c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim10.1002/14356007.a04 475

2-Butanone 1

2-ButanoneWilhelm Neier, Deutsche Texaco AG, Moers, Federal Republic of Germany

Guenter Strehlke, Deutsche Texaco AG, Moers, Federal Republic of Germany

1. Introduction . . . . . . . . . . . . . . . . . 12. Physical Properties . . . . . . . . . . . . 23. Chemical Properties . . . . . . . . . . . 24. Production . . . . . . . . . . . . . . . . . . 34.1. Catalytic Dehydrogenation of

sec-Butyl Alcohol (SBA)in the Gaseous Phase . . . . . . . . . . . 3

4.2. Liquid-Phase Oxidation of n-Butane . 4

4.3. Direct Oxidation ofn-Butenes (Hoechst-Wacker Process) 4

5. Quality, Storage, Transportation . . . 56. Uses . . . . . . . . . . . . . . . . . . . . . . 57. Economic Aspects . . . . . . . . . . . . . 68. Toxicology . . . . . . . . . . . . . . . . . . 69. References . . . . . . . . . . . . . . . . . . 7

1. Introduction

2-Butanone [78-93-3], methyl ethyl ketone,MEK, is the second link in the homologous se-ries of aliphatic ketones and, next to acetone, themost important commercially produced ketone.2-Butanone is produced primarily by dehydro-genation of 2-butanol, analogous to the produc-tion of acetone by dehydrogenation of gaseousisopropyl alcohol on copper, zinc, or bronze cat-alysts at 400 550 C. At 80 95 % sec-butylalcohol conversion, MEK selectivity is > 95 %.In some casesMEK can be produced in the samefacilities as acetone. Butenes (dehydration) andhigher ketones (autocondensation) are byprod-ucts. In 1995, 730 000 t of MEK were producedworldwide.

2-Butanone is produced by ARCO (US),AKZO (NL), Biochimica (ES), BP (GB), Car-bochlor (Argent.), Celanese (US, CA, Mexico),Esso (GB, US), Maruzen (JP), PCUK (FR),Shell (FR, NL, US, CA), Texaco (FRG), Tonen(JP), UCC (US), Sasol (ZA). Interest in MEK asa solvent for paints and adhesives has been grow-ing since the 1980s. In general, MEK is consid-ered to be a competitor for ethyl acetate, espe-cially as a low-boiling solvent. It has broad ap-plication as a solvent for nitrocellulose, celluloseacetate butyrate, ethylcellulose, acrylic resins,vinylacetates, and vinylchloride vinylacetatecopolymer (based on synthetic surface-coatingpreparation). It is favored as a lacquer solventbecause of its low viscosity, high solids concen-tration, and great diluent tolerance.

Moreover, MEK can be used as an activatorfor oxidative reactions, as a selective extractant,as a special solvent for dewaxing mineral oilfractions, and as a chemical intermediate. (seeTable 1).Table 1. Physical data of 2-butanone [9], [10]

Mr 72.11mp, C 86.9bp, C 79.6Relative density,

d204 0.8045d2020 0.80615

Refractive index, n20D 1.3788Evaporation number (ether=1) 2.6Critical temperature, C 262.45Critical pressure, MPa 4.15Critical density, , g/L 0.270Dynamic viscosity at 20 C, mPa s 0.323Surface tension at 20 C, mN/m 24.6Molar heat cp at 23.8 C, J mol1 K1 160.8Heat of fusion, J/mol 7456Heat of vaporization at 79.6 C, J/mol 31.2Combustion enthalpy at constant

pressure, 25 C, kJ/mol 2444.3Thermal conductivity, Wm1 K1

at 0 C 0.15020 C 0.14550 C 0.137

Solubility at 20 C2-butanone in water, mass fraction, % 27.5water in 2-butanone, mass fraction, % 12.5

Flash point (DIN 51755), C 1Explosion limits in air at 20 C, 101.3KPa,

lower, volume fraction, % 1.8upper, volume fraction, % 11.5

Ignition temperature, C 505Ignition class (VED) G 1Explosion class (VED) 1Electric conductivity at 20 C, Ohm1 cm1 5108Dipole moment, Debye 3.18Dielectric constant of the liquid at 20 C 15.45

