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1.INTRODUCTION ............................................................................................................................1
1.1PHYSICAL PROPERTIES ........................................................................................................1
1.2USES...........................................................................................................................................2
2. MANUFACTURING PROCESS ....................................................................................................4
2.1 PROCESS SELECTION ...........................................................................................................4
2.2 OVERALL PROCESS DESCRIPTION ...................................................................................6
3. MATERIAL BALANCE .................................................................................................................9
4. ENERGY BALANCE ...................................................................................................................16
5. EQUIPMENT DEIGN ...................................................................................................................31
5.1 LIST OF ITEMS TO BE REPORTED ....................................................................................31
5.2 AVAILABLE INFORMATION .............................................................................................31
5.3 ADDITIONAL INFORMATION ...........................................................................................31
5.4 DESIGN METHODOLOGY...................................................................................................35
5.5 DESIGN COMPUTATION (PROCESS)................................................................................41
5.6 DESIGN METHEDOLOGY (MECHANICAL) .....................................................................46
5.7 DESIGN COMPUTATIONAL (MECHANICAL) .................................................................50
6. DESIGN DATA SHEET ...............................................................................................................55
7. NOMENCLEATURE ....................................................................................................................56
8. REFERENCES ..............................................................................................................................58
1.INTRODUCTION
Methyl isobutyl ketone (MIBK) (CAS no. 108-10-1), also known as 4-methyl-2-pentanone,
(chemical formula C6H12O) is a chemically stable compound possessing a bland, ketonic odor and
used generally as a solvent. The structure of MIBK is as follows.
It is by far the most important of all the acetone derivative solvents. In terms of production volume
MIBK lies behind acetone and 2-butanone. The total produced amount of MIBK in world in 1987
is 1,80,000 ton and in 1996 3,80,000 ton [1]. MIBK is a medium evaporating solvent. This higher
ketone homolog of acetone methyl ethyl ketone is miscible with most organic solvents. MIBK also
exhibits strong solvency for many natural and synthetic resins, gums, waxes, oils, cellulose esters
and other coating systems. Water solubility of MIBK is not good compare to other ketone solvents
like acetone and MEK (methyl ethyl ketone). This property makes MIBK an useful liquid-liquid
extraction solvent.
1.1PHYSICAL PROPERTIES
MIBK is a colorless liquid with a less pronounced ketone like odor. Some physical properties are given
below.
Melting point
-80 0C
Boiling point
116 0C
Density20
0.8004
nD20
1.3959
Enthalpy of evaporation
36.15 kJ/mol
1922 kJ/g
Enthalpy of combustion
3740 kJ/mol
14 0C
Ignition temperature
475 0C
G1
MIBK is poorly soluble in water but is miscible with common organic solvents. It forms an
azeotrope with water and a large number of solvents. For example, the azeotrope with water (bp
87.9 0C) contains 75.7 wt.% and that with n-butanol (bp 114.4 0C) 70 wt.% MIBK.
Use
Percentage
68
Rubber anti-ozonates
miscellaneous
Export
10
Total
100
Surface Coating:
In surface coatings, MIBK is often used as the medium-boiling component of nitrocellulose lacquer
solvent blends. It is frequently blended with cheaper aromatic solvents to achieve blended active
solvent characteristics in high solid lacquers.
Due to its strong solvency and low density, MIBK finds application in the higher-solid coating
systems. MIBK has demonstrated that it can be successfully used in high solids acrylic,
acrylic/urethane polyesters, and oil-modified polyesters formulations. These high-solids coatings
are required in many applications where EPA air quality regulations limit the maximum weight of
organic solvent per unit volume of coating. Because of its strong solvency, MIBK can be used to
increase solids content of the coating solution while maintaining desirable viscosity characteristics.
A further use is as a solvent for dyes in printing industry.
Rare Metal Extraction:
A rapidly growing field of application for MIBK is in the recovery, separation and purification of
rare transition elements, usually as their complexes. Typical applications include zirconium from
hafnium for nuclear reactors, tantalum from niobium for electronics and nuclear applications,
tungsten from molybdenum, and uranium from thorium.
2
Others:
A derivative of MIBK, n-(1,3-dimethylbutyl)-n-phenyl-p-phenylenediamine is used as an
antioxidant for rubber. Miscellaneous end uses for MIBK include pharmaceuticals, where it is used
by major antibiotic producers in the extraction and purification of penicillin from the fermentation
broth, in adhesive formulations based on nitrile rubber and acrylics, and in pesticides, in the
removal of paraffins from mineral oil, for the production of lubricating oils where it is used as a
solvent for active ingredients. The importance of MIBK as an intermediate for synthesis is
relatively low. The most important product is 4-methyl-2-pentanone obtained by hydrogenation of
ketone. It has some importance as a polymerization initiator for ethylene and for handling of
unsaturated polyester resins [1].
3. STORAGE AND TRANSPORTATION
MIBK is available with a purity of >99%. Typical specification is given below
Content
>99 wt.%
0.1 % max.
10 max.
114-117 0C
Conditions that could lead to auto-oxidation (presence of air, light, heat or heavy metals) or
condensation (strongly acidic or basic media) should be avoided during storage. Containers of V2A
steel are recommended for both storage and transportation. Hazard codes for transportation are as
follows:
IMDG code: class 3.2
RID/ADR: class 3, number 3 b
CFR 49: 172.101 flammable liquid
UN number: 1245
2. MANUFACTURING PROCESS
There are several commercial processes discussed in the literature for the manufacture of MIBK
from acetone. These include:
i. Low temperature condensation of acetone in the presence of a base catalyst in the liquid phase to
yield di-acetone alcohol (DAA) followed by dehydration of the DAA to mesityle oxide (MO) in the
presence of acid catalyst. MO is then hydrogenated to MIBK in the presence of a nickel catalyst
[2].
ii. Higher temperature condensation of acetone in the liquid phase in the presence of either a basic
or acid catalyst directly to MO followed by hydrogenation to MIBK. Isophorone is a by-product of
this reaction [3,4]. This process is of commercial significance only if Isophorone is recovered as a
co-product since MO yields are lower than low temperature condensation process. Catalyst such as
copper chr..omite[1]or zirconium phosphate [1]is used for condensation, and palladium on
aluminum oxide for the hydrogenation.
iii.Vapour phase condensation of acetone and hydrogen in the presence of a catalyst to directly
form either MO or MIBK [5].
iv. Direct liquid phase condensation-dehydration-hydrogenation of acetone in the presence of
hydrogen using a bi-functional catalyst to form MIBK. For this process a combination of a cation
exchanger with palladium is generally used as a catalyst [1]. The acetone is fed with hydrogen over
the palladium charged catalyst at 1300C and 0.5-5.0 MPa. A selectivity of >95% at a conversion of
< 50% is thereby attained. As a result of the increasing production of acetone by dehydrogenation
of isopropyl alcohol, the production of 4-methyl-2-pentanone as a byproduct in this process is
becoming more important [1].
