TECHNOLOGICAL INSTITUTE OF THE PHILIPPINES

363 P. CASAL ST., QUIAPO, MANILA

CHEMICAL ENGINEERING DEPARTMENT

EQUIPMENT DESIGN

PRODUCTION OF METHYL ETHYL KETONE

Submitted by:
ABUEL, Johannah Jane C.
ANG, Queenie Anne F.
LAYAG, Vincent Jamille C.
PITORAL, Anna Teresa S.

Submitted to:
Engr. Jopeth Ramis

November 14, 2014

Production of Methyl Ethyl Ketone by Direct oxidation Hoechst-Wacker Process

I.

Process Description
An aqueous solution of PdCl2 and CuCl2 is used as catalyst. Methyl Ethyl Ketone (MEK) formation
had already been observed in the reaction between n-butene and aqueous palladium chloride. The
degree of oxidation lost by the palladium must then be restored so that the following reaction
sequence is involved:

a) Methyl Ethyl Chloride production

n-butene + palladium chloride + water
MEK + palladium + hydrochloric acid
n-C4H8 + PdCl2 + H2O
C4H8O + Pd + 2HCl
b) Oxidation of palladium by cupric chloride
In the Wacker-Hoechst process, metallic palladium is reoxidized by CuCl2, which is then
regenerated with oxygen:
Pd + 2CuCl2
PdCl2 + 2CuCl
2HCl + 1/2 O2
H2O + Cl2
2CuCl + Cl2
2CuCl2
The n-butene and oxygen are charged into the lower part of the reaction tower. On the whole, the
following overall reaction takes place:
n-butene + oxygen
methyl ethyl ketone
n-C4H8 +1/2O2
C4H8O
to which the catalyst solution takes is also added and is circulated via the separating vessel, preheated
to the same temperature, and operating at 1.200 kPa absolute. The exit stream leaving at 120 0C are
flashed at 500 k Pa absolute, to enable the separation of the reactants and products of the reaction
medium in gaseous form, and the regeneration of the catalyst kept in the liquid phase. The reaction
products are separated by cooling and washing with water the unconverted gas is returned to the
reactor after the condition of make-up hydrochloric acid and chlorides to offset any losses.. The organic
compounds, stripped in the gas phase, are recoververd by water scrubbing in an absorption column
operating aat atmospheric pressure around 50 OC, and recycled with the catalyst solution.
Crude MEK obtained during washing of the reaction products is distilled in two stages. The first stage is
an extractive distillation with water in which lights ends having lower boiling points than MEK are
separated at the top, while water and higher-boiling byproducts, are withdrawn together with MEK at
the bottom. In the second column MEK is purified by fractional distillation.

II.

Availability of Raw Materials

In direct oxidation of n-butanes by Hoechst-Wacker process, oxygen is transferred in a
homogenous phase on to n-butanes using redox salt pair, PdCl 2 / CuCl2.

Splitting of 2-phenyl butane hydroperoxide into phenol and methy ethyl ketone, this intermediate
being itself obtained by the alkylation of benzene by means of n-butenes. A number of differences
nevertheless appear between the purification schemes of acetone and methyl ethyl ketone. The
existence of a water/methyl ethyl ketone heteroazeotrope complicates the separation of the
products. (Chauvel & Lefebvre, 1986).

III.

Costing
Methyl ethyl ketone is a mature product with most of its applications only growing slowly.
Regionally, the European and U.S. markets are flat while future growth will be concentrated in Asia.
The Chinese market is the main driver and demand here will rise by 6-7%/year.
Asian methyl ethyl ketone (MEK) prices fell by more than 40% in the three months to mid-August
as a result of weak consumer demand. Prices in northeast Asia settled at $1,6501,750/tonne CFR
(cost & freight), down from $3,0003,300/tonne in mid-May.
Record high prices in April following an extended outage at a 170,000 tonne/year Japanese facility
led end users from downstream sectors such as polyurethane (PU), ink and coatings to switch to
more affordable substitutes.

