Aqueous

OH
H
2
SO
4

OH
Zn or Brass
400-550C
Butene
Dehydrogenation Process Description
Methyl ethyl ketone manufacture by secondary-butyl alcohol dehydrogenation is a
two-step process where the first step involves the hydration of butenes to produce
secondary-butyl alcohol. The second step consists of the dehydrogenation of
secondary-butyl alcohol yielding MEK and hydrogen gas. These steps are illustrated
by the following reactions:

(1) CH
3
CH=CHCH
3
CH
3
CH2CH
3



(2)
CH
3
CHCH
2
CH
3


Since the first reaction (1) does not involve MEK as a product, this discussion will
focus on the second step of the reaction. Figure 3 illustrates the process of
secondary-butyl alcohol dehydrogenation. Initially, preheated vapours of secondary-
butyl alcohol are passed through a reactor (Step 1) containing a catalytic bed of zinc
oxide or brass (zinc-copper alloy) which is maintained between 400 and 550C (750
and 1,025F). A mean residence time of two to eight seconds at normal atmospheric
pressures is required for conversion from secondary-butyl alcohol to MEK.
Product gases from the reaction vessel are then condensed via a brine-cooled
condenser (Step 2) and sent to a distillation column for fractioning (Step 3). The main
fraction (methyl ethyl ketone) is typically obtained at an 85 to 90 percent yield based
on the mass of secondary butyl alcohol charged. The uncondensed gas may be
scrubbed with water or a non-aqueous solvent to remove any entrained ketone or
Sec-butyl alcohol
Sec-butyl alcohol
MEK
CH
3
CCH
2
CH
3
+ H
2

Hydrogen gas
Solvent Hydrogen
Alcohol to recovery
alcohol from the hydrogen-containing gas (Step 4).The hydrogen may then be re-
used, burned in a furnace, or flared.









A liquid-phase process for converting secondary-butyl alcohol to methyl ethyl ketone
has been developed and is used sometimes. In this process, secondary-butyl alcohol
is mixed with a high-boiling solvent containing suspended finely divided Raney or
copper chromite catalyst. The reaction occurs at a temperature of 150C (300F) and
at atmospheric pressure allowing MEK and hydrogen to be driven off in vapour form
and separated as soon as each is formed. The advantages of this process include a
better yield (typically 3 percent better), longer catalyst life, simpler product
separation, and lower energy consumption.






Preheater Reactor
Product
storage and
loading
Condenser
S
c
r
u
b
b
e
r

C
o
l
u
m
n

Fig. methyl ethyl ketone from secondary butyl alcohol
by dehydrogenation
1 2
4
3
2-butanol MEK Hydrogen
PROCESS DESCRIPTION
DEHYDROGENATION OF 2-BUTANOL
Methyl ethyl ketone (MEK) is manufactured by the dehydrogenation of 2-butanol.A
description of the processes listing the various units used is given below:
Reactor
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 is taken as 100 per
cent.Initially, preheated vapours of secondary-butyl alcohol are passed through a
reactor (Step 1) containing a catalytic bed of zinc oxide or brass (zinc-copper alloy)
which is maintained between 400C and 550C (750F and 1,025F). A mean
residence time of two to eight seconds at normal atmospheric pressures is required
for conversion from secondary-butyl alcohol to MEK.
Cooler-condenser
In the cooler-condenser the reactor off-gases (i.e. product gases) are cooled and
most of the MEK and un reacted alcohol are condensed. Two exchangers are used
but they are modeled 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 second distillation column which
is the final purification stage. The MEK is cooled to a temperature of 32C.The water
is fed to the cooler at a temperature of 24 C.

Absorption column
In the absorption column 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 flare stack.
Extraction column
In the extraction column the MEK and alcohol in the solution from the absorber are
extracted into trichloroethylane (TCE). The raffinate, 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 the
first distillation column.
Distillation column I
In the distillation column the unit separates the MEK and alcohol from the solvent
TCE. The solvent containing a trace of MEK and water is recycled to the extraction
column. The recovery is 99.99%.
Distillation column II
In the second distillation column, also known as the final the purification stage which
produces a 99.9% pure MEK product from the crude product from the first column.
The residue from this column, which contains the bulk of the un reacted 2-butanol, is
recycled to the reactor. The steam generated by the re-boiler in this unit is at a
temperature of 140 C.
The following is the block diagram for the production process of methyl ethyl
ketone.

2-butanol
Un reacted
alcohol and
MEK
Gaseous
products
Uncondensed
MEK & alcohol
To flame
stack
Water
0.5% w/w MEK
MEK and
alcohol
Extract
TCE
(trichloroethyl
ane)
Crude product
H
2

Pure MEK
(99.9%)
Un reacted
2-butanol
























Fig. Block diagram for the production of
methyl ethyl ketone
Reactor
(dehydrogenation)

Cooler-
condenser

Absorption
column

Extractor

Distillation
column 1

Distillation
column 2