Methyl Ethyl Ketone: A Techno-Commercial Profle INTRODUCTION M ethyl ethyl ketone [1] (MEK) (CAS No.: 78-93-3), is a fammable, colourless liquid with a sharp, sweet butterscotch odour reminiscent of acetone. It is soluble in four parts water and miscible with al- cohol, ether, acetone, and benzene. It is lighter than water and may be expected to foat while rapidly dissolving . It is unsymmetrical or mixed ali- phatic ketone. Its IUPAC name is 2-Butanone. Other names are: Methyl- acetone and Meetco. MEK is the second link in the ho- mologous series of aliphatic ketones and next to acetone, the most important commercially produced ketone. It is produced in large quantities. Nearly half of it is used in paints and other coatings. It dissolves many sub- stances and is used as a solvent in pro- cesses involving gums, resins, cellulose acetate, nitrocellulose coatings, in vinyl flms, in the synthetic rubber industry, plastics, textiles, in the production of paraffn wax, and in household pro- ducts such as lacquer, varnishes, paint remover, a denaturing agent for de- natured alcohol, glues and as a cleaning agent. MEK is also used in dry erase markers as the solvent of the erasable dye and in synthesis of MEK peroxide, a catalyst for some polymerization reactions. Natural occurrence[g] MEK occurs naturally in volcanoes, forest fres, and products of biologi- cal degradation. It is made by some trees and found in some fruits and vegetables in small amounts. Sources of MEK in the environment are exhaust from jet and internal combustion en- gines, and industrial activities such as gasifcation of coal. It is also found in substantial amounts in tobacco smoke. Properties Physical properties[1] MEK is a colourless liquid. Its odor resembles that of acetone. It is only partially miscible with water and it is completely miscible with most organic solvents. In fact, it forms binary and ternary azeotropic mixtures in combi- nation with water and several other organic solvents (Table 1). Chemical properties[1] MEK is stable under normal condi- tions and in absence of air. It is unsa- ponifable and does not form corrosive products under hydrolysis. It is heat and light stable. It only decomposes after prolonged exposure of UV. It can be widely utilized in chemical synthesis. Its reactivity centres on the carbonyl group and its adjacent hydrogen atoms. Con- densation, ammonolysis, halogenations and oxidation can be carried out under the proper conditions. Some typical re- actions are described below. Self-condensation Aldol condensation of 2 moles of MEK yields a hydroxyketone, which readily dehydrates to an unsaturated ketone:
Condensation with other compounds Reaction with aldehydes gives higher ketone, as well as ketals and cy- clic compounds, depending on reaction conditions. Ketones are produced by the condensation of MEK with alipha- tic esters. Sec-Butyl amine is formed by reacting MEK with aqueous ammonia and hydrogen: An excess of MEK in this reaction will produce di-sec-butylamine. React- ing MEK with acetylene gives methyl pentynol, a hypnotic compound. Applications[1] MEK is consumed in large quanti- ties in a variety of industries and appli- cations (Table 2). Environmental impact[g] When released into the soil, MEK may leach into groundwater & may evaporate to a moderate extent. When released into water, it may biodegrade to a moderate extent, may evaporate to a moderate extent & is expected to have a DIVYESH ARORA & MOHIT SHARMA Jaypee Institute of Engineering & Technology E-mail: divyesh_134@yahoo.co.in Table 1 Physical properties of MEK Value Molecular weight 72.10 Boiling point 79.6 o C Melting point -86.35 o C Vapour pressure 90.6 mm Hg at 25 o C Vapour density 2.41 (air = 1) Density/specifc gravity 0.805 at -20/4 o C O II CH 3 CCH 2 CH 3 + H 2 O 2 OH I CH 3 CCH 2 CH 3 I OOH O NH 2 II I CH 3 CCH 2 CH 3 + NH 3 +H 2