Strong Chinese exports also helped offset the decline in supply from Japan. Consumption levels
are likely to remain weak in the near-term as prices have not fallen to levels low enough for end
users to consider switching back to MEK.
However, the start of the peak production season in the downstream PU sector in September
may help to support prices. (Yeow, 2007)

IV.

Efficiency
A soluble mixture of P-V-MO oxides and an acetonitrile ligand is used to improve activity and
selectivity with a yield of 85 to 88% efficiency. (Takaoka, 1972).

V.

Manufacturability and Sustainability

In nature, Methyl ethyl ketone (MEK) is made by some trees. It is also found in small amounts in
some fruits and vegetables. Manmade MEK is released into the air from car and truck exhausts.
MEK worldwide is, primarily, produced with n-butene/2-butene as the raw material. A newer
technology involves the direct oxidation of n-butene is solution using palladium and cupric chloride
as catalysts. The main disadvantage of this process is the formation of chlorinated butanones and
b-butryaldehyde and corrosion caused due to free acids. (Chemical Weekly, 2010)

Production of Methyl Ethyl Ketone by Vapor Phase Dehydrogenation of 2-butanol

Process

I.

Process Description
A reactor in which the butanol is dehydrated to produce MEK and hydrogen, according to
the reaction:
CH 3 CH 2 CH 3 CHOH CH 3 CH 2 CH 3 CO+ H 2
The conversion of alcohol to MEK is 88 per cent and the yield can be taken as 100 per cent. A
cooler-condenser, in which the reactor off-gases are cooled and most of the MEK and unreacted
alcohol are condensed. Two exchangers are used but they can be modelled as one unit. Of the
MEK entering the unit 84 per cent is condensed, together with 92 per cent of the alcohol. The
hydrogen is non- condensable. The condensate is fed forward to the nal purication column. An
absorption column, in which the uncondensed MEK and alcohol are absorbed in water. Around 98
per cent of the MEK and alcohol can be considered to be absorbed in this unit, giving a 10 per cent
w/w solution of MEK. The water feed to the absorber is recycled from the next unit, the extractor.
The vent stream from the absorber, containing mainly hydrogen, is sent to a are stack. An
extraction column, in which the MEK and alcohol in the solution from the absorber are extracted
into trichloroethylane (TCE). The rafnate, water containing around 0.5 per cent w/w MEK, is
recycled to the absorption column. The extract, which contains around 20 per cent w/w MEK, and a
small amount of butanol and water, is fed to a distillation column . A distillation column, which
separates the MEK and alcohol from the solvent TCE. The solvent containing a trace of MEK and
water is recycled to the extraction column. A second distillation column, which produces a pure
MEK product from the crude product from the rst column. The residue from this column, which
contains the bulk of the unreacted 2-butanol, is recycled to the reactor.

II.

Availability of Raw Materials

MEK is prepared by vapor phase dehydrogenation of 2-butanol. A 2 step process from
butanes, which are first hydrated to give 2-butanol, is used. The dehydrogenation of 2-butanol is an
exothermic reaction (51 kJ/kmol). The reaction is as follows:

The equilibrium constant for 2-butanol can be calculated as follows:

Where: T = reaction temperature, K

Kp = equilibrium constant, bar

The MEK concentration in the reaction mixture increases and reaches its maximum at approximate
350C. Copper, zinc or bronze are used as catalysts in gas phase dehydrogenation. Sec-butyl
alcohol is dehydrogenated in a multiple tube reactor, the reaction heat being supplied by heat
transfer oil. The reaction products leave the reactor as gas and are split into crude MEK and
hydrogen on cooling. The hydrogen is purified by further cooling. The crude MEK is separated from
uncreated reactants and by-products by distillation.
III.

Costing
Several economic studies have been performed on the production of butanol (traditional
ABE fermentation) from corn, whey permeate, and molasses. New developments in process
technology for butanol production could allow for a significant reduction in the price of butanol.
Petrochemical industries gave capacity to reduce the price of butanol.

IV.

Efficiency
Have a higher conversion of 2-butanol of about 80-95% and high selectivity of MEK of about 95
mole %.

