Methyl ethyl ketone from 2-butanol

D.G. Austin and G.V. Jeffreys, The Manufacture of Methyl Ethyl Ketone from 2-Butanol, IChemE, UK (1979). 

Austin, D.G., and Jeffreys, G.V., The Manufacture of Methyl Ethyl Ketone from 2-Butanol (A Worked Solution to a Problem in Chemical Engineering Design), The Institution of Chemical Engineers (UK) and George Godwin Ltd. London (1979). 

In the manufacture of methyl ethyl ketone from butanol, the product is separated from unreacted butanol by distillation. The feed to the column consists of a mixture of methyl ethyl ketone, 2-butanol and trichloroethane. What would be a suitable phase equilibrium correlation to use in modelling this process ... 

A 125 ml flask fitted with a magnetic stirring bar, a reflux condenser, a thermometer and a separatory funnel is charged with 7.2 g (9 ml, 0.1 mol) of 2-butanone (methyl ethyl ketone). From the separatory funnel a solution of 1.5 g (0.04 mol, 60% excess) of sodium borohydride in 15 ml of water is added dropwise with stirring at such a rate as to raise the temperature of the readion mixture to 40° and maintain it at 40-50°. Cooling with a water bath may be applied if the temperature rises above 50°. After the addition has been completed (approximately 30 minutes) the mixture is stirred until the temperature drops to 30°. It is then transferred to a separatory funnel and saturated with sodium chloride. The aqueous layer is drained and the organic layer is dried with anhydrous potassium carbonate. Distillation affords 5.5-6.0g (73-81%) of 2-butanol, b.p. 90-95°. 

Catalytic vapor-phase processes for the dehydrogenation of isoalcohols and side-chain aromatics are of great industrial importance. Examples of such processes are the preparation of acetone and methyl ethyl ketone from isopropanol and secondary butanol ... 

Synthol coproducts include alcohols, ketones, and lower paraffins. They are used mainly as solvents in the paint and printing industries, although some alcohols are blended into fuels. In 1992 Sasol began producing 17,500 t/yr 1-butanol [71-36-3] from 5-07-acetaldehyde [75-07-0] and plaimed to start a plant to produce high purity ethanol [64-17-5] in 1993. Acetone [67-64-1] and methyl ethyl ketone [78-93-3] are two ketone coproducts sold as solvents. 

Direct oxidation yields biacetyl (2,3-butanedione), a flavorant, or methyl ethyl ketone peroxide, an initiator used in polyester production. Ma.nufa.cture. MEK is predominandy produced by the dehydrogenation of 2-butanol. The reaction mechanism (11—13) and reaction equihbtium (14) have been reported, and the process is in many ways analogous to the production of acetone (qv) from isopropyl alcohol. 

In petroleum and oxygenate finish removers, the major ingredient is normally acetone, methyl ethyl ketone [78-93-3], or toluene. Cosolvents include methanol, / -butanol [71-36-3], j -butyl alcohol [78-92-2], or xylene [1330-20-7]. Sodium hydroxide or amines are used to activate the remover. Paraffin wax is used as an evaporation retarder though its effectiveness is limited because it is highly soluble in the petroleum solvents. CeUulose thickeners are sometimes added to liquid formulas to assist in pulling the paraffin wax from the liquid to form a vapor barrier or to make a thick formula. Corrosion inhibitors are added to stabili2e tbe formula for packaging (qv). 

In the manufacture of methyl ethyl ketone (MEK) from 2-butanol, the reactor products are precooled and then partially condensed in a shell and tube exchanger. A typical analysis of the stream entering the condenser is, mol fractions MEK 0.47, unreacted alcohol 0.06, hydrogen 0.47. Only 85 per cent of the MEK and alcohol are condensed. The hydrogen is non-condensable. 

Fig. 11. Separation of a mixture of organic solvents using 50 cm long 100 (left) and 320 pm i.d. (right) monolithic capillary columns (Reprinted with permission from [112]. Copyright 2000 Wiley-VCH). Conditions temperature gradient 120 - 300 °C, 20 °C/min, inlet pressure 0.55 MPa, split injection. Peaks methanol (1), ethanol (2), acetonitrile (3), acetone (4), 1-propanol (5), methyl ethyl ketone (6), 1-butanol (7),toluene (8), ethylbenzene (9),propylbenzene (10),butyl-benzene (11)...

Capello et al.16 applied LCA to 26 organic solvents (acetic acid, acetone, acetonitrile, butanol, butyl acetate, cyclohexane, cyclohexanone, diethyl ether, dioxane, dimethylformamide, ethanol, ethyl acetate, ethyl benzene, formaldehyde, formic acid, heptane, hexane, methyl ethyl ketone, methanol, methyl acetate, pentane, n- and isopropanol, tetrahydrofuran, toluene, and xylene). They applied the EHS Excel Tool36 to identify potential hazards resulting from the application of these substances. It was used to assess these compounds with respect to nine effect categories release potential, fire/explosion, reaction/decomposition, acute toxicity, irritation, chronic toxicity, persistency, air hazard, and water hazard. For each effect category, an index between zero and one was calculated, resulting in an overall score between zero and nine for each chemical. Figure 18.12 shows the life cycle model used by Capello et al.16... 

Schmid et al. described a rapid and sensitive high-performance liquid chromatographic method for the determination of dipyridamole in human plasma [69], The column used was a 12.5 cm x 4.6 mm filled with Lichrosorb RP 18, 5 pm. The mobile phase consisted of methanol-0.2 M Tris HC1 buffer (80 20), eluted at a flow rate of 1 mL/min. Spectrofluorimetric detection at an emission wavelength of 478 nm (excitation at 415 nm) was used for detection. The results were confirmed by re-chromatographing the eluate from the column on silica gel G thin-layer plates, which were developed using a solvent system composed of toluene-isopropanol-ethanol-ammonia (70 15 15 1) and ra-butanol-methyl ethyl ketone (80 20). The Rf values of dipyridamole for the two solvent systems are 0.60 and 0.80, respectively. The plates were dried in a stream of cold air, and then inspected under ultraviolet light at 254 nm. 

During the manufacture of methyl ethyl ketone (MEK) from 2-butanol it is necessary to condense a stream of MEK(1) and 2-butanol(2) in the presence of hydrogen (3). In this example, adapted from Austin and Jeffreys (1979), the gas-vapor mixture is fed to the shell side of a shell and tube heat exchanger as shown in Figure 15.6. The heat exchanger has the... 

Deliquescent, orthorhombic, elongated, six-sided tablets from dimethyl phthalate. dj 1.282. mp 45-46. bp0J 83. Fomin of dicyandiamide begins at 122. Dipole moment in benzene at 2Cryoscopic constant (water) 26.8-28.4. Sp ht 0.547 cal/g/ C between 0° and 39. Heat of formation 14.05 kcal/mole (25 ) heat of combustion —176-4 kcal/-mole (25 ) heat of fusion 2.1 kcal/mole. Heat of vaporization 16.4 kcal/mole. Soly (g/100 g soln) in water at 15 77.5, at 43 100 in butanol at 20 28.8, in methyl ethyl ketone 50.5, in ethyl acetate 42.4. Sol in alcohols, phenols, amines, ethers, ketones. Very sparingly sol in benzene, haJogeaated hydrocarbons. Practically insol in cyclohexane. Solid cyanamide should be stored in a cool, dry place. Polymerizes at 122. Optimum pH for storage of solns is 4, Attacks various metals. Solns can be stored in grass provided they are stabilized with phosphoric, acetic, sulfuric, or boric acid. LDM in rats 125 mg /kg orally. 

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