CH 3 CHCH 2 CH 3 + H 2 O Ni 190 Chemical Weekly April 27, 2010 Special Report while demand in the rest of Asia, ex- cluding Japan, is expected to increase at about 2.6%/year. Growth in Western Europe will be almost fat over the next four years (Table 3). Application-wise consumption pattern[h] Coating solvents are the largest end- use for MEK, accounting for almost half of worldwide demand. Adhesives are the second-largest end use, accounting for almost 20% of demand (Table 4,5). Indian Scenario[j] The current demand in India for MEK is around 10,000-11,000 tons. India is not self-suffcient to meet its demand, so it imports MEK from various coun- tries (Table 6). Cetex Petrochemicals Ltd. is the only producer of MEK in the country. Processes available[2] There are a few pro- cesses listed for the pro- duction of MEK. Catalytic dehydro- genation of secondary butyl alcohol in gaseous phase MEK is prepared by half-life between 10 and 30 days. MEK is not expected to signifcantly bio-accumu- late. When released into the air, this ma- terial is expected to be readily degraded by reaction with photochemically pro- duced hydroxyl radicals & is expected to have a half-life between 1 and 10 days. Global scenario In 2007, publicly available sources reported global production for MEK reached 1,141-kt (kilotons) (2.5 billion pounds). Global demand for MEK was 1,100-kt (2.4 billion pounds). Worldwide[h] MEK demand is forecast to grow at 3.5% over next fve years, to 1.3-mt (million tons) by 2010, according to SRI Consulting. Demand growth will be driven by China, the largest single consumer. Chinese de- mand is projected to grow at 8.5%/year, Table 2 How MEK is used in industries Industry Application Adhesives manufacture Carpet adhesive solvents Electroplating Cold-cleaning solvents Electroplating Vapour degreasing solvents Laboratory chemicals Solvents - extraction Machinery manufacture and repair Solvents Metal degreasing Solvents Paint manufacture Solvents Paint stripping Solvents Paper coating Solvents Pesticide manufacturing (insecticides) Solvents Printing Solvents for fexography & gravure printing Table 3 MEK growth prospects Country Growth (%) China 8.5 Rest of Asia (excluding China & Japan) 2.6 Western Europe 0.0 North America 1.0 Table 4 Applications of MEK by end-use Sector Share of demand [%] Coatings/solvents 58 Adhesives 11 Printing inks 8 Chemicals & pharmaceuticals 7 Magnetic tapes 4 Lube oil dewaxing 2 Others 10 Total 100 Table 5 Major companies producing MEK[i] Country / Company Capacity (ktpa) USA Shell 136 Exxon Mobil 135 Idemitsu Petrochem 135 Japan Toren Chemical 70 Maruzen Petrochem 40 Brazil Oxiteno 90 Germany Sasol Solvents 65 Taiwan Tasco Chemical 60 Taiwan Synthetic 15 France Atofna 50 Romania Petro Brazi 40 Thailand Bangkok Synt. 20 South Korea SK Corp. 15 vapor phase dehydrogenation of 2-bu- tanol. The dehydrogenation of 2-buta- nol is an exothermic reaction (51 KJ/ Kg mol). Special Report Chemical Weekly April 27, 2010 191 Global production of MEK 296 350 300 200 150 100 50 0 250 245 234 170 62 0 39 2007 2002 296 254 234 170 62 0 39 T h o u s a n d s
o f
M e t r i c
T o n s N o r t h
A m e r i c a W e s t e r n
E u r o p e M i d d l e
E a s t J a p a n E a s t e r n
E u r o p e &
A f r i c a O t h e r
A s i a n C o u n t r i e s C e n t r a l
&
S o u t h
A m e r i c a Global consumption of MEK 213 600 500 300 200 100 0 400 180 129 400 14 36 25 2007 2002 220 193 133 490 17 47 28 T h o u s a n d s
o f
M e t r i c
T o n s N o r t h
A m e r i c a W e s t e r n
E u r o p e M i d d l e
E a s t J a p a n E a s t e r n
E u r o p e &
A f r i c a O t h e r
A s i a n C o u n t r i e s C e n t r a l
&
S o u t h
A m e r i c a This is a primary process. The MEK concentration in the reaction mixture increases and reaches its maximum at approximately 350 o C. Copper, zinc or bronze are used as catalysts in gas phase dehydrogena- tion. Commercially used catalysts are reactivated by oxidation, after 3 to 6 months use. They have a life expect- ance of several years. Advantages of the process are: High conversion of 2-butanol; High selectivity of MEK of about 95 mole %; Better yield; Longer catalyst life; Simple production separation; and Lower energy consumption. The disadvantages are: Less economic advantage than liquid phase oxidation of n-Butane.
