Pursuant to instruction from our lecturer we proceeded to come up with a preliminary design
of a process to manufacture 1000kg/h of methyl ethyl ketone from dehydrogenation of 2-
butanol. The design work included coming up with a block diagram, a detailed mass and energy
balance, a flow sheet diagram and a detailed design of a distillation column.
Nature of methyl ethyl ketone (product description)
Methyl ethyl ketone, also known as 2-butanone, is a colorless organic liquid with an acetone-
like odor and a low boiling point. It is partially miscible with water and many conventional
organic solvents and forms azeotropes with a number of organic liquids. MEK is distinguished
by its exceptional solvency, which enables it to formulate higher-solids protective coatings .The
molecular formula of methyl ethyl ketone is CH 3COCH2CH3; its molecular structure is
represented as:
Some physical and chemical properties of MEK are presented in Table 1 below. Because of
MEK’s high reactivity, it is estimated to have a short atmospheric lifetime of approximately
eleven hours. Atmospheric lifetime is defined as the time required for the concentration to decay
to 1/e (37percent) of its original value.
Jvhcghnm,;lkjcbhv bmjbivhjk
Overview of production and use
Generally, Methyl ethyl ketone production is accomplished by one of two processes:
(1) Dehydrogenation of secondary butyl alcohol or
(2) As a by-product of butane oxidation.
Table1: Physical and chemical properties of MEK
Property Value
Structural formula: CH3COCH2CH3
Synonyms: 2-butanone, ethyl methyl ketone, MEK, methyl
acetone
Molecular weight (grams) 72.1
Melting point, °C -86.3
Boiling point, °C 79.6
Density at 20°C, g/L 804.5
Vapor density (air at 101 kPa, 0°C = 1) 2.41
Critical temperature, °C 2
6
0
Critical pressure, MPa 4
.
4
Surface tension at 20°C, dyne/cm 24.6
Dielectic constant at 20°C 15.45
Heat of combustion at 25°C, kJ/mol 2435
Heat of fusion, kJ/(kg*K) 103.3
Heat of formulation at constant pressure, kJ/mol 279.5
Specific heat:
vapor at 137°C, J/(kg*K) 1732
liquid at 20°C, J/(kg*K 2084
Latent heat of vaporization at 101.3 kPa, kJ/mol 32.8
Flashpoint (closed cup), °C -6.6
Ignition temperature, °C 515.5
Explosive limits, volume % MEK in air
lower 2
upper 1
2
Vapor pressure at 20°C, mm Hg 77.5
Viscosity, MPa*s (=cP)
at 0°C 0.54
at 20°C 0.41
at 40°C 0.34
Solubility at 90°C, g/L of water 1
9
0
METHYL ETHYL KETONE PRODUCTION
This section discusses the methods which are used for production of methyl ethyl ketone.
OH
Aqueous
(1) CH3CH=CHCH3 CH3CH2CH3
Butene H2SO4
Sec-butyl alcohol
(2)
OH Zn or Brass CH3CCH2CH3 + H2
CH3CHCH2 400-
550°C MEK Hydrogen gas
CH3
Sec-butyl alcohol
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 550°C (750° and 1,025°F). 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 alcohol from the hydrogen-containing gas (Step 4).The hydrogen
may then be re-used, burned in a furnace, or flared.
Solvent Hydrogen
Scrubber
1
2
4
Condens
Preheater Reactor
er
Product
storage and
loading
Column
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 150°C (300°F) 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.
PROCESS DESCRIPTION
DEHYDROGENATION OF 2-BUTANOL
Reactor
A reactor in which the butanol is dehydrated to produce MEK and hydrogen, according to the
reaction:
CH3CH2CH3CHOH CH3CH2CH3CO + H2
2-butanol MEK Hydrogen
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 400°C and
550°C (750°F and 1,025°F). A mean residence time of two to eight seconds at normal
atmospheric pressures is required for conversion from secondary-butyl alcohol to MEK.
5.1.1 Cooler-condenser
In the cooler-condenser the reactor off-gases (i.e. product gases) are cooled and most of the MEK
and unreacted 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 32 °C. The
water is fed to the cooler at a temperature of 24 °C.
5.1.2 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.
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 unreacted 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.
SBA
Reactor
(dehydrogenation)
Unreacted Gaseous
alcohol and products
MEK
To flame
Co
stack co ole
H nd r-
Unreacted 2 en
se
SBA r
Uncondensed
Ab
co sor MEK & alcohol
lu pti
m
n on
Extractor
TCE
(trichloroethyl Extract
ane)
Distillation
column 1
Crude product
Distillation
column 2
Material balances are the basis of process design. A material balance taken over the complete
process will determine the quantities of raw materials required and products produced.
