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0 INTRODUCTION
Design is a creative process whereby an innovative solution to a problem is conceived.
In this modern age of industrial competition, a successful chemical engineer needs more than a
knowledge and understanding of the fundamental sciences and the related engineering
subjects such as thermodynamics, reaction kinetics, and computer technology. The engineer
must also have the ability to apply this knowledge to practical situations for the purpose of
accomplishing something that will be beneficial to society. However, in making these
applications, the chemical engineer must recognize the economic implications which are
involved and proceed accordingly.
All design starts with a perceived need. In the design of a chemical process, the need is the
public need for the product, creating a commercial opportunity, as foreseen by the sales and
marketing organization. Within this overall objective, the designer will recognize sub-objectives,
the requirements of the various units that make up the overall process.
Before starting work, the designer should obtain as complete, and as unambiguous, a
statement of the requirements as possible. If the requirement (need) arises from outside the
design group, from a customer or from another department, then the designer will have to
elucidate the real requirements through discussion. When writing specifications for others,
such as for the mechanical design or purchase of a piece of equipment, the design engineer
should be aware of the restrictions (constraints) that are being placed on other designers. A
well-thought-out, comprehensive specification of the requirements for a piece of equipment
defines the external constraints within which the other designers must work.
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Some physical and chemical properties of MEK are presented in Table 1 below. Because of
MEKs 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.
3.1.2 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.
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Property
Value
72.1
Melting point, C
-86.3
Boiling point, C
79.6
804.5
2.41
Critical temperature, C
260
4.4
24.6
15.45
2435
103.3
279.5
Specific heat:
vapor at 137C, J/(kg*K)
liquid at 20C, J/(kg*K
1732
2084
32.8
-6.6
Ignition temperature, C
515.5
2
12
77.5
0.54
0.41
0.34
190
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Figure 2 illustrates the production and use of MEK. Major end-users of MEK include protective
coating solvents (61 percent), adhesives (13 percent), and magnetic tapes (10 percent).
Vinyls are the primary resins that employ MEK as a solvent. Methyl ethyl ketone is commonly
used as a solvent in rubber cements, as well as in natural and synthetic resins for adhesive use.
It is also the preferred extraction solvent for dewaxing lube oil and is used in printing inks.
Overall, the projected use of MEK is expected to gradually decline. The growing trend towards
water-based, higher-solids, and solvent-less protective coatings, inks and adhesives is reducing
the demand for MEK. The installation of solvent recycling facilities will also reduce
requirements for fresh solvent production. Although MEK is favored as a solvent due to its low
density, low viscosity, and high solvency, its addition on the EPAs hazardous air pollutants list
will likely cause potential users to consider other comparative solvents such as ethyl acetate.
END USE
Protective coating solvent
Adhesive solvent
PRODUCTION
Dehydrogenation of secondary
butyl alcohol
By-product of Butane
oxidation
Magnetic tapes
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3.2 APPLICATIONS
3.2.1 as a solvent
Butanone is an effective and common solvent and is used in processes involving gums, resins,
cellulose acetate and nitrocellulose coatings and in vinyl films. For this reason it finds use in the
manufacture of plastics, textiles, in the production of paraffin wax, and in household products
such as lacquer, varnishes, paint remover, a denaturing agent for denatured alcohol, glues, and
as a cleaning agent. It has similar solvent properties to acetone but has a significantly slower
evaporation rate. Butanone is also used in dry erase markers as the solvent of the erasable dye.
3.2.2 as a welding agent
As butanone dissolves polystyrene, it is sold as "polystyrene cement" for use in connecting
together parts of scale model kits. Though often considered an adhesive, it is actually
functioning as a welding agent in this context.
3.2.3 Other uses
Butanone is the precursor to methyl ethyl ketone peroxide, a catalyst for some polymerization
reactions. It can also initiate crosslinking of unsaturated polyester resins.
3.3 SAFETY
3.3.1 Flammability
Butanone can react with most oxidizing materials, and can produce fires. It is moderately
explosive; it requires only a small flame or spark to cause a vigorous reaction. Butanone fires
should be extinguished with carbon dioxide, dry chemicals or alcohol foam. Concentrations in
the air high enough to be flammable are also intolerable to humans due to the irritating nature
of the vapor.
