocal space velocity W/F (hr kg mole 1) in the parallel-consecutive hydrogenation of crotonaldehyde. Temperature 160°C, catalyst Pt-Fe/Si02 (1% wt. Pt, 0.7% Fe), initial molar ratio of reactants G = 10. The curves were calculated (1—crotonaldehyde, 2—butyraldehyde, 3—crotyl alcohol, 4—butanol) the points are experimental values.

Hydroformylation is an important industrial process carried out using rhodium phosphine or cobalt carbonyl catalysts. The major industrial process using the rhodium catalyst is hydroformylation of propene with synthesis gas (potentially obtainable from a renewable resource, see Chapter 6). The product, butyraldehyde, is formed as a mixture of n- and iso- isomers the n-isomer is the most desired product, being used for conversion to butanol via hydrogenation) and 2-ethylhexanol via aldol condensation and hydrogenation). Butanol is a valuable solvent in many surface coating formulations whilst 2-ethylhexanol is widely used in the production of phthalate plasticizers. 

Within the reactor, however, 6 per cent of the n-butyraldehyde product is reduced to n-butanol, 4 per cent of the isobutyraldehyde product is reduced to isobutanol, and other reactions occur to a small extent yielding high molecular weight compounds (heavy ends) to the extent of 1 per cent by weight of the butyraldehyde/butanol mixture at the reactor exit. 

Organic constituents in the first wastestream totaled about 14,000 mg/L (acetaldehyde, acetal-dol, acetic acid, butanol-1, butyraldehyde, chloroacetaldehyde, crotonaldehyde, phenol, and propionic acid) and about 5200 mg/L inorganic constituents. The pH ranged from 4 to 6, and TDS ranged from 3000 to 10,000 mg/L. 

Jones, J.H. and McCants, J.F. Ternary solubility data. 1 -Butanol-methanol 1-butyl ketone-water, 1-butyraldehyde-ethyl acetate-water, 1-hexane-methyl ethyl ketone-water, Ind. Eng. Chem., 46(9) 1956-1958, 1954. 

According to Scheme 6.2, the hydrogenation products for crotonaldehyde were butyraldehyde (SAL), crotyl alcohol (UOL), butanol (SOL) and cracking products only at trace levels. Selectivities to UOL, SAL and SOL were maintained from one cycle to the next [20]. 

Ethylhexanol is produced by aldol condensation of butyraldehyde followed by reduction. It can also be made in one step from propylene and synthesis gas converted to butanols and 2-ethylhexanol without isolating the butyraldehydes. See Chapter 10, Section 6. 

Condensation of butanol has been carried out on alkaline earth metal oxides at 273 K (13,121). This condensation reaction yields 2-ethyl-3-hydroxy-hexanal as a main product other products, such as 2-ethyl-2-hexenal (arising from the dehydration of 2-ethyl-3-hydroxy-hexanal), n-butyl-K-butyrate (arising from the Tishchenko reaction of butyraldehyde), and 2-ethyl-3-hydroxy- -hexyl butyrate (arising from the Tishchenko reaction of 2-ethyl-3-hydroxy-hexanal), are also formed (Scheme 12). 

The hydroformylation reaction, also known as the oxo reaction, is used extensively in commercial processes for the preparation of aldehydes by the reaction of one mole of an olefin with one mole each of hydrogen and carbon monoxide. The most extensive use of the reaction is in the preparation of normal- and iso-butyraldehyde from propylene. The ratio of the amount of the normal aldehyde product to the amount of the iso aldehyde product typically is referred to as the normal to iso (N I) or the normal to branched (N B) ratio. In the case of propylene, the normal- and iso-butyraldehydes obtained from propylene are in turn converted into many commercially-valuable chemical products such as n-butanol, 2-ethyl-hexanol, trimethylol propane, polyvinylbutyral, n-butyric acid, iso-butanol, neo-pentyl glycol,... 

Under the same reaction conditions, acetaldehyde and butyraldehyde displayed near-complete conversion (greater than 95%). The photocatalytic oxidation of the alcohol 1-butanol displayed similarly high conversion levels, although conversion of methanol was somewhat lower. The oxygenated compounds methyl-t-butyl ether (MTBE), methyl acrylate, 1,4 dioxane, and vinyl acetate displayed conversion levels ranging from 92% to 100%. The lowest conversion levels of the oxygenated compounds studied were seen with the ketones used [acetone and 2-butanone (methylethylketone)], which displayed conversions of approximately 80%. The initial conversion levels seen with -hexane were similar... 

Zeolite catalysts in many forms are used for important commercial processes. The studies were extended to L zeolites, mordenite, erionite, and dealuminated faujasites and mordenites. More attention is paid now to zeolites with univalent and multivalent cations and to multicomponent catalysts. Among these some important examples are the tellurium-containing catalyst for hydrocarbon dehydrocyclization (42), the difunctional Ni- and Pd-zeolite catalysts for benzene hydrodimerization to phenylcyclohexane (42), the catalyst for the hydrogenation of phenol cyclohexanol (44), the 4% Ni/NaY which forms butanol, 2-ethylhexanol, 2-ethylhexanal, and 2-ethylhexanol from a mixture of n-butyraldehyde and hydrogen. 

Hie principal commercial source of 1-butanol is n-butyraldehyde. obtained from tile Oxo reaction of propylene. 

The highest volume oxo chemical in the United States, n-butyraldehyde, is converted mainly into u-butanol, employed chiefly to produce butyl acrylate and methacrylate. In contrast, the principal -butyraldehyde derivative in Europe and Japan is 2-ethylhexanol, the precursor to the polyi vinyl chloride) (PVC) plasticizer, DOP. 

Butadiene Nitrosite, C4H6N203 mw 130.10 N 21.53% formed when large concns of butadiene Butanol. Same as Butyraldehyde... 

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