V.

Manufacturability and Sustainability

Commercially used catalysts are reactivated by oxidation with a longer catalyst life after 3 to 6
months use and have a better yield compare to other processes. They have a life expectance of
several years.

Production of Methyl Ethyl Ketone from n-butane by Liquid Phase Oxidation

I.

Process Description

The process starts with the n-butane and compressed air/oxygen being fed to the reactor.The
following reaction will take place in the reactor

nbutane+ oxygen acetic acid+ MEK +other by products +water

In the reactor, air is bubbled through the reactant solution at 150C to 225C with pressures of
about 5.5 MPa. From the reactor, the product mixture is passed through heat exchangers, coolers and then
through a decanter where the vapors containing crude acetic acid and various by-products including methyl
ethyl ketone are separated from unreacted n-butane and inert gases. Then they are stripped or flashed to
remove dissolved butane and inert gases and is sent to the purification section. The unreacted n-butane
and inert gases are sent to a separator for removal/recycling of unreacted hydrocarbons. In the purification
section, three-phase distillation columns are used with straight extraction to recover MEK.

II.

Availability of Raw Materials

The liquid phase of butane is one of the most efficient modern petrochemical processes. The
products of this process are acetic acid, methyl ethyl ketone (MEK), methyl acetate and other substances
which are important chemicals. (M.G. Bulygin, 1965) During this process, the main raw materials are
butane and oxygen.
Butane comes from natural gas, which is colorless, odorless and shapeless in its natural form. This
type of gas is relatively inexpensive to mine and produce since it is extremely abundant in many parts of
the world.
Oxygen is a highly reactive element and is capable of combining with most other elements, it is the
third most abundant element in the universe and makes up nearly 21% of the earth's atmosphere. Oxygen
accounts for nearly half of the mass of the earth's crust, two thirds of the mass of the human body and nine
tenths of the mass of water. Large amounts of oxygen can be extracted from liquefied air through a process
known as fractional distillation. Oxygen can also be produced through the electrolysis of water or by heating
potassium chlorate (KClO3).

III.

Costing

Source: U.S. Energy Information Administration based on Bloomberg Financial-reported prices at Mont
Belvieu, Texas.

IV.

Efficiency
Production of Methyl Ethyl Ketone via liquid phase oxidation will have low conversion and very low
yield which will lead to low production efficiency. (Arora & Sharma, 2010)

V.

Manufacturability and Sustainability

One way to produce methyl ethyl ketone is by liquid phase oxidation of n-butane. In this process
MEK is produced as a by-product in the liquid phase oxidation of n-butane to acetic acid. Autoxidation of nbutane takes place in the liquid phase according 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 oxidation at 180oC
and 53 bars with remixing. Continuous oxidation under plug flow conditions at 150oC, 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
economic advantage over the dehydrogenation of 2-butanol. But the key factor is availability and price of
butane. It also has a very low energy consumption and very high economic feasibility which will result to a
sustainable manufacturing process. (Arora & Sharma, 2010)

SUMMARY OF METHYL ETHYL KETONE (MEK) PRODUCTION SELECTION

References

Arora, D., & Sharma, M. (2010, April 27). Methyl Ethyl Ketone: A Techno-Commercial Profile. Chemical
Weekly.
Chauvel & Lefebvre, (1986). Petrochemical Processes Major Oxygenated, Chlorinated, and Nitrated
Derivatives, 2nd Ed., Editions Technip, 1986.
Divyesh Arora, M. S. (2010). Methyl Ethyl Ketone: A Techno-Commercial Profile. Chemical Weekly.
M.G. Bulygin, E. B. (1965). The Continuous Liquid-Phase Oxidation of n-Butane. Petroleum Chemistry,
U.S.S.R., Volume 6, 55-63.
Sampat, B. G. (2011). Methyl Ethyl Ketone - A Techno-Commercial Profile. Chemical Weekly.
Takaoka, S. (1972). Acetone, Methyl Ethyl Ketone and Methyl Isobutyl Ketone.