2.1 PROCESS SELECTION
The low temperature condensation of acetone route and the direct liquid phase condensationdehydration-hydrogenation processes are of commercial significance. Several advantages are
clamed for the one step MIBK synthesis including:
1. Proton catalysis and metal catalysis with one specific resin.
2. The thr..ee steps of condensation, dehydration and hydrogenation all takes place at the same
time.
3. High conversion rate of acetone because MO is removed from the equilibrium.
4. No need for additional separate hydrogenation unit.
But this one step synthesis of MIBK is relatively latest technology and most of the advancement of
the process is copyright protected. The process description of this process is not usually available in
literature. On the other hand the low temperature condensation route is the oldest process for
4
manufacturing MIBK. Most of the plants in world producing MIBK follow this route. Thats why
the low temperature condensation of acetone route is selected for the plant design purpose and
reaction chemistry is discussed in further details.
MIBK Via Low Temperature Condensation Of Acetone
As said earlier, thr..ee distinguished steps are involved in this route of MIBK manufacture, viz.
condensation, dehydration and hydrogenation. These steps are discussed below in detail.
DAA
Acetone
The industrial production of DAA takes place in the liquid phase using an alkaline catalyst. Water
inhibits the condensation reaction, so it is advantageous to use acetone containing not more than 0.5
wt.% water [6]. According to a Shell patent [7], solid catalysts, e.g., Ba(OH)2 or Ca(OH)2 ,
impregnated on a suitable carrier, are used in a fixed bed reactors the condensing agent. Dilute
NaOH can also be used as catalyst in a well-mixed reactor. When dilute catalyst are employed, they
must be removed from the reactor product or neutralized prior to recovery of the DAA.
The reaction of acetone to DAA is equilibrium controlled. Increasing the temperature decreases the
equilibrium concentration of DAA [2]. Temperatures of 10-30 0C are used commercially and at 20
0C
the yield of DAA is about 6 mol/1000 mol catalyst/h using the solid catalyst system. When
using a soluble catalyst in the liquid phase, the reactor residence time is reported to be 5-10 min [2].
The reaction is exothermic and the heat of reaction is 4.9 kcal/g-mol[2].
About 8-10 % conversion (80-90 % of equilibrium conversion) is obtained per pass thr..ough the
reactor. Selectivity to DAA is reported to be 90-95 % [2]. By products are mainly MO and higher
molecular weight condensation products according to the following reaction.
(
acetone
MO
MO [2].Mesitylene and phorone(EQ. 4 and 5) are main by-products of the reaction. The reaction
scheme is shown below.
DAA
)
MO
(
Acetone
Mesitylene
Acetone
Phorone
Hydrogenation of MO to MIBK:
MIBK is produced by hydrogenation of MO either in the liquid or vapour phase. Catalyst employed
for either vapour or liquid phase hydrogenation are nickel [2,8], copper-chr..omium [9], or
palladium on carbon or alumina [10]. The vapour phase hydrogenation is usually carried out at 150170 0C and atmospheric pressure using a space velocity of 0.5 to 1.5 volumes/h/volume of catalyst,
based on the liquid MO feed. The liquid phase reaction is carried out at 60-130 0C and pressure
ranging from 3 to 30 atm. [2]. Liquid hourly space velocities are about 10h-1 when feeding pure MO
to 1h-1 when feeding lower concentrations of MO. Over-hydrogenation to MIBC can occur if the
MIBK concentration in the reactor outlet increases above 90 %. Selectivity to MIBK is 90-98 % if
the conversion of MO is less than 95%. By-products of this reaction include acetone and
isopropanol.
(
MO
MIBK
(
)
(
MIBK
isipropanol
Acetone
MIBC
stabilized with phosphoric acid and stripped free of acetone, producing a 90 % DAA mixture.
Recovery of acetone from DAA should be carried out at low pressure to avoid reversion of the
DAA back to acetone at temperature greater 120 . The crude DAA is mixed with 0.05 wt.%
phosphoric acid and fed to a dehydrating column where acetone and MO-water azeotrope mixture
are distilled overhead. Heavy by-products are purged from the bottom of the column. Acetone is
then recovered for recycle from MO in the MO recovery column. The can further purified from
water prior to hydrogenation if required.