2 2-Butanone

2. Physical Properties

2-Butanone, methyl ethyl ketone, MEK,CH3COCH2CH3, is a relatively mobile, col-orless liquid. Its typical odor resembles that ofacetone. The compound is only partially water-miscible, whereas it is completely miscible withmost organic solvents. 2-Butanone forms binaryand ternary azeotropic mixtures in combinationwith water and several other organic solvents(see Table 2).Table 2. Binary azeotropic mixtures containing MEK [11]

Second component Mass bp atfraction 1013 hPa,of MEK C

Water 88.7 73.4Benzene 37.5 78.4n-Hexane 29.5 64.3n-Heptane 73.0 77.0Cyclohexane 40 721,3-Cyclohexadiene 40 73Methanol 30.0 63.5Ethanol 60.9 74.0Isopropyl alcohol 68.0 77.5tert-Butyl alcohol 73 77.5Ethyl acetate 18.0 77.0Methyl propionate 52 79.25Propyl formate 55 79.45Chloroform 96.0 79.65Carbon tetrachloride 71.0 73.8Carbon disulde 15.3 45.85Propyl mercaptan 75 55.5Thiophene 55.0 76.0Ethyl sulde 20 77.5

2-Butanonedoes not formabinary azeotropicmixture with toluene, m-xylene, n-butanol,isobutanol, sec-butyl alcohol, 4-methyl-2-pentanol, allyl alcohol, acetic acid methyl es-ter, acetic acid isopropyl ester, acetic acid n-butyl ester, acetic acid isobutyl ester, 1,1-di-chloroethane, isobutyl chloride, propyl bro-mide, ethyl iodide, trichloroethylene, dichloro-bromomethane, isobutyl bromide, formic acid,and acetic acid.

2-Butanone forms ternary azeotropes withwater/benzene and water/carbon tetrachloride[11].

3. Chemical Properties

Under normal conditions and in the absence ofatmospheric oxygen MEK is stable. Care mustbe taken after prolonged storage because perox-ides may form in the presence of oxygen [12].

2-Butanone is unsaponiable and, unlike es-ters, does not form corrosive products upon hy-drolysis. It is heat and light stable. It decom-poses only after prolonged UV exposure (yield-ing ethane, methane, carbon monoxide, ethyl-ene, and diacetyl) [13].

Diacetyl [431-03-8] is formed by oxidationwith airin the presence of special catalysts [14].

Methyl ethyl ketone peroxide [19393-67-0],a polymerization catalyst, is formed by oxida-tion with a 30 % solutionof hydrogen peroxide[15]. Nitric acid and other strong oxidants oxi-dize MEK to a mixture of formic and propionicacids [15].

sec-Butyl alcohol [78-92-2] is obtained bycatalytic reduction with hydrogen [15]. It canalso be formed by electrolytic reduction insodium acetate solution or by reduction withammonium amalgam or lithium aluminum hy-dride. 3,4-Dimethyl-3,4-hexanediol is obtainedby electrolytic reduction in an acidic medium orby reduction with magnesium amalgam [15].

Methyl ethyl ketone forms addition productswith hydrogen cyanide as well as with sodiumand potassium hydrogen sultes. In an alkalinemediumMEKcondenseswith aldehydes to formhigher unsaturated ketones. Condensation withformaldehyde to form methyl isopropenyl ke-tone [563-80-4], an intermediatefor further syn-theses, is of particular interest. During base-catalyzed autocondensationin the liquid phaseand during gase-phase condensation on alkalin-ized copper catalysts, the carbonyl group reactswith the methyl group, whereas during acid-catalyzed condensation the methylene group in-position to the carbonyl group is attacked [16].

Methyl ethyl ketone and citral [5392-40-5]condense toform methylpseudoionone that canbe cyclized to methylionone, a compound usedfor producing synthetic violet perfume.