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OH
(1)
CH3CH=CHCH3
Butene
(2)
OH
CH3CHCH2CH3
Aqueous
H2SO4
Zn or Brass
400-550C
CH3CH2CH3
Sec-butyl alcohol
CH3CCH2CH3
MEK
H2
Hydrogen gas
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 550C (750 and 1,025F). A mean residence time of two to eight
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Preheater
Reactor
Condenser
Hydrogen
Scrubber
Solvent
Column
Product
storage and
loading
3
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 highboiling 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
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advantages of this process include a better yield (typically 3 percent better), longer catalyst life,
simpler product separation, and lower energy consumption.
4.2 N-BUTANE OXIDATION
Another method of manufacturing Methyl ethyl ketone is by liquid-phase oxidation of nbutane. However, MEK has occasionally been commercially available in significant quantities
from the liquid-phase oxidation of butane to acetic acid. Depending on the demand for acetic
acid, this by-product methyl ethyl ketone can be marketed or recycled. This subsection
discusses MEK production via n-butane oxidation.
4.2.1 N-butane oxidation description process
Figure 4 illustrates the liquid-phase oxidation of n-butane. Initially, n-butane and compressed
air or oxygen are fed into a reactor (Step 1) along with a catalyst, typically cobalt, manganese or
chromium acetate to produce acetic acid, MEK and other by-products such as ethanol, ethyl
acetate, formic acid, and propionic acid. This process produces the following chemical reaction:
O
CH3CH2CH2CH3 +
n-butane
O2
Oxygen
or air
CH3COH + CH3CCH2CH3 +
Acetic acid
MEK
Other byproducts
H2O
Water
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Air is bubbled through the reactant solution at 150 to 225C (300 to 440F) with pressures of
about 5.5 MPa (800 psi). Conditions must be carefully controlled to facilitate MEK production
and prevent competing reactions that form acetic acid and other by-products. Process
conditions can be varied producing different ratios of product components through the choice
of raw material, reaction conditions, and recovery methods.
Vapors containing crude acetic acid and the various by-products including MEK are separated
from unreacted n-butane and inert gases (Step 2), then stripped or flashed to remove dissolved
butane and inert gases (Step 3), and sent to the purification section (Step 4). Unreacted
nitrogen leaving the reactor carries various oxidation products (formic, acetic, and propionic
acids; acetone, MEK, methanol, etc.) and some unreacted butane and is sent to a separator
(condenser) for removal/recycling of unreacted hydrocarbons (Step 5).
The purification section of the plant is complex and highly specialized utilizing three phase
distillation in conjunction with straight extraction. The low-boiling organics such as MEK are
separated from the crude acetic acid by conventional distillation. Azeotropic distillation is used
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to dry and purify the crude acetic acid. Recovery and purification of the various by-products
require several distillation columns and involve extractive distillation or azeotrope breakers or
both. Liquid organic wastes are typically burned in boilers to recover their heat value.
4.3 N-BUTENE OXIDATION
A new one-step process that converts olefins to ketones called OK technology was developed.
Specifically, MEK is produced via direct oxidation of n-butenes at about 85C (185F) and 690
kPa (100 psi), using a proprietary, and homogenous non-chloride catalyst. Advantages of this
process are that it is noncorrosive, environmentally clean, and economical because of low
capital investment and low energy needs. The process is currently in lab-scale operation;
however, plans are underway to design a facility for large scale production.
4.4 JUSTIFICATION OF THE PROCESS USED
The justification of the method used was based on the problem statement given to the group
by the supervisor.
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4.5 DISTILLATION
Distillation as a separation process is indispensable in the production of methyl ethyl ketone
from dehydrogenation of 2-butanol.
The separation of liquid mixtures by distillation depends on differences in volatility between the
components. In distillation, the greater the relative volatilities, the easier the separation.
The basic equipment required for continuous distillation consists of column, a re-boiler and a
condenser system.
Vapor flows up the column and liquid counter-currently down the column. The vapor and liquid
are brought into contact on plates, or packing. Part of the condensate from the condenser is
returned to the top of the column to provide liquid flow above the feed point (reflux), and part
of the liquid from the base of the column is vaporized in the re-boiler and returned to provide
the vapor flow.
In the section below the feed, the more volatile components are stripped from the liquid and
this is known as the stripping section. Above the feed, the concentration of the more volatile
components is increased and this is called the enrichment, or more commonly, the rectifying
section.
If the process requirement is to strip a volatile component from a relatively non-volatile
solvent, the rectifying section may be omitted, and the column would then be called a stripping
column.