Liquid phase oxidation of n-Butane MEK is produced as a by-product in the liquid phase oxidation of n-butane to acetic acid. Autoxidation of n-butane takes place in the liquid phase accord- ing to the radical mechanism yielding MEK as an intermediate and acetic acid as end-product with mass ratio 0.2:1.0 by non-catalyzed liquid phase oxida- tion at 180 o C and 53 bars with remix- ing. Continuous oxidation under plug Table 6 Imports of MEK into India [2007-08] [Tons] Country Import Taiwan 672 Japan 2,036 China 1,467 South Africa 3,286 Singapore 39 UK 1,087 Netherlands 45 fow conditions at 150 o C, 65 bars and a residence time of 2-7 minutes forms MEK and acetic acid at a mass ratio of 3:1. This process has slight econo- mic advantage over the dehydrogena- tion of 2-butanol. But the key factor is availability and price of butane. Direct oxidation of n-Butenes (Hoechst-Wacker process) In direct oxidation of n-butanes by Hoechst-Wacker process, oxy- gen is transferred in a homogenous phase on to n-butenes using redox salt pair, PdCl 2 / CuCl 2 . 95 per cent con- version of n-butanes can be obtained with MEK selectivity of about 86 per cent. Disadvantages of the process are: Formation of chlorinated butanone and n-butryaldehyde; and Causes corrosion due to free acids. 192 Chemical Weekly April 27, 2010 Special Report Direct oxidation of n-Butanes, Maruzen process The Maruzen process is similar to the Hoechst-Wacker process except that oxygen is transferred by an aque- ous solution of palladium sulphate and ferric sulphate. The process is commercially good to get MEK via direct oxidation of n- butenes, but is generally not accepted due to formation of undesirable by products. The process is patented and not much information is available. Table 7 Comparative study of all the processes Catalytic dehydro- genation Liquid phase oxidation Direct oxidation Direct oxidation Sec-Butyl benzene hydro peroxide Raw material/(s) Sec-Butyl alcohol Butane Butenes Butenes Sec-Butyl benzene Main products MEK Acetic acid MEK MEK Phenol & MEK By-products MEK Chlorinated butanone and n- butryaldehyde Chlorinated buta- none and n-butry- aldehyde
Current status 88-90% 10-12% Not accepted. Not accepted Uneconomical.
Catalysts Copper, zinc or bronze Non-catalysed PdCl 2 / CuCl 2 Palladium sulphate & ferric sulphate Zeolite beta Conversion Higher conversion rate; 80-95% Low conversion 95% 95% Catalyst life Several years Small Small Selectivity 95% 86% 90% Yield Very high Very low High High Equivalent to phenol Energy consump- tion Very low Very low High Economical feasi- bility Less than liquid phase oxidation Very high Not known Uneconomical Process separation Very simple Not known as process is patented Not known as pro- cess is patented. Phenol & MEK are both produced Sec-Butylbenzene hydroperoxide process This process comprises the steps of oxidizing sec-butylbenzene to ob- tain a reaction liquid containing sec- butylbenzene hydroperoxide as the main product, concentrating the reac- tion liquid by means of a distillation column to obtain a bottom liquid con- taining sec-butylbenzene hydroper- oxide as the main component from the column bottom and decomposing the bottom liquid to obtain phenol and MEK. This process is good in that it manufactures both phenol and MEK, which are important products in chemical industry. However, the dis- advantage is that the process is uneco- nomical. Detailed process description - catalytic dehydrogenation of SBA in gaseous phase Preheater (Steam Heater) In the dehydrogenation of 2-buta- nol, the cold feed of SBA is mixed with Special Report Chemical Weekly April 27, 2010 193 recycle stream and then pumped from the feed tank to a steam heater and heat- ed up to 374K (Stream 1), the heating medium being used is dry saturated steam at 160C. Vaporizer This Stream 1 is further fed to ther- mosyphon vaporizer which is heated by the reactor vapor. The heating medium in vaporizer is heated reaction products discharged from the reactor at 673K i.e. (Stream 5) and itself gets cooled down to 425K. Knockout drum Stream 2 is further fed to knock- out drum to remove entrained liquid. Knockout drum consists of a hollow vertical drum having inclined sieve plates known as demister for the pas- sage of clean gas. Separation