During condensation with low-molecularaldehydes (during base-catalyzed and acid-catalyzed aldolization) the -position of the car-bonyl group is rst occupied [17], [18].

2-Butanone 3

Thus, the base-catalyzed aldolization withless than amounts of formaldehyde yields 2-methyl butane-1-ol-3-one [17] and exhaustivehydroxymethylation, with reduction of the car-bonyl group (crossed Cannizzaro reaction), pro-duces desoxyanhydroeneaheptite [19].

When MEK is reacted with primary and sec-ondary alcohols, higher ketones are obtained.Reactionwith sec-butyl alcohol gives ethyl amylketone [106-68-3] [20].

Methyl ethyl ketone reacts with polyoxycompounds or epoxides to form cyclic products.

Amyl nitrite [110-46-3] attacks the CH2groupin -position to the carbonyl group andyields themonooxime of diacetyl.

The keto group reacts with amino groupswith elimination of water. In combination withhydroxylamine [7803-49-8], methyl ethylke-toxime, an antiskinning agent, is formed.

Condensation of MEK with aliphatic estersand anhydrides gives -diketones.

Phenols react with MEK to form oxypheny-lene compounds. In combination with phenol,2,2-hydroxyphenyl butane is obtained, a ho-molog of hydroxyphenyl propane (Bisphenol A[80-05-7] ), an importantmaterialfor the produc-tion of synthetic resins.

Methyl ethyl ketone can be halogenated inthe -position. Methyl ethyl ketone reacts withGrignard compounds to form tertiary alcohols.With acetylene in the presence of sodium amide3-methyl-1-pentyn-3-ol [77-75-8] is formed.N-Methyl-formyl-aminobutaneis obtained fromMEK plus N-methylformamide. The Refor-matzky reaction produces the -oxyester frommonobromine-substituted esters [20].

4. Production

Most MEK (88 %) is produced today by dehy-drogenation of sec-butyl alcohol (SBA). SBAcan easily be produced byhydration ofn-butenes(from petrochemically produced C4 rafnates)in a two-step process (catalyst: sulfuric acid),or in a single-step process by direct addition ofwater, acidic ion-exchange resins being used asa catalyst [21]. The remaining 12 % MEK isproduced by processes in which liquid butaneis catalytically oxidized, giving both acetic acidand MEK [22].

The direct oxidation of n-butenes (Hoechst-Wacker process, Maruzen process, [23], [24] )has not been generally accepted, because of un-desired byproducts.

The sec-butylbenzenehydroperoxide routegiving phenol and MEK by acid-catalyzed split-ting [25] is uneconomical. The autoxidation ofliquid sec-butyl alcohol, givingMEKandhydro-gen peroxide [26], and the catalytic oxidative hy-dration of gaseousn-butenes [27] are also uneco-nomical. The oxidation of n-butenes with ethyl-benzenehydroperoxide to form butylene oxides,and subsequent hydration and formation of ke-tones appears to be moderately attractive [28].Styrene, n-butanol, and MEK are obtained incoupled production.

4.1. Catalytic Dehydrogenation ofsec-Butyl Alcohol (SBA) in the GaseousPhase

The catalytic dehydrogenation of SBA is an en-dothermic reaction (51 kJ/mol). The equilibriumconstant for SBA can be calculated as follows[29]:

logKp= 2.790 T1+1.51logT +1.865(T = reactiontemperature, inK)

The MEK concentration in the reaction mixtureincreases with the temperature and reaches itsmaximum at approx. 350 C [30].

Copper [31], zinc [32], or bronze [33] areused as catalysts in gas-phase dehydrogena-tion. The latter two require high dehydrogena-tion temperatures (400 C).Dehydration of SBAto butenes takes place as a side reaction on

4 2-Butanone

zinc oxide. Platinum on alumina [34], copperor chromium [35], [36] as well as copper, andzinc on alumina [34] are recommended as dehy-drogenation catalysts for aqueous SBA.

