2- Butanol Conversion

Microporous, amorphous Mg-Si-O metallosilicates with a very narrow pore size distribution around 6 A diameter and a typical surface area of ca 350 m /g were obtained from the controlled calcination of compound 22. The resulting Mg-Si-O material was found to be very active in 1-butanol conversion even at 200 °C giving both dehydrogenation and dehydration. 

Butanol conversion to butyl butyrate employing different concentrations of immobilized lipase was examined in the presence of butyric acid and n-butanol at a 1.25 1 molar ratio. Syntheses were performed at 37°C, and immobilized lipase concentration varied from 5 to 50 mg/mL. As expected, completion of the reaction was very dependent on the enzyme... 

With oxygen present a much lower selectivity was attained in acetic acid/CCAld condensations than with either water present or with no additive. Although CCA production was greater, this did not enhance the production of ketones. It was impossible to say whether the inhibition resulted from more total oxidation or from deactivation of active sites for condensation. Flint et al. found that the yield to 4-heptanone from butanol was maximized at a butanol/oxygen ratio of 6/1, using a 40% Ce02/MgO catalyst, at one particular flow rate. At other flow rates the optimum ratio varied from 3/1 to 1/1. They also found that butanol conversion was positive order with respect to oxygen. But they con-... 

Typic2il examples of acid-catalysis of heteropoly compounds are as follows Dehydration of methanol, - > ethanol, - - propanol - - - -"- "- > and butanol, conversion of metanol or dimethyl ether to hydrocarbons, etheration to form methyl /-butyl ether, esterifications of acetic acid by ethanol and pentanol, decomposition of carboxylic acid and formic acid, alkylation of benzene by ethylene and isomerization of butene, o-xylene and hexane. ... 

However, a hquid phase dehydrogenation process, using Raney nickel or Raney copper catalysts in a high-boiling solvent at about 150°C, gave 80-95% secondary butanol conversion to MEK at more than 95% selectivity. 

Figure lA and B. Butanol conversion in oxidation process for supported Zr02 catalysts and Ru catalysts ( 2RuZr, 2Ru5CuZr, 5CuZr, 2RuCe, 2RuTi) at 623 K. 

The main conclusions of this study are the following (a) the metal active phase has influence on the BuOH conversion the Ru seems to be more active toward BuOH conversion, while the type of the support has not a high influence on n-butanol conversion, (b) the type of support improves the selectivity toward the oxidation products the Ce02 is the most selective. 

An example of a specialty olefin from an amyl alcohol is Phillips Petroleum s new process for 3-methyl-1-butene (used in the synthesis of pyrethroids) from the catalytic dehydration of 3-methyl-1-butanol (21,22). The process affords 94% product selectivity and 94% alcohol conversion at 310°C and 276 kPa (40 psig). 

Hydroperoxide Process. The hydroperoxide process to propylene oxide involves the basic steps of oxidation of an organic to its hydroperoxide, epoxidation of propylene with the hydroperoxide, purification of the propylene oxide, and conversion of the coproduct alcohol to a useful product for sale. Incorporated into the process are various purification, concentration, and recycle methods to maximize product yields and minimize operating expenses. Commercially, two processes are used. The coproducts are / fZ-butanol, which is converted to methyl tert-huty ether [1634-04-4] (MTBE), and 1-phenyl ethanol, converted to styrene [100-42-5]. The coproducts are produced in a weight ratio of 3—4 1 / fZ-butanol/propylene oxide and 2.4 1 styrene/propylene oxide, respectively. These processes use isobutane (see Hydrocarbons) and ethylbenzene (qv), respectively, to produce the hydroperoxide. Other processes have been proposed based on cyclohexane where aniline is the final coproduct, or on cumene (qv) where a-methyl styrene is the final coproduct. 

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). 

Methyl-l-butanol [137-32-6 RS 34713-94-5 S(-)- 1565-80-6] M 88.2, b 130°(/ S), 128.6°(S), [a]p -5.8° (neat), d 0.809, n 1.4082. Refluxed with CaO, distd, refluxed with magnesium and again fractionally distd. A small sample of highly purified material was obtained by fractional crystn after conversion into a suitable ester such as the trinitrophthalate or the 3-nitrophthalate. The latter was converted to the cinchonine salt in acetone and recrystd from CHCI3 by adding pentane. The salt was saponified, extracted with ether, and fractionally distd. [Terry et al. J Chem Eng Data 5 403 7960.]... 

The chloranil dehydrogenation of A -3-ketones offers a convenient direct conversion to A -ketones. t-Butanol and xylene are the most suitable solvents. Slightly higher yields have been claimed with mixed organic acid-inert solvent systems, although somewhat lower yields (50-60%) are... 

Sensitized by Acetophenone. A -butanol solution of (114) (2.10 M) and acetophenone (0.8 M) is irradiated for 6 hr at 30° under nitrogen with a Hanau Q 81 high-pressure mercury lamp through a Pyrex-acetone filter (path length 1 cm, cut-off of wavelengths below 3270 A). Better than 98 % of the incident light is absorbed by the acetophenone. A 70% conversion of (114) to the same products as listed above is observed. The ratio (118) (120) is again -2 1. 

Both types of processes, 7r -assisted y, -bond cleavage and P -bonding, have been invoked to operate in the phototransformations of the aldehyde-ketone (153) to products (155), (156) and (158). The conversions have been observed at room temperature in dioxane, t-butanol, ethanol and benzene using light of wavelengths 2537 A or above 3100 A or sensitization by acetophenone. The phosphorescing excited triple state of (153) is very similar to that of testosterone acetate (114), but its reactions are too rapid... 

Ethylenediamine, butanol, 90°, 67-96% yield. These conditions were used when heating with butylamine failed to give clean conversions. 

When [AH] is high, or the reaction is studied at low conversions so that [AH] is nearly constant, the rate constant of interest can be calculated from the yields of acetone and tm-butanol by... 

Finally, epoxides can be converted into other functional groups under certain well-defined conditions. For example, ceric ammonium nitrate (CAN) catalyzes the efficient conversion of epoxides to thiiranes (i.e., 124 125) at room temperature in te/t-butanol <96SYN821>. 

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. 

Chlorine-enhancement may offer a partial solution. The addition of the chlorinated olefin TCE, PCE, or TCP to air/contaminant mixtures has recently been demonstrated to increase quantum yields substantially [1, 2, 6]. We recently have extended this achievement [3], to demonstrate TCE-driven high quantmn efficiency conversions at a reference feed concentration of 50 mg contaminant/m air not only for toluene but also for other aromatics such as ethylbenzene and m-xylene, as well as the volatile oxygenates 2-butanone, acetaldehyde, butsraldehyde, 1-butanol, methyl acrylate, methyl-ter-butyl-ether (MTBE), 1,4 dioxane, and an alkane, hexane. Not 1 prospective contaminants respond positively to TCE addition a conventional, mutual competitive inhibition was observed for acetone, methanol, methylene chloride, chloroform, and 1,1,1 trichloroethane, and the benzene rate was altogether unaffected. 

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