In some operations, where the top product is required as a vapor, only sufficient liquid is
condensed to provide the reflux flow to the column, and the condenser is referred to as a
partial condenser. When the liquid is totally condensed, the liquid returned to the column will
have the same composition as the top product. In a partial condenser the reflux will be in
equilibrium with the vapor leaving the condenser. Virtually pure top and bottom products can
be obtained in a single column from a binary feed, but where the feed contains more than two
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components; only a single pure product can be produced, either from the top or bottom of
the column.
In engineering terms, distillation columns have to be designed with a larger range in capacity
than any other types of processing equipment, with single columns 0.310 m in diameter and
375 m in height. Designers are required to achieve the desired product quality at minimum
cost and also to provide constant purity of product even though there may be variations in feed
composition.
A distillation unit should be considered together with its associated control system, and it is
often operated in association with several other separate units.
The vertical cylindrical column provides, in a compact form and with the minimum of ground
requirements, a large number of separate stages of vaporization and condensation.
A complete unit will normally consist of a feed tank, a feed heater, a column with boiler, a
condenser, an arrangement for returning part of the condensed liquid as reflux, and coolers to
cool the two products before passing them to storage.
The reflux liquor may be allowed to flow back by gravity to the top plate of the column or, as in
larger units, it is run back to a drum from which it is pumped to the top of the column. The
control of the reflux on very small units is conveniently effected by hand-operated valves and
with the larger units by adjusting the delivery from a pump.
In many cases the reflux is divided by means of an electromagnetically operated device which
diverts the top product either to the product line or to the reflux line for controlled time
intervals.
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CH3CH2CH3CHOH
2-butanol
CH3CH2CH3CO
MEK
H2
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 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.
5.1.2 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.
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2-butanol
Reactor
(dehydrogenation)
Unreacted
alcohol and
MEK
To flame
stack
Unreacted
2-butanol
Gaseous
products
Coolercondenser
H2
Uncondensed
MEK & alcohol
Absorption
column
MEK and
alcohol
Water
0.5% w/w MEK
Extractor
TCE
(trichloroethyl
ane)
Extract
Distillation
column 1
Crude product
Distillation
column 2
Pure MEK
(99.9%)
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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.
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5.2.2 MATERIAL BALANCE FOR THE PRODUCTION METHYLETHYLKETONE (MEK) FROM 2BUTANOL
Basis used: 1 hour
The material balance was done around the following units:
(1) Reactor
2-butanol XF
MEK
Reactor
X (kg)
2-butanol
H2
XR
Yields
CH3CH2CH3CO + H2
72=0.8554
Mass of 2-butanol is
Mass of then H2 is 0.01188 2=0.0276
X (kg)
Reactor
MEK = 0.8554
2-Butanol=
H2 =0.02376
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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:
84% MEK= 0.8 0.8554
92% 2-Butanol=0.92
Incondensable stream comprises:
H2=
2-Butanol
MEK
MEK = 0.8554
Coolercondenser
2-Butanol=
(Non-condensable)
MEK
2-Butanol
H2=
H2=
(Condensate)
MEK
2-butanol
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MEK
(non-condensable)
MEK
H2O
K
MEK
Absorption
column
2-Butanol
2-Butanol
H2=
H2=
J
MEK
2-Butanol
H2O=
Overall balance
-value in terms of
MEK
2-Butanol
H2O
Absorption
column 2
MEK
Butanol
H2
H2=
MEK
H2O
and
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Raffinate: MEK
H2O
{
Stream J: MEK
H2O
2-butanol
MEK
2-butanol =
H2O
Raffinate
: MEK
H2O
Extractor
R
MEK
2-butanol
TCE
Overall balance
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(Which is approximately = )
(5) Distillation column 1
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
2-Butanol
Distillation
column 1
MEK
2-Butanol
TCE
The material balance for the second distillation column is given as follows;
MEK
2-Butanol
Distillation
column 2
2-Butanol:
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H2
3) Absorption column
Entering stream:
MEK
2-Butanol
H2
Raffinate stream:
MEK
H2O
Leaving stream:
MEK
H2O
2-butanol
4) Extractor
Entering stream:
MEK
H2O
2-butanol
Recycle stream = TCE (Tri chloro ethylane)
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TCE:
Leaving stream:
MEK:
2-butanol
5) Distillation column 1
Entering stream:
MEK:
2-butanol
Leaving stream:
MEK:
2-butanol
TCE:
6) Distillation column 2
In = out
Entering stream:
MEK:
2-butanol:
Leaving stream
99.99% pure MEK at 1000kg/hr
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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.