Commercially used catalysts are reactivatedby oxidation, after 3 to 6 months use. They havea life expectancy of several years. Catalyst lifeand alcohol conversion are impaired by contam-inationwithwater, butene oligomers, and di-sec-butyl ether [37].

Deutsche Texaco developed a process inwhich practically anhydrous sec-butyl alco-hol has been produced since 1983 by di-rect hydration of n-butene, catalyzed by acidicion-exchange resin; it is then dehydrogenatedon a copper-based precipitating catalyst at240 260 C under normal pressure [21], [31].The LHSV (4 L/L of catalyst h), the conversion(90 95 %), and the catalyst life until reactiva-tion becomes necessary (3 4 months) renderthe process economically attractive. (see Fig-ure 1).

Figure 1. Gaseous-phase dehydrogenation of sec-butyl al-cohol (Deutsche Texaco AG process)a) Reactor; b) Oil circulation heating; c) Condenser; d) Sep-arator; e) Refrigerator; f) Distillation

sec-Butyl alcohol is dehydrogenated in amulti-tube reactor. The reaction heat (51 kJ/mol)is supplied by heat transfer oil. The reactionproducts leave the reactor as a gas and are splitinto liquid crudeMEKand hydrogen on cooling.The hydrogen is puried by further cooling. Thereaction is highly selective. Autocondensationto higher ketones (e.g., 5-methyl-3-heptanone)is much lower in comparison to acetone. In ad-dition, the dehydration to butenes on copper cat-alysts is for the most part prevented.

During reaction and subsequent treatment,practically no waste disposal problems arise.

Table 3 lists further processes for the pro-duction of MEK by gas-phase hydrogenation ofsec-butyl alcohol.

4.2. Liquid-Phase Oxidation of n-Butane2-Butanone is a byproduct in the liquid-phaseoxidation of n-butane to acetic acid. Autoxida-tion of n-butane takes place in liquid phase ac-cording to a radicalmechanismyieldingMEKasan intermediate and acetic acid as the end prod-uct. The continuous plug owprocess developedby Union Carbide allows the partial collectionof MEK intermediate [42]. MEK and acetic acid(mass ratio 0.15 0.23 : 1.0) are obtained bynon-catalyzed liquid-phase oxidation at 180 Cand 5.3MPa (53 bar) with remixing. Continuousoxidation under plug ow conditions at 150 C,6.5MPa (65 bar), and a residence time of 2.7minformsMEKandacetic acid atmass ratios of up to3 : 1 [42]. Celanese uses acetic acid as a solventand cobalt acetate and sodium acetate as homo-geneously dissolved catalysts [43]. It is a batchprocess performed at 160 165 C and 5.7MPa(57 bar). MEK and acetic acid are obtained at amass ratio of 0.4 : 1.0.

4.3. Direct Oxidation of n-Butenes(Hoechst-Wacker Process)In the direct oxidation of n-butenes accordingto the Hoechst-Wacker process, oxygen is trans-ferred in a homogeneous phase onto n-butenesusing a redox salt pair, PdCl2/2 CuCl [44], [45].The salt pair is subsequently reoxidized.

n-Butenes can be converted into the follow-ing reaction products (conversions of up to 95 %are attained):Reaction products: Selectivities, mol %MEK 86n-Butyraldehyde 4Chlorinated products 6Carbon dioxide 1

The main disadvantages are: formation ofchlorinated butanones and n-butyraldehyde andcorrosion caused by free acids.

2-Butanone 5Table 3. Further processes for producing methyl ethyl ketone by gase-phase dehydrogenation of sec-butyl alcohol

Company Catalyst H2O Tem- Pressure, Con- Selec- Yield, Ref-content, perature, version, tivity, er-vol % C MPa % mol % mol % ence

Standard Oil ZnO/Bi2O3 0 400 0.1 0.3 80 [38]Esso Research&Eng. ZnO/Na2CO3 /Al2O3 0 413 96 97 97 93 94 [39]Maruzen Oil bronze 0 390 0.3 80 99 79.2 [33]Knapsack Griesheim CuO/CrO 0 270 320 88 93 93 96 [40]Toyo Rayon CuO/NaF/SiO2 300 96 100 [41]Ruhrchemie 60 % Cu, Cr2O3, 260 90 100 90 [35]