Balances over individual process units set the process stream flows and compositions.
Material balances are also useful tools for the study of plant operation and trouble shooting.
They can be used to check performance against design; to extend the often limited data
available from the plant instrumentation; to check instrument calibrations; and to locate
sources of material loss.
All mass/material balances are based on the principle of conservation of mass that is massr can
neither be created nor destroyed with an exception of nuclear processes according to Einstein’s
equation; E=mc2.
The general conservation equation for any process system can be written as:
For a steady state process the accumulation term is zero and thus for a continuous steady state
process, the general balance equation for any substance involved in the process can be written
as:
If no chemical reaction takes place, material balance is computed on the basis of chemical
compounds mass basis that are used whereas if a chemical reaction occurs molar units are
used.
Also it is worthwhile to note that when a reaction occurs an overall balance is not appropriate
but a reactant balance (a compound balance) is.
5.1.4 Choosing a Basis
The correct choice of the basis for a calculation will often determine whether the calculation
proves to be simple or complex.
A time basis was chosen in which the results will be presented. The basis for calculations was
chosen as 1 hour and thus results will be presented in kg/h.
5.1.5 MATERIAL BALANCE FOR THE PRODUCTION METHYLETHYLKETONE (MEK) FROM
2- BUTANOL
(1) Reactor
Reactor MEK
SBA XF X (kg)
SBA H2
XR
X (kg )
=0.01335x
74
Moles of the2-Butanol that reacted 0.88 * 0.01369x = 0.01188x
MEK = 0.8554
X (kg) Reactor
SBA= 0.12X
H2 =0.02376
All the components leaving the reactor are discharged directly into the cooler condenser for the
next operation.
(2) Cooler-condenser
Condensate (which is then directly sent to the final purification column) comprises:
H2= 0.0236x
SBA =0.0096x
MEK = 0.01369x
(Condensate)
MEK =
0.7185x
SBA= 0.1104x
MEK
(non-condensable)
K H2O
MEK =0.01369
MEK
Absorption
SBA= 0.0096x column 2-Butanol
H2=
H2= 0.02376x
J
MEK
2-Butanol
H2O=
Overall balance
Performing a new balance around the absorption column to express the -value in terms of
in the above equations gives the following values:
MEK
MEK K H2O
2-Butanol Absorption MEK
H2 column 2 Butanol
H2=
MEK
H2O and
Raffinate: MEK
H2 O
Stream J: MEK { }
H2 O
2-butanol
Raffinate
: MEK
B H2O
MEK
MEK
2-butanol = Q ϑ
H2O Extractor 2-butanol
TCE
R
Overall balance
(Which is approximately = )
For this unit operation, the balances were obtained from the previous unit operation i.e. the
extraction column and are indicated in the block diagram below.
TCE
MEK Distillation
MEK
2-Butanol column 1
2-Butanol
TCE
MEK
Distillation 1000kg/hr (flow rate as given)
2-Butanol column 2
MEK:
2-Butanol:
(Returning to the reactor)
1) Reactor
From the balances carried out in the previous exercise the value of X was obtained as 1172.883
kg based on the 1 hour basis.
In = out
Entering stream:
Leaving streams:
MEK = 2-
butanol H2
2) Cooler condenser
In = out
MEK
2-butanol
Non-condensable
MEK
2-Butanol
H2
3) Absorption column
Entering stream:
MEK
2-Butanol
H2
Raffinate stream:
MEK
H2 O
Leaving stream:
MEK
H2 O
2-butanol
4) Extractor
Entering stream:
MEK
H2 O
2-butanol
Leaving stream:
MEK:
2-butanol
5) Distillation column 1
Entering stream:
MEK:
2-butanol
Leaving stream:
MEK:
2-butanol
6) Distillation column 2
In = out
Entering stream:
MEK:
Leaving stream
As with mass, energy can be considered to be separately conserved in all but nuclear processes.
The conservation of energy, however, differs from that of mass in that energy can be generated
(or consumed) in a chemical process. Material can change form, new molecular species can be
formed by chemical reaction, but the total mass flow into a process unit must be equal to the
flow out at the steady state. The same is not true of energy. The total enthalpy of the outlet
streams will not equal that of the inlet streams if energy is generated or consumed in the
processes; such as that due to heat of reaction.
Energy can exist in several forms: heat, mechanical energy, electrical energy, and are the total
energy that is conserved.