The hydrogenation may be carried out in the liquid phase or the gaseous phase. Hydrogenation in
the liquid phase is a simpler process, since inter alia it is possible to operate at lower temperatures,
the mesityl oxide does not need to be previously evaporated, and there is no need to recondense the
reaction product after completion of the reaction. However, that hydrogenation in the liquid phase
has the drawback that the life of the catalyst is very short. It has now been found that this drawback
can be obviated by treating the crude mesityl oxide with hydrogen peroxide and inorganic base
solution prior to the hydrogenation [11]. Any suitable inorganic base can be used in the treatment,
but relatively strong inorganic bases such as aqueous caustic alkali solutions are particularly
advantageous. Sodium or potassium hydroxides are examples of suitable caustic alkalis which can
be used successfully. The treatment with hydrogen peroxide and inorganic base solution can be
carried out simply by adding an aqueous solution of hydrogen peroxide and base solution to the
mesityl oxide. A good contact between the reagents can be ensured by stirring or other suitable
measures. The contact time does not need to be long; in most cases 10 seconds is quite sufficient. In
practice, however, it is more convenient to work with longer contact times and there is no objection
to this. There is generally no advantage in extending the time of treatment beyond about 30
minutes, however. The hydrogen peroxide and the inorganic base solution can be added to the
mesityl oxide in any given sequence, or simultaneously. In view of the comparatively low degree of
stability of hydrogen peroxide in an alkaline medium, but generally it is advised first to admix the
hydrogen peroxide well with the mesityl oxide and only then to add the inorganic base solution, in
order to prevent unnecessary consumption of hydrogen peroxide. The reaction may be carried out
at room temperature, although there is no abjection to using higher or lower temperatures. The
operating temperature normally lies between about 5 and about 50 C. The quantities of the
reagents required are not large. They can, for example, be used in amounts, per liter of crude
mesityl oxide, ranging from about 0.3 to about 1.0 ml. of hydrogen peroxide solution of 8%
concentration and from about 0.3 to about 1.0 ml. of caustic alkali solution of 10% concentration,
or in equivalent amounts of solutions of other concentrations. The concentrations of the solutions
are not critical, in practice they are so chosen as to make it easy to proportion with the desired
accuracy the small amounts of the reagents required. Hydrogen peroxide solutions of about 5 to
7
about 15% w. concentration in water and aqueous inorganic base solutions of about 5 to about 15
wt.% concentration are conveniently used. After the treatment with hydrogen peroxide and
inorganic base according to the invention, it is sufficient to separate the aqueous phase from the
mesityl oxide in a simple manner, as, for instance, by decantation. Washing with water is possible
but is not generally necessary.
MIBK is produced from MO by hydrogenation in a reactive distillation tower or in a fixed bed
reactor over Ni catalyst in the presence of hydrogen [11]. Raney nickel is preferably employed as
nickel catalyst. Pure MIBK is finally recovered from uncovered MO in a two-step distillation
scheme where lights are removed in the first tower and pure MIBK is recovered as an overhead
product in the second tower.
3. MATERIAL BALANCE
Data required for calculation:
Compound
Chemical
Formula
Molecular
weight
(kg/kmol)
Sp. Heat
(kJ/kg 0C)
Boiling
point @
1atm. (0C)
Heat of
vaporization
(kJ/kg)
Acetone
C3H6O
58
0.084
56.5
523.00
DAA
C6H12O2
116
3.49
166
MO
C6H10O
98
3.84
129
2001.93
-253.54
MIBK
C6H120
100
1.25
117
462.94
-288.54
Mesitylene
C9H12
120
1.16
164.7
Phorone
C9H14O
138
1.50
198.5
60
1.26
108
Isopropanol C3H8O
Hydrogen
H2
14.304
Water
H2O
18
4.188
Standard
heat of
formation
(kJ/mol)
-551.69
880.12
0
100
2245.00
-241.83 (as
vapour)
Inlet (kg/hr.)
Outlet (kg/hr.)
MO
910.00
84.63
Acetone
43.68
18.00
Hydrogen
17.19
MIBK
841.67
Isopropanol
25.79
Total
970.87
9970.87
Inlet (kg/hr.)
DAA
1073
Acetone
79.20
Outlet (kg/hr.)
50.101
MO
910.00
water
170.79
Mesitylene
10.65
Phorone
10.66
Total
1152.20
1152.20
3. DAA REACTOR:
Assumption:
Conversion
and selectivity of reaction (1) is 9% and 59% respectively.
11
Component
Acetone
11993.37
10895.01
Water
24.13
34.06
DAA
1073
MO
15.43
Total
12017.50
12017.50
wt.% water.
Calculation:
Acetone at top: (10895.01 79.01) = 10816
Total distillate flow rate: (100/99.8) 10816 kg/hr. = 10837.67 kg/hr.
Water at top: (10837.67 - 10816) kg/hr. = 21.67 kg/hr.
Component
Outlet (kg/hr.)
Top [4A]
Bottom [5]
Acetone
10895.01
10816.00
79.01
Water
27.67
21.67
5.998
DAA
1079.40
1079.40
MO
15.43
15.43
10837.67
Total
12017.50
1179.85
12017.50
Since in the DAA reactor, some amount of MO and water is produced as the side product, they will
enter into the dehydrating column (MO reactor). So the material balance of the MO reactor and
thereafter that of the MIBK reactor will be changed accordingly. The revised material balances of
these reactors are shown below sequentially.
5. DEHYDRATING COLUMN (MO REACTOR):
The change in material balance is not complex. There is some amount of MO and water in the inlet
stream and they will carry forward. Since the MO reactor is a reactive distillation (RD) tower, the
material balance table is arranged like a distillation tower.
12
Component
Outlet (kg/hr.)
Top [7]
DAA
1079.40
Acetone
79.01
50.10
MO
15.43
927.34
Water
5.998
181.06
Bottom [6A]
Mesitylene
10.65
Phorone
10.66
1158.51
Total
1179.84
21.32
1179.84
6. MO RECOVERY COLUMN:
Assumption:
Distillate composition is similar to raw material composition i.e. 99.8 wt.% acetone and rest 0.2
wt.% water.
Calculation:
Acetone at top: (250.53 225.79) kg/hr. = 24.74 kg/hr.
Total distillate flow rate: (100/99.8) 24.74 kg/hr. = 24.78 kg/hr.
Water at top: (24.78 24.74) kg/hr. = 0.04 kg/hr.
Component
Outlet (kg/hr.)
Top [7A]
Bottom [8]
Acetone
50.10
4.94
45.15
Water
181.066
0.008
181.05
MO
927.35
927.35
4.95
Total
1158.52
1153.56
1158.52
7. DECANTER:
Assumption:
Volume of mixing is neglected.
1ml 8 wt.% H2O2 solution and 1ml 10 wt.% NaOH solution is required per liter of crude MO
solution [11].
Calculation:
Calculation of the volume of the inlet stream:
13
Component
Volume (L/hr.)
Acetone
45.15
792.5
56.97
Water
181.05
1000
181.05
MO
927.35
858.0
1080.82
Total
1318.84
Inlet (kg/hr.)
Outlet (kg/hr.)
Feed stream
Settling
Aqueous
Organic
[9]
agent [9A]
phase [9B]
phase [10]
Acetone
45.15
Water
181.05
MO
927.35
45.15
181.05
927.352
H2O2 solution
6.755
6.755
NaOH solution
6.655
6.655
13.41
194.46
1153.55
Total
1166.96
972.502
1166.96
MO
927.35
102.52
Acetone
45.15
19.47
Hydrogen
17.72
MIBK
841.67
Isopropanol
26.56
Total
990.22
990.22
Outlet (kg/hr.)