MgO, 12 % SiO2,10 % H2O

Veba-Chemie 22 % Cu, 90.4 180 57.3 a 63 b 97.8 c [36]8 % BaCrO4,2 % Cr2O3,0.5 % Na2O,61 % SiO2

Shell-Chemie 0.05 % Pt/Al2O3 0 358 0.6 92.5 93.5 96.3 90 [37]Shell-Chemie 5 % Cu, 5 % Cr/Al2O3 0 286 0.6 81 85 86 92 73 77 [37]a Relative to sec-butyl alcohol.b Relative to di-sec -butyl ether.c Total yield.

The Maruzen process is similar [46], [47].Oxygen is transferred by an aqueous solution ofpalladium sulfate and ferric sulfate.

Other processes employing the same oxygentransfer principle were developed by Consor-tium fur Elektrochemie [48] andEastmanKodak[49]. For further processes, see [5053].

5. Quality, Storage, TransportationIt is possible to produce high-purity MEK(DIN 53247, ASTMD740, BS 1940).

The present sales specications of DeutscheTexaco AG are listed in Table 4.Table 4. Sales specications for MEK

Purity, wt % GC min. 99.7d204 (DIN 51757) 0.804 0.806d2020 0.805 0.807Boiling range, C DIN51751 within 0.5

ASTM D1078 incl. 79.6Acidity

(as acetic acid), mg KOH/g 0.0001Water content, wt %, DIN 51777

ASTM D1364 max. 0.1Color (Pt Co, APHA), ASTM D1209 max. 10Nonvolatile matter, wt % max. 0.002

A stable dilute potassium permanganate so-lution indicates high purity (permanganate timeaccording to ASTMD1363).

Storage life of MEK is limited. Carbon steelcontainers (ST 3529) are suitable for short-term storage and transportation. Stainless steel

(316 SS) or containers with a tin lining are rec-ommended for long-term storage. Once auto-catalysis has started, it continues even if storageis continued in inert containers. During long-term storage the formation of peroxide mustbe prevented. Since MEK is somewhat hygro-scopic, water is absorbed from the air.

The following regulations for transportationof MEK must be observed [54].

IMDG-Code: D 3308, Kl. 3.2 UN no. 1193,RID, ADR, ADNR: class 3, Rn 301, 2301, and6301 respectively, no. 1 a, category Kl n; Eu-ropean Council, Yellow Book 78/79: no. 606-002-00-3; European Communities: Guideline/DVgAst, no. 606-002-00-3; UK: Blue Book,Fla.L. IMDG-Code E 3080; USA: CFR49,172.101, Fla.L.; IATA RAR: art. no. 726 Fla.L.

6. Uses

MEK is an important solvent with propertiessimilar to those of acetone. MEK has the fol-lowing advantages in comparison to other sol-ventswith comparable rates of evaporation: veryhigh power of dissolution, high ratio of dissolvedmatter to viscosity, miscibility with a large num-ber of hydrocarbonswithout impairing the solidscontent or viscosity, favorable volume/mass ra-tio due to its low density.

6 2-Butanone

The following natural substances, plas-tics, and resins can be dissolved in MEK:rosin, ester resins, pentaerythritol ester resins,Congo ester, dammar (dewaxed), nitrocellu-lose, low-molecular cellulose acetate, celluloseacetobutyrate, cellulose acetostearate, methyl-cellulose, epoxy resins, nearly all alkyd andphenolic resins, polyvinylacetate, vinylchlo-ride/acetate mixed polymerizates, vinylchlo-ride/vinylidene chloride mixed polymer-izates, coumarone indene resins, sulfonamideresins, cyclohexanone resins, acrylic resins,polystyrene, chlorinated rubber, polyurethane.

Cellulose triacetate, high-molecularcellulose acetate, poly(vinylchloride),poly(vinylbutyral), polysulde rubber cannotbe dissolved in MEK. Shellac is only partiallysoluble.