In process design, energy balances are made to determine the energy requirements of the
process: the heating, cooling and power required. In plant operation, an energy balance (energy
audit) on the plant will show the pattern of energy usage, and suggest areas for conservation
and savings.
This is a statement of the first law of thermodynamics. An energy balance can be written for
any process step. Chemical reaction will evolve energy (exothermic) or consume energy
(endothermic). For steady-state processes the accumulation of both mass and energy will be
zero.
The energy balance was carried out around cooler condenser and the second distillation
column. In chemical processes the kinetic and potential energy terms are usually small
compared with heat and work terms, and can normally be neglected.
If the kinetic and potential energy terms are neglected the energy equation reduces to
For many processes the work term will be zero, or negligibly small, and equation above reduces
to the simple heat balance equation:
Hence:
For a practical reactor, the heat added (or removed) Qp to maintain the design reactor
temperature will be given by:
Where
is the total enthalpy of the product streams, including unreacted materials and by-
products, evaluated from a datum temperature of 25°C;
is the is the total enthalpy of the feed streams, including excess reagent and inerts,
evaluated from a datum of 25°C;
Qr is the total heat generated by the reactions taking place, evaluated from the standard heats
of reaction at 25°C (298 K).
∑∫ ∑∫ ∑[ ]
5.3.1 ENERGY BALANCE FOR THE PRODUCTION METHYLETHYLKETONE (MEK) FROM 2-
BUTANOL
The energy balance was carried around the cooler condenser and the second distillation
column (final purification stage). The balances are as indicated below.
Condensate
QR
MEK =
2-butanol
The temperature at which the products of the reactor leave is 400 °C. The condenser cooler
lowers cools the products to a temperature of 32 °C. The energy balance is given as shown in
the calculations below.
Sensible heat to lower the temperature of the condensate MEK from 400 °C to 79.6 °C,
Sensible heat to lower the temperature of the incondensable MEK from 400 °C to 80 °C,
Sensible heat to lower the temperature of the condensate MEK from 79.6 °C to 32 °C,
No of moles of MEK
condensed
QC
F=1140.52kg/h
XF=0.88 R D=1000kg/h
XD=0.999
QR
B=140.52kg/h
XB=0.0088
R D
HR HD
HV = Q C + H R + H D
Values of enthalpy of product (distillate) and reflux are zero as they are both at the reference
temperature. Both are liquid and the reflux will be at the same temperatures as the distillate.
Enthalpy of vapour:
Ln =
=∑ ∫
=79.6 ℃ (352.6 K)
=0.026362 ∫
[ ]
The quantity of heat that needs to be extracted from the condenser by the cooling fluid is
obtained as follows.
QR is obtained by an overall energy balance around the column.
6.0 DESIGN OF DISTILLATION COLUMN 2
Separation of components from a liquid mixture via distillation depends on the differences in
boiling points of the individual components. Also, depending on the concentrations of the
components present, the liquid mixture will have different boiling point characteristics.
Therefore, distillation processes depends on the vapor pressure characteristics of liquid
mixtures.
The vapor pressure of a liquid at a particular temperature is the equilibrium pressure exerted
by molecules leaving and entering the liquid surface. Here are some important points regarding
vapor pressure:
a liquid is said to ‘boil’ when its vapor pressure equals the surrounding
pressure
liquids with high vapor pressures (volatile liquids) will boil at lower
temperatures
the vapor pressure and hence the boiling point of a liquid mixture depends
on the relative amounts of the components in the mixture
Distillation columns are designed using the vapor-liquid equilibrium data for the mixtures to be
separated.
The vapor liquid equilibrium characteristics of the mixture will determine the number of stages
and hence the number of trays required for the separation.
Most distillation columns are designed by use of the McCabe Thiele method.
The McCabe Thiele approach is a graphical one and use the VLE plot to determine the
theoretical number of stages required to effect the separation of the mixture (binary in our
case).
The method assumes constant molar overflow and this implies that:
The design process is simple. Given the VLE data/relationship for the more volatile component,
operating lines are drawn first.
Operating lines define the mass balance relationships between the liquid and
vapor phases in the column.
There is one operating line for the bottom (stripping) section of the column and
one for the top (rectifying) section of the column.
Use of the constant molar overflow assumption also ensures that the operating
lines are straight.
In the design done for the distillation column 2 the following criteria was followed.
The feed to the distillation column contains 88 mol % of the less volatile component (methyl
ethyl ketone) and 12 mol % of the more volatile component (2-butanol).