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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:
is taken as
Where
is the total enthalpy of the product streams, including unreacted materials and byproducts, evaluated from a datum temperature of 25C;
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is the is the total enthalpy of the feed streams, including excess reagent and inerts,
evaluated from a datum of 25C;
Qr is the total heat generated by the reactions taking place, evaluated from the standard heats
of reaction at 25C (298 K).
This equation can be written in the form:
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5.3.1 ENERGY BALANCE FOR THE PRODUCTION METHYLETHYLKETONE (MEK) FROM 2BUTANOL
The energy balance was carried around the cooler condenser and the second distillation
column (final purification stage). The balances are as indicated below.
4.3.1.1 Cooler condenser
MEKMEK = 0.8554
2-Butanol=
2-butanol 140.74 kg
H2=
H2 27.87
kg
Coolercondenser
MEK=
(Non-condensable)
2-Butanol
H2=
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.
Energy balance for MEK
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,
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Sensible heat to lower the temperature of the condensate MEK from 79.6 C to 32 C,
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QC
F=1140.52kg/h
XF=0.88
D=1000kg/h
XD=0.999
QR
B=140.52kg/h
XB=0.0088
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QC
V
HV
R
HR
D
HD
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Sensible heat
=
Boiling point of methyl ethyl ketone
=79.6 (352.6 K)
Sensible heat of MEK,
=0.026362
The quantity of heat that needs to be extracted from the condenser by the cooling fluid is
obtained as follows.
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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
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Heat effects (heats of solution, heat losses to and from the column etc.) are
negligible.
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.
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In the design done for the distillation column 2 the following criteria was followed.
1. Specification of degree of separation required
2. Selection of the operating conditions
3. Selection of the type of contacting device e.g. plates , pickings
4. Determining the stage and reflux requirements.
5. Sizing the column e.g diameter and height.
Assumptions made in the design of the distillation column:
Equimolar overflow
Total condenser
Partial reboiler
Theoretical plates i.e perfect phase equilibrium exists between both phases
leaving the plate.
A reflux ratio of 16 was used as calculated based on the minimum reflux ratio.
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QC
F=1140.52kg/h
XF=0.88
D=1000kg/h
XD=0.999
QR
B=140.52kg/h
XB=0.0088
The following vapour liquid equilibrium data was used to draw the VLE curve.
0.088
0.278
0.383
0.467
0.478
0.582
0.702
0.803
0.855
0.900
0.192
0.468
0.583
0.644
0.655
0.737
0.823
0.885
0.905
0.940
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1.2
1
y'
0.8
0.6
0.4
0.2
0
0
0.2
0.4
0.6
0.8
xF
1.2
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The above equation is plotted in the curve as shown below, and the McCabe Thiele method is
used to determine the number of stages.
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1.2
q-line
1
stripping
operating line
0.8
VLE curve
rectifying
operating
line
0.6
45 line
0.4
0.2
xB
xD
0
0
0.2
0.4
0.6
0.8
1.2
From the above analysis using the McCabe Thiele method, the theoretical number of stages
was obtained as 12 stages.
Ideal number of stages obtained= 12
i.e.
Where
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To obtain the mass flow rate of the gas and the liquid the following balance is carried out as
below.
VR
R=LR
VS
LS
) (
)
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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.
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7.0 CONCLUSION
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.
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8.0 REFERENCES
1. Chemical Engineering Design, 4th Edition by R.K Sinnot.
2. Unit Operations of Chemical Engineering, 5th Edition by McCabe and Smith.
3. Li, Y.L., Production technology and market analysis of methyl ethyl ketone, Fine and
Specialty Chemicals, 12(18), 2225(2004). (in Chinese)
4. Zhang, Y.X., Production technology and application status of methyl ethyl ketone,
Journal of Henan Chemical Industry, 11(1), 5155(2003). (in Chinese)
5. Distillation: An Introduction by M. T Tham.
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).
8. Perrys Chemical Engineering Handbook.
9. Coulson and Richardsons Chemical Engineering, Volume 2, Fifth Edition.
10. Lecture notes from CHP 461 (Chemical Engineering Design I) and CHP 372 (Mass
Transfer I)
11. www.wikipedia.org.
12. www.basf.com
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