Other areas of application are productionof synthetic leather, transparent paper, print-ing inks, aluminum foil lacquers; degreasing ofmetal surfaces; extraction of fats, oils, waxes,natural resins; dewaxing of mineral oils [55].

In contrast to its uses as a solvent, use as achemical feedstock is of minor importance de-spite the great number of possible reaction; how-ever, condensation with formaldehyde to ob-tain methyl isopropenyl ketone, autocondensa-tion to form ethyl amyl ketone, and mixed con-densation with acetone to obtain methyl amylketone are of interest. Methyl ethyl ketoxime,used as an antiskinning agent in lacquers, is ofminor importance. Methyl ethyl ketone perox-ide is used as a polymerization initiator for un-saturated polyesters. Diacetyl serves as a but-ter avorer. The perfume industry reacts MEKwith citral to obtain perfume components suchas methylpseudoionone. Since 1962 MEK ispermitted as an alcohol denaturant in the Fed-eral Republic of Germany (by decree of Bun-desmonopolverwaltung in Offenbach).

7. Economic Aspects

Table 5 shows the 1979 sales (in %) for the vari-ousmarkets in the Federal Republic ofGermany.

The worldwide consumption of MEK in1979 amounted to 642000 t (Western Eu-rope 166000 t, Eastern Europe 18000 t, NorthAmerica 315000 t, Central and South Amer-

ica 34000 t, Asia, Australia, Oceania 100000 t,Africa 9000 t).Table 5. Sales survey (FRG, 1979)

%

Paints, lacquers, printing inks, aluminum foillacquers 40

Coating and printing of plastics 20Chemical industry (incl. sound carrier),

pharmaceutical industry 13Adhesives 11Miscellaneous 16

MEK is also available under the followingnames:

German: Ethylmethylketon, Acetonersatz, -Ketobutan, 2-Butanon

English: Butanone, 2-butanone, MEK, methy-lacetone, meetco

French: Methylethylcetone, butane-2-one,ethylmethylcetone, MEC

8. Toxicology

The odor threshold of MEK is 10 ppm; both,MAK and TLV are established at 200 ppm. Theinhalation of MEK vapor has narcotic effects.The vapor irritates the eyes and the nasal andpharyngeal mucous membranes [54]. Frequentand prolonged contact with liquid MEK causesskin moisture loss and slight irritation [56]. Sen-sitive persons may develop dermatoses [57].Liquid MEK temporarily irritates the eye andcorneas [56].

MEK is usually absorbed through the respira-tory tract. Itmay also be absorbedby the skin, butthe cutaneous LD50 in rabbits is above 8mL/kg[57]. The MEK metabolism has been studied inguinea pigs. MEK is both reduced to 2-butanoland oxidized to 3-hydroxy-2-butanone. How-ever, unlike 2-hexanone and n-hexane, whichare further oxidized to form neurotoxic 2,5-hexanedione after oxidation of the -1 C atom,the hydroxybutanone is not further oxidized, butconverted to 2,3-butanediol [58].

Animal tests have shown that the neurotoxiceffect of 2-hexanone may be potentiated by si-multaneous administration of MEK [59], [60].The chronic inhalation of 200 ppm (MAK, TLV)does not seem to be harmful [61].

2-Butanone 7

Even workroom concentrations of 500 700 ppm over an extended period of time do notcause permanent damage.

The LD50 (oral, rat) is 2500 3400mg/kg[62], [63].

Toxic concentrations for water organisms[54]: average lethal concentration for sh:5600mg/L. Maximum permissible concentra-tions for Pseudomonas putida: 1150mg/L,for Scenedesmus quadricanda: 4300mg/L,for Microcystis aeruginosa: 120mg/L. Forsmall crabs (Daphnia magma) the LC0 is2500mg/L, the LC50 is 8890mg/L, and theLC100 > 10000mg/L.

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8 2-Butanone

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1,4-Butenediol Butanediols, Butenediol, and ButynediolButene Polymers Polyolens