An overhead purity of 99.9 mol percent is desired while a bottoms purity of 0.1 mol % is
obtained thus the following mole fraction value relate to the more volatile component:
A reflux ratio of 16 was used as calculated based on the minimum reflux ratio.
QC
F=1140.52kg/h
XF=0.88 R D=1000kg/h
XD=0.999
QR
The following vapour liquid equilibrium data was used to draw the VLE curve.
X 0.088 0.278 0.383 0.467 0.478 0.582 0.702 0.803 0.855 0.900
Y 0.192 0.468 0.583 0.644 0.655 0.737 0.823 0.885 0.905 0.940
1.2
y'
0.8
0.6
Y
0.4
0.2
0
0 0.2 0.4 0.6 0.8 xF 1 1.2
X
The theoretical number of stages was determined by the McCabe Thiele method. This is a
graphical method for the determination of the ideal number of stages. This was procedure was
carried as follows.
The minimum reflux rate can be determined mathematically from the endpoints of the
rectifying line at minimum reflux – the overhead product composition point (x D, yD) and the
point of intersection of the feed line and equilibrium curve(x’, y’).
The above equation is plotted in the curve as shown below, and the McCabe Thiele method is
used to determine the number of stages.
1.2
q- line
1
stripping
operating
line
0.8
Y
VL E rve
cu rec ifyi ng
toperati ng
0.6
lin
e
45° ne
li
0.4
0.2
xD
xB
0
0 0.2 0.4 0.6 0.8 1 1.2
X
From the above analysis using the McCabe Thiele method, the theoretical number of stages
was obtained as 12 stages.
The sizing of the column was carried out using Carrillo, Martin and Roselle’s correlation (2000).
[ ]
⁄⁄
Where
VR R=LR
VS
LS
( ) ( )
( )
( ) ( ) ⁄
√
⁄
⁄
⁄
[ ]
√
[ ]
Raschig rings will be used as the contacting device in the distillation column. They are ceramic
in nature are 1/3 mm in size.
Raschig rings are pieces of tube (approximately equal in length and diameter) used in large numbers as
a packed bed within columns for distillations and other chemical engineering processes. They are usually
ceramic or metal and provide a large surface area within the volume of the column for interaction
between liquid and gas or vapour.
They form what is now known as random packing, and enable distillations of much greater
efficiency than the use of fractional distillation columns with trays.
In a distillation column, the reflux or condensed vapour runs down the column, covering the
surfaces of the rings, while vapour from the re-boiler goes up the column. As the vapour and
liquid pass each other counter-currently in a small space, they tend towards equilibrium. Thus
less volatile material tends to go downwards, more volatile material upwards.
Raschig rings made from borosilicate glass are sometimes employed in the handling of nuclear
materials, where they are used inside vessels and tanks containing solutions of fissile material,
for example solutions of enriched uranyl nitrate, acting as neutron absorbers and preventing a
potential criticality accident.
Distillation column design requires the selection of the right various packing and tower sizing to
meet the process, hydraulic, efficiency, and mechanical requirements of the service. Process
considerations include operating conditions, flexibility, and solid handling requirements.
Hydraulic and efficiency criteria involve selection of a suitable packing material that allows for
cost-effective optimization of vessel height vs. diameter.
Determining the number of stages required for the desired degree of separation and the
location of the feed tray is merely the first steps in producing an overall distillation column
design.
Other things that need to be considered are tray spacing; column diameter; internal
configurations; heating and cooling duties. All of these can lead to conflicting design
parameters. Thus, distillation column design is often an iterative procedure. If the conflicts are
not resolved at the design stage, then the column will not perform well in practice.
It can be deduced from the previous section on distillation column design that the number of
trays will influence the degree of separation.
As the feed stage is moved lower down the column, the top composition becomes less rich in
the more volatile component while the bottoms contains more of the more volatile
component. However, the changes in top composition are not as marked as the bottoms
composition.
8.1 REFERENCES
3. Li, Y.L., “Production technology and market analysis of methyl ethyl ketone”, Fine
and Specialty Chemicals, 12(18), 22—25(2004). (in Chinese)
4. Zhang, Y.X., “Production technology and application status of methyl ethyl ketone”,
Journal of Henan Chemical Industry, 11(1), 51—55(2003). (in Chinese)
6. Qi, J., Gao, N., “Market analysis of methyl ethyl ketone”, Petrochemical
Industry Technology, 10(3), 61 — 64(2003). (in Chinese)
7. Ma, Y.S., Su, J., Wang, C.M., “A process of ketone from secondary alcohol
by dehydrogenation”, C.N Pat., 1289753(2001).