Top [14A] Bottom [15]
Acetone
19.47
19.47
Isopropanol
26.56
26.56
MO
102.52
102.52
MIBK
841.67
841.67
46.03
Total
990.18
944.08
990.18
15
The composition of the distillate is 99.8 wt.% MIBK and rest 0.2 wt.% water.
Calculation:
MIBK at top: 4166.67 kg/hr.
Total distillate flow rate: (100/99.8) 4166.67 kg/hr. = 4175.02 kg/hr.
Water at top: (4175.02 4166.67) kg/hr. = 8.35 kg/hr.
Component
Outlet (kg/hr.)
Top [17]
Bottom [16A]
MO
102.41
1.67
100.74
MIBK
841.67
833.33
8.34
835
109.08
Total
944.08
944.08
4. ENERGY BALANCE
1. ACETONE RECYCLED STREAM
Assumption:
Temperature of the make up acetone: 35 0C.
Temperature of the recycled stream: 50 0C
Reference temperature: 25 0C
Calculation:
Heat content of the make up stream [1]: (1172.43 0.084 (35-25)) + (2.34 4.188 (35-25))
kJ/hr.= 1082.84 kJ/hr..
16
Heat content of the recycled stream [20]: (10820.944 0.084 (50-25)) + (21.68 4.188 (5025)) kJ/hr.. = 24993.87 kJ/hr.
Heat content of the mixed stream [2]: (11993.37 0.084 (T-25)) + (24.03 4.188 (T-25))
kJ/hr.
Now,
Heat content of the mixed stream = Heat content of the make up stream + Heat content of the
recycled stream
Or, (11993.37 0.084 (T-25)) + (24.03 4.188 (T-25)) = 1082.84 + 24993.87 Solving we get
0
T = 48.53 C
0
Let chilling water is available at 5 C and 5 C increase in the outlet temperature is possible.
Reference temperature: 25 C
Calculation:
0
mi (kg/hr.)
niHi (kJ/s)
mo (kg/hr.)
noH0 (kJ/s)
Acetone
11993.37
10895.01
Water
24.13
34.06
DAA
1073
MO
15.43
17
Heat content of the outlet stream: (10895.01 0.084 (15-25)) + (34.06 4.188 (15-25)) +
(1073 3.49 (15-25)) + (15.43 3.84 (48.53-25)) kJ/hr. = - 49420.12 kJ/hr..
Extent of reaction, : (no-ni)/ = (10895.01-11993.37)/(-2 58) = 9.4686 kmol/hr.. = 9468.62
mol/hr.
The standard heat of reaction, Hr..o[4]: - 4.9 kcal/mol = - 20.58 kJ/mol Then the enthalpy change
of the reaction, H = Hr..0 + noHo - niHi Putting all the values we get, H = -270367.30
kJ/hr..
Energy balance:
Q Ws = H + Ek + Ep
Q = H = -270367.30 kJ/hr.
26082.99
49420.12
Reaction
293704.43
Chilling water
270367.30
Total
319787.42
319787.42
18
Calculation:
Component
Feed [4]
Massflow rate
(kg/hr..)
10822.87
27.64
1079.16
15.62
Acetone
Water
DAA
MO
Wt %
90.66
0.23
8.98
0.13
Top [4A]
Massflow rate
Wt %
(kg/hr..)
10816.00
99.80
21.66
0.20
Bottom [5]
Massflow rate
Wt %
(kg/hr..)
79.05
6.70
6.01
0.51
1079.44
91.49
15.33
1.30
220563.37
31576.49
512736.08
Reboiler
6687311.91
Condenser
Total
6273397.11
6907875.28
6907875.28
Inlet (kg/hr..)
Mass flowrate
(kg/hr..)
Outlet (kg/hr..)
`Top
Wt %
Massflowrate
(kg/hr..)
Bottom
Wt %
DAA
1079.404
91.49
Acetone
70.01
6.70
50.106
4.33
MO
15.436
1.31
927.34
80.04
Water
5.998
0.50
181.066
15.63
Massflowrate
(kg/hr..)
Wt %
Mesitylene
10.65
10.06
Phorone
10.67
9.99
The standard heat of reaction, Hr..o is calculated from standard heat of formation using the
formula: Hr..o = i Hfproduct - i Hfreactant
The standard heat of reaction, Hr..o: - 56320 kJ/kmol
QB = HD + HW + QC + QL HF - Hr..o = 2049042.42 kJ/hr..
Description
366371.59
41721.52
4441.02
17024536.38
Reboiler
14258739.42
Condenser
Reaction
524068.86
Total
2939635.63
2939635.63
5. MO RECOVERY COLUMN:
Assumption:
The solutions are ideal in nature.
Calculation:
Component
Feed
Massflow rate
(kg/hr.)
Top
Wt %
Massflow rate
(kg/hr.)
Bottom
Wt %
Massflow rate
(kg/hr.)
Wt %
Acetone
50.106
4.33
4.94
99.80
45.158
3.91
Water
181.06
15.63
0.008
0.20
181.05
15.70
MO
927.35
80.04
927.35
80.39
Saturation temperature of mixture is determined using the formula Tsat = Tisat xi Boiling point
of feed: 121.3 0C
Boiling point of distillate: 56.6 0C Boiling point of residue: 121.6 0C
21
417218.88
14.92
417611.13
Reboiler
3291.31
Condenser
Total
3205.89
420756.98
420756.98
6. DECANTER:
Assumption:
Since the concentration of H2O2 and NaOH solution is very low, their specific heat is approximated
as of pure water.
Temperature of H2O2 and NaOH solution is 30 0C
Temperature of the feed stream is 40 0C
Temperature of the organic phase outlet is 40 0C
Calculation:
Heat content of the inlets: (45.158 0.084 (40-25)) + (181.05 4.188 (40-25)) + (927.353.84
(40-25)) + (13.41 4.188 (40-25)) kJ/hr. = 65692.02 kJ/hr.