in knock- out drum is based on the principle of density difference of the liquid and the clean gas. Super heaters The liquid separated will be re- cycled and the dry alcohol (Stream 3) will be fed to super heaters steam and stream attains a temperature of 673K (Stream 4). The combustion reaction of hydrogen takes place in a furnace and the hydrogen is taken from the absorp- tion column. The heat of combustion of hydrogen is very high so its heat is be- ing utilized here. Reactor (Multi-Tubed Reactor) Stream 4 is fed to the multi-tubed reactor where dehydrogenation reac- tion takes place. The reaction is endo- thermic and the reactor is isothermal, so in order to maintain 400C temperature we need to supply heat from outside and that is being supplied by the fue gas, which is produced in the furnace. The MEK concentration in the re- action mixture increases and reaches its maximum at approximately 500 o C. Copper, zinc or bronze are used as cata- lysts in gas phase dehydrogenation. Commercially used catalysts are reacti- vated by oxidation, after 3 to 6 months use. They have a life expectance of se- veral years. Condenser In the condenser about 80% MEK and SBA are condensed (Stream 7), which is sent for storage while the other stream (Stream 8), which contains satu- rated non-condensable hydrogen along with MEK and SBA at the temperature of 358K. Figure 1: Flow sheet of preparation of MEK from SBA 194 Chemical Weekly April 27, 2010 Special Report Absorption column The vapour is passed on to the bottom of the packed bed absorption column where MEK and SBA are ab- sorbed in water. Absorption of MEK is 98% and SBA is 96% in water. The water (Stream 9) is recycled from the extraction column and its rate is con- trolled to provide an aqueous effuent containing 10% MEK. Extraction column The aqueous effuent (Stream 10) from the absorber is pumped into an extraction column where it is contact- ed with solvent 1,1,2-trichlorethane (Stream 11) to extract MEK and SBA. This solvent is selected because it has the maximum partition coeffcient (3.44), in comparison to other solvents. The raffnate comprises of mainly wa- ter, which is fed back to the absorption column. Solvent recovery column The trichloroethane extract phase (Stream 14) is pumped to a distillation column for the separation of solvent. Initially it is preheated to 371K. The bottom product is solvent, i.e. 1,1,2-tri- chloroethane and the distillate from this column (Stream 15) is MEK and alcohol. The recovery of solvent is 99.5%. The solvent is frst cooled down to room temperature and then fed to the extraction column. MEK product still The distillate from the Solvent Re- covery Column is fed to this distillation column along with the liquid from the condenser (Stream 7), which is mixed frst and then preheated to 354K and then fed into the column (Stream 16). The distillate is MEK and the bottom product is SBA. The SBA discharged from the bottom of this column (Stream 19) will be sent back to alcohol feed tank; therefore it is cooled and then stored (Stream 20). The MEK product will be cooled and stored in a storage tank (Stream 18). The MEK produced is 99% pure. REFERENCES 1. Ullmanns Encyclopaedia Indus- trial Organic Chemicals, Volume 2, (pp. 971- 981). 2. John J McKetta, William A. Cun- ningham, Encyclopaedia Chemical Processes, (pp. 32-49). 3. Distillation, in Robert E. Treybal, Mass Transfer Operations, pp. 435-441. 4. Liquid Liquid Extraction, in Robert E. Treybal, Mass Transfer Operations, pp. 505. WEBSITES a. MEK sales specifcations, www. exxonmek.com/publicfiles/fluids/ aliphatic/northAmerica/sales_spe- cifcations_pdf, as on 2nd July 2009. b. Chemical Profle, MEK; www. scorecard.org; as on 4th July 2009. c. PERP Program, www.nexant.com, as on 5th July 2009. d. MEK, www.weblakes.com, as on 7th July 2009. e. Production sec-Butyl alcohol via n- butane hydration, www.fripps.com, as on 8th July 2009. f. Unit operations, www.chemistry- react.org, as on 10th July. g. Dr. R.B. Williams, International programs of chemical safety, www. inchem.org , as on 12th July. h. Eluira Greiner, MEK, Chemical Weekly, January 17th, 2007. i. ICB, Global MEK capacity, www. ICIS.com, as on 13th July. j. Subhadip Sarkar, Cetex Petrochemi- cals, www.expressindia.com; as on 15 July.