Let the temperature of the aqueous phase outlet is T
Heat content of the outlets: (45.158 0.084 (40-25)) + (927.35 3.84 (40-25)) +
(183,764.188 (T-25)) kJ/hr. = 267361.87 + 3847.51 (T-25)
We know, Heat content of the inlets = Heat content of the outlets
Or, 324512.99 = 267361.87 + 3847.51 (T-25)
22
65692.02
56.16
11430.22
53472.37
Total
64902.59
64902.59
mi (kg/hr..)
niHi (kJ/s)
mo (kg/hr..)
noH0 (kJ/s)
MO
927.35
102.41
Acetone
45.158
19.47
Hydrogen
17.72
MIBK
841.668
Isopropanol
26.58
The standard heat of reaction, Hr.o is calculated from standard heat of formation using the
formula: Hr.o = i Hfproduct - i Hfreactant
The standard heat of reaction, Hr.o: -35.00 kJ/kmol
Then the enthalpy change of the reaction, H = Hr.0 + noHo - niHi
Putting all the values we get, H = -2511362.29 kJ/hr.
Energy balance:
Q Ws = H + Ek + Ep
Q = H = -2511362.29 kJ/hr..
3436932.7
135906.75
294583.8
Cooling water
Total
502272.45
638178.57
638178.57
24
Calculation:
Component Feed
Massflow rate
Top
Bottom
Massflow rate
Massflow rate
(kg/hr.)
Wt %
(kg/hr.)
Wt %
19.47
1.97
19.47
42.30
Isopropanol 26.56
2.68
26.56
57.70
MO
102.41
MIBK
841.66
Acetone
(kg/hr.)
Wt %
10.35
102.41
10.85
85.00
841.66
89.15
Saturation temperature of mixture is determined using the formula Tsat = Tisat xi Boiling point
of feed: 116.8 0C
Boiling point of distillate: 86.3 0C Boiling point of residue: 118.3 0C
We know, R = L0/D or, L0 = R D = 4.60 kg/hr.
G1 = L0 + D = 253.24 kg/hr.
HG = (21.42 0.084 (86.3-25)) + (29.22 1.26 (86.3-25)) + (21.42 523) + (29.22 880.12)
kJ/hr. = 39286.96 kJ/hr.
HL = (1.94 0.084 (86.3-25)) + (2.65 1.26 (86.3-25)) kJ/hr. = 214.67 kJ/hr.
HD = (19.47 0.084 (86.3-25)) + (26.56 1.26 (86.3-25)) kJ/hr. = 2151.69 kJ/hr.
HW = (102.41 3.84 (118.30-25)) + (841.66 1.25 (118.30-25)) kJ/hr. = 134849.23 kJ/hr. HF =
(19.47 0.084 (116.8-25)) + (102.41 3.84 (116.8-25)) + (841.66 1.25 (116.8-25)) +
(26.56 1.26 (116.8-25)) kJ/hr.. = 132831.34 kJ/hr.
QC = HG - HL - HD = 36920.6 kJ/hr.
QB = HD + HW + QC + QL HF = 137255.74 kJ/hr.
Description
Inlet stream [14]
2151.69
132831.34
Reboiler
36920.6
184626.89
Condenser
Total
173928.6
173928.6
Feed
Massflow rate
(kg/hr.)
Top
Wt %
Massflow rate
(kg/hr.)
Bottom
Wt %
Massflow rate
(kg/hr.)
Wt %
MO
102.41
10.85
1.67
0.20
100.74
92.36
MIBK
841.66
89.15
833.33
99.80
8.33
7.64
Saturation temperature of mixture is determined using the formula Tsat = Tisat xi Boiling point
of feed: 161.9 0C
Boiling point of distillate: 159.7 0C Boiling point of residue: 179.77 0C
We know, R = L0/D or, L0 = R D = 1945.56 kg/hr.
G1 = L0 + D = 13902.82 kg/hr.
HG = (2775.002 1.25 (159.7-25)) + (5.56 3.84 (159.7-25)) + (400.38 27.81) + (2775.002
462.94) kJ/hr. = 1765910.85 kJ/hr..
HL = (1941.66 1.25 (159.7-25)) + (3.89 3.84 (159.7-25)) kJ/hr. = 328939.09 kJ/hr. HD =
(833.33 1.25 (159.7-25)) + (1.67 3.84 (159.7-25)) kJ/hr. = 141175.74 kJ/hr. HW = (8.33
1.25 (179.8-25)) + (100.74 3.84 (179.8-25)) kJ/hr. = 61494.93 kJ/hr.
HF = (841.66 1.25 (161.9-25)) + (102.41 3.84 (161.9-25)) kJ/hr.. = 197865.59 kJ/hr. QC =
HG - HL - HD = 1295796.02 kJ/hr.
QB = HD + HW + QC + QL HF = 292836.23 kJ/hr.
26
Description
197865.59
141175.74
61494.93
Reboiler
292836.23
Condenser
Total
1295796.02
1498467.47
1498467.47
10. PRE-HEATER 1:
Assumption:
High pressure (12.5 bar) saturated steam of temperature 190 0C is available for heating.
Calculation:
Heat load: (1007922.47 (- 242871.32)) kJ/hr. = 68732.72 kJ/hr.
Latent heat of vaporization of saturated steam [15]: 1977.4 kJ/kg
Steam required: (68732.72 /1977.4) kg/hr. = 34.758 kg/hr.
11. REBOILER 1:
Calculation:
Heat load: 6619328.626 kJ/hr.
Latent heat of vaporization of saturated steam: 1977.4 kJ/kg
Steam required: (6619328.626 /1977.4) kg/hr. = 3347.49 kg/hr.
12. CONDENSER 1:
Calculation:
Heat load: 6275974.58 kJ/hr.
Cooling water required: (6275974.58 /4.188 10) kg/hr. = 149856.12 kg/hr.
13. COOLER 1:
Calculation:
Heat load: (366524.344-513359.93) kJ/hr. = -146835.586 kJ/hr.
Cooling water required: (146835.586 /4.188 10) kg/hr. = 3506.102 kg/hr.
14. REBOILER 2:
Calculation:
Heat load: 2049042.538 kJ/hr.
Latent heat of vaporization of saturated steam: 1977.4 kJ/kg
Steam required: (2049042.538 /1977.4) kg/hr. = 1036.23 kg/hr.
15. CONDENSER 2:
27
Calculation:
Heat load: 2517973.77 kJ/hr.
Cooling water required: (2517973.77 /4.188 10) kg/hr. = 60123.53 kg/hr.
Calculation:
Heat content of the outlet stream:
(53.38 1.16 (30-25)) + (53.32 1.50 (30-25)) kJ/hr.. = 709.50 kJ/hr.
Heat load: (709.50 -22221.66) kJ/hr. = -21512.16 kJ/hr.
Cooling water required: (21512.16 /4.188 10) kg/hr. = 513.66 kg/hr.
16. REBOILER 3:
Calculation:
Heat load: 15658.64 kJ/hr.
Latent heat of vaporization of saturated steam: 1977.4 kJ/kg
Steam required: (15658.64 /1977.4) kg/hr. = 7.92 kg/hr.
17. CONDENSER 3:
Calculation:
Heat load: 3131.72 kJ/hr.
Cooling water required: (3131.72 /4.188 10) kg/hr. = 74.778 kg/hr.
18. COOLER 4:
Calculation:
Heat content of the outlet stream: (225.79 0.084 (40-25)) + (905.29 4.188 (40-25)) +
(4636.76 3.84 (40-25)) kJ/hr.. = 64846.43 kJ/hr.
Heat content of the inlet stream: 417611.06 kJ/hr.
Heat load: (64846.43 - 417611.06) kJ/hr. = -352764.622 kJ/hr.
Cooling water required: (1763823.11/4.188 10) kg/hr. = 8423.22 kg/hr.
19. PRE-HEATER 2:
Calculation:
Heat content of the outlet stream: (45.158 0.084 (115-25)) + (927.35 3.84 (115-25)) kJ/hr..
= 320834.22 kJ/hr.
Heat content of the inlet stream: (45.158 0.084 (40-25)) + (927.35 3.84 (40-25)) kJ/hr.. =
53472.37 kJ/hr.
Heat load: (320834.22 53472.37) kJ/hr. = 267361.87 kJ/hr. Latent heat of vaporization of
saturated steam: 1977.4 kJ/kg Steam required: (267361.87 /1977.4) kg/hr. = 135.20 kg/hr.
20. REBOILER 4:
Calculation:
Heat load: 38022.49 kJ/hr.
28
30
5. EQUIPMENT DEIGN
The mass transfer equipment which is selected for detailed design is the final purification column.
It is a distillation column which separates MIBK from MO and gives a product purity of 99.8 wt%
MIBK solution. The column handles 4720.4 kg/hr.. mixture of MIBK and MO having composition
89.15 wt% MIBK and 10.85 wt% MO. A sieve tray column operating at 3 kg pressure is to be
designed for this job.
5.1 LIST OF ITEMS TO BE REPORTED
1. Column sizing (diameter and height)
2. Tray hydraulic design
3. Tray support specification
4. Material of construction
5. Pressure drop
6. Roof and bottom specification
7. Shell, nozzle, bolt, and flange specification.
8. Other accessories and fittings.
9. Condenser Reboiler setup.
10. Column support.
11. Drawing of the column.
31
)+
And the form of this equation which is used to determine the saturation temperature of MIBK is as
follows.
Minimum for these equations is triple point and the maximum is critical temperature (Tc). The
pressure is in bar and the temperature is in kelvin [13].The values of the constants: a, b, c, d are
given below [13]
Component
Tc (K)
Pc (bar)
Tmax (K)
MIBK
605
-8.68118
3.99203
-4.81662
-1.73164
34.1465
605
MO
571.40
3.8222
1190.6904
195.45
571.40
Putting P= 3kg = 2.94 bar, saturation temperature and the saturation pressure is calculated. From
these values vapour-liquid equilibrium (VLE) data is calculated using Raoults law because we
assumed the mixture and the vapour phase ideal.
(Tsat)MIBK = 159.7
(Tsat)MO = 179.8
From the saturation temperature values it is clear that MIBK is more volatile than MO. So MIBK is
designated as component 1 and MO is designated as component 2.
2. The VLE data is calculated using
( )
( )
( )
( )
P1 sat (bar)
P2 sat (bar)
X1
Y1
159.7
160
161
162
163
164
165
166
167
2.940000
2.957839
3.022597
3.088397
3.155251
3.223168
3.292157
3.362229
3.433394
1.870336
1.883699
1.928778
1.974686
2.021431
2.069026
2.117479
2.166802
2.217005
1
0.983392128
0.924487848
0.866754293
0.810153982
0.754650685
0.70020938
0.646796194
0.594378366
1
0.989359
0.95046
0.910504
0.869469
0.827335
0.784081
0.739686
0.694128
32
168
169
170
171
172
173
174
175
176
177
178
179
179.77
3.50566
3.579038
3.653537
3.729168
3.80594
3.883862
3.962945
4.043198
4.12463
4.207252
4.291073
4.376103
4.442405
2.268097
2.320091
2.372995
2.426821
2.481579
2.537281
2.593936
2.651556
2.710151
2.769733
2.830312
2.891899
2.94
0.542924197
0.492403007
0.442785099
0.394041713
0.346144996
0.299067958
0.252784443
0.207269096
0.162497327
0.118445284
0.075089821
0.032408473
0
0.647384
0.599432
0.550249
0.499812
0.448098
0.395081
0.340738
0.285044
0.227973
0.1695
0.109597
0.048239
0
3.The relative volatility at top and bottom is determined by using the formula [14]
And
= 1.572
= 1.511.
product respectively.
Top temperature = 159.7
Bottom temperature = 179.8
5.Feed temperature = (159.7 0.8915)+(179.8 0.1085) = 161.90
The overall material balance equation isF=D+W
Where, F= Feed rate, kmol/hr.
D= Overhead product rate, kmol/hr.
W= bottom product rate, kmol/hr.
Doing component balance for MIBK
FXf= DXd+ WXw
Where, Xf= mole fraction of MIBK in feed
Xd= mole fraction of MIBK in distillate
Xw= mole fraction of MIBK in residue
Given,
F = 944.08 kg/hr.. = 9.47kmol/hr..
Xf= 0.8891
Xd= 0.9980
Xw= 0.0750
33
Density (g/ml) =
Where, A,B and n are regression coefficient. T and Tc are in Kelvin. The values of the coefficient
for MIBK and MO are given bellow [15]:
component
Tc
MIBK
0.26654
0.25887
0.28571
571.40
MO
0.27648
0.25438
0.28484
600.00
Tc
34
MIBK
57.130
1.2040
571.4
MO
66.120
1.2560
600.0
The surface tension of distillate and residue is calculated applying same procedure for density
which gives the following value.
(top) = 10.394 dyne/cm
(bottom) = 11.115 dyne/cm.
5.4 DESIGN METHODOLOGY
STEP 1: TO FIND NUMBER OF THEORETICAL STAGES
To determine the number of theoretical stages, here we used the method of McCABE and THIELE
[16]. In this method what we need first is the equilibrium curve (x Vs y). The VLE data obtained by
Raoults lay is plotted. The operating line equations for both top and bottom section are determined
by appropriate mass balance. The equations of enriching section and stripping section operating
lines are respectivelyYn+1
Ym+1
Lb, Gb= liquid & vapour flow rate in bottom section respectively
The q-line equation is-
y = (q/q-1).x (Zf/q-1).(5.3)
where, q = (HG-HF)/(HG-HL)
HG = enthalpy of vapour from any tray.
HF = enthalpy of feed
HL = enthalpy of liquid
Therefore if the feed is saturated liquid then q = 1 and q/q-1 = . So q-line would be vertical.
The general procedure of finding number of equilibrium stage is as follows.
1. The distillate composition is marked on x-axis and travelled vertically upward upto the diagonal
line.
2. Travel vertically upward from the point of feed composition on the x-axis upto the diagonal.
Extend the line according to the slope of q-line and mark the point of intersection with the
equilibrium line.
35
3. Draw a line joining these two points and extend up to y-axis. The intercept on y-axis is
Xd/(Rm+1), from which we can find Rm.
4. Assume an operating reflux ratio 1.2-1.5 times of Rm and find the intercept (Xd/R+1) on y-axis.
5. Join the intercept and the corresponding point of the distillate composition on diagonal. This is
the enrichment section operating line.
6. By staircase construction we will get the number of theoretical stage in enrichment section.
7. Similarly we can find the number of theoretical stage in the striping section. Mark the position of
bottom product on x-axis and find the corresponding on the diagonal. Join this point with the q-line
intersection point on the equilibrium curve. This is the striping section operating line.
8. By staircase construction we will get the number of equilibrium stage in the striping section.
9. The feed point should be located closest to the intersection of two operating line.
10. The equilibrium curve is given below.
1.0
0.9
0.8
0.7
Y1
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
X1
In this design problem the driving force for separation is very small. The equilibrium curve is very
close to the diagonal. Since the top and bottom product composition is very close to unity, it is very
difficult to mark the points on the graph. So determination of theoretical stage by graphical method
is difficult in this case.
Based on the basic logic of the McCABE and THIELE method, a computer program is written in
Turbo-C language. The logic is given bellow.
36
The equation of the equilibrium line is determined by polynomial curve fitting. The
equation and the R2 value is given above. The position of the points required for drawing
the graph were determined by solving equilibrium line equation and q-line equation.
The equation of the connecting lines between the two points (mentioned above in 1. & 2.)
was determined. The intercept of the line with y-axis was determined and from there the
minimum reflux ratio was calculated.
The actual reflux ratio was determined and the operating line equation was generated.
Then the values of L, G, q, L, G were calculated using the following equations and the
striping section operating line equation was stablished.
L=R.D .(5.4)
G=D(R+1) .(5.5)
L=qF+1 .(5.6)
G=F(q-1)+G ..(5.7)
The mathematical logic behind staircase construction is employed in the program to
calculate number of theoretical stage separately in top and bottom section to get an idea
about the feed tray location. The program section for enrichment section will terminate
when calculated x value crosses the feed composition. Similarly program section for
striping section will terminate when calculated x value crosses the residue composition. The
program is shown below.
37
#include<stdio.h>
#include<conio.h>
#include<math.h>
main()
{
intn,b;
float m1,m2,c1,c2,a,x,y;
printf("\n enter the slope of the operating line of the enriching section:");
scanf("%f",&m1);
printf("\n enter the intersect of the operating line of the enriching section:");
scanf("%f",&c1);
printf("\n enter the slope of the operating line of the stripping section:");
scanf("%f",&m2);
printf("\n enter the intersect of the operating line of the stripping section:");
scanf("%f",&c2);
n=1;
y=0.9981;
x=0.9981;
while(x>0.8895)
{
x=(1.415-(sqrt((1.415*1.415)-(4*0.428*y))))/(2*0.428);
a=y;
y=(m1*x)+c1;
n=n+1;
}
y=a;
printf("\n the no of top tray is= %d",n);
b=n;
while(x>0.0755)
{
x=(1.415-sqrt(1.415*1.415-(4*0.428*y)))/(2*0.428);
y=(m2*x)+c2;
n=n+1;
}
printf("\n the calculated theoritical stages are= %d",n);
n=n-b;
printf("\n the no of bottom tray is= %d",n);
getch();
}
38
5. Assume:
a. Hole diameter (dh)
b. Hole Area= (3.14*dh2)/4.
c. Plate thickness.
d. Weir height (hw).
e. Downcomer area (Ad).
6.
Find
Fairs
co-efficient
(K),
From
graph
find
k1,then
k1
/.02)0.2..(5.11)
7.Find flooding velocity
Flooding velocity (uf) = K [(v-l)/v]0.5..(5.12)
8. Assume % flooding.
9. Find actual velocity assuming % flooding.
a. Actual velocity (ut) = uf* % flooding
b. Volumetric flow rate = Vw/v.........................(5.13)
c. Net flow area = (Flow rate/actual velocity)
(5.14) d. Column area = (Net area * 100 ) / (
100%- allowance) (5.15)
e. Diameter = [(column area *4)/3.14]0.5 (5.16)
10. The column diameter is rationalized with respect to that available in the market
11. Recalculate:
39
b) Assume hw.
c) Find K from the graph.
d) Find minimum vapour velocity (Uh):Uh = [K- 0.9 (25.4-dh)] / (v)0.5(5.23)
e) Check whether uh > uh (min). If uh < uh (min),decrease the hole area & recalculate.
Find
total
pressure
drop,
ht
hd
hw
how)
hb= (hw+how)+ht+hdc..(5.29)
STEP 8: CALCULATION OF FROTH HEIGHT
To be on the safer side, it is taken as twice the down comer back up. Thus, Fb= 2*hb(5.30)
STEP 9: CALCULATION OF DOWNCOMER RESIDENCE TIME
Down comer residence time, tr= (Ad*hb*l)/Lwd.(5.31)
To get most efficient design, all the calculations are to be repeated to get minimum column
diameter and minimum tray spacing.
5.5 DESIGN COMPUTATION (PROCESS)
S/L No
Variables
Top portion
Bottom portion
Temperature ( )
159.7
179.8
Pressure (kg)
27.81
27.81
19.46
28.93
0.7724
0.7724
0.5404
0.7884
8.173
7.666
656.89
687.39
10.394
11.115
10
0.010394
0.011115
41
42
13. The column diameter is rationalized with respect to that available in the market. And the
diameter is selected 0.55 m for both top and bottom.
Recalculation:
43
45
mm
47
Where,
d0 = outer diameter of the gasket
di= inner diameter of the gasket = 10 mm greater than the outside dia of shell
Y = minimum yield stress
m = gasket factor
P = design internal pressure
Actual gasket width N= (d0- di)/2
Basic seating width=N/2
G= diameter at location of gasket load reaction G= di+N
48
P)/4
Where,
HP = load to achieve adequate compression of gasket under operating condition
G = diameter of location of gasket load
2b= effective gasket pressure width
Total operating load:
Design equation: Wo = H + Hp
Determination of bolt load under bolting up condition
Design equatio :Wg = (3.14
Y)
Where,
b = effective gasket seating width = 0.24 ft
Y = minimum gasket seating stress
Determination of minimum bolting area:
If A0 is the bolt area required under operating condition and Ag is the area required under bolting up
condition then,
Design equation: A0 = W0/S0 & Ag = Wg/Sg
Where,
S0 = allowable stress for bolting material at design temperature
Sg = allowable stress for bolting material at atm temperature
Among A0 and Ag , greater is selected.
STEP 9: FLANGE CALCULATION
Flange outside diameter (A) = [C + d +25] mm
Where,
d = bolt diameter
C = bolt circle diameter
Flange thickness can be calculated by,
49
STEP 4: CHECK WHETHER THE THICKNESS OBTAINED CAN WITHSTAND THE LOAD OF
WHOLE TOWER
Insulation material & insulation thickness, i
Felt wool is selected as insulating material and insulation thickness is 5 cm.
Dead weight calculation
Outer diameter of the shell=D=0.562 m
Outer radius of the shell=R= 0.281 m
Inner radius of the shell= r = 0.275m
50
54
TOP
Equipment no.(tag)
Description(func.)
Sheet no.
BOTTOM
OR TOP AND BOTTOM
550
500
33
550
500
19
550
500
27.81
8.173
27.81
7.666
3.48
19.46
656.89
28.93
687.39
Carbon steel
5
Carbon steel
Carbon steel
Hot rolled Carbon steel
Carbon steel
60
nil
DATE OF ORDER
DRG NO.
`
NOTES
(1) INTERNAL VAPOUR AND LIQUID LOADINGS AT THE LIMITING SECTION ARE REQUIREDTO ENSURE
PROPER TRAY DESIGNS.
DENSITIES ARE REQUIREDAT ACTUAL INSIDE TOWER CONDITIONS OF TEMPERATURE AND PRESSURE.
VISCOSIY IS NOT REQUIRED UNLESS GREATER THAN O.7 Cp.
(2) CROSS OUT DIMENSION UNITS WHICH DO NOT APPLY TRAY SUPPLIES TO ADVISE
REMARKS
55
7. NOMENCLEATURE
A= area
Aa= Active area
Ac = column area
Ad = down comer area
Aeff= effective area
Ah = tray deak full open hole area
An = net area
Cp=specific heat
d = diameter
D, = density
Fdl= Stress due to dead load
Flv = flow factor
g = gravitational constant
G, L = gas and liquid flow rate
Hi = enthalpy of ith stream.
hw= weir height
Lwi= weir length n=number of moles
Pc, Tc = critical pressure and temperature
Psat, Tsat = saturation pressure and saturation temperature
Pvp = vapour pressure
QB= reboiler load
Qc = condenser load
r = radius
R= optimum reflux ratio.
R= reflux ratio
Rm= minimum reflux ratio.
t = actual thickness of the plate
th= skirt thickness
W= residue flow rate
Wex= weight of external connections
Wh= weight of head
Wh= weight of head
Wint= weight of column internal
Wl= weight of liquid inside the column
56
57
8. REFERENCES
1.Ullmanns Encyclopedia of Industrial Chemistry, Vol. 18, p. 735, 6th edition (2003), WileyVCH
2. J.J. McKetta, Encyclopedia of Chemical Processing and Design, Vol. 30, p. 50, 1st edition
(1989), Marcel Dekker Inc.
3. K. Schmitt, New acetone chemistry in Germany, Chem. Ind. Int., p. 204 (September 1966)
4. S.I.D.A. U.S. Patent 3,802,999 (October 31, 1961); Shell Development Co., U.S. Patent
2,344,226 (March 14, 1944)
5. Esso Research and Engineering Co., U.S. Patent 3,361,828 (January 2 , 1968)
6. Nippon Sekiyu, British Patent 968,151 (July 2, 1964)
7. McAllister et al., Shell Development Co., U.S. Patent 2,130,592 (September 20, 1938)
8. Esso Research and Engineering Co., U.S. Patent 3,153,068 (September 13, 1964)
9.Kgowa Hakko Kogyo, U.S. Patent 3,449,435 (June 10, 1969)
10.Scholven-Chemie, U.S. Patent 3,361,822 (January 2, 1968)
11. Shell Oil, U.S. Patent 3,374,272 (March 19, 1968)
12.R.M. Felder, R.W. Rousseau, Elementary Principles of Chemical Process, 3rd edition (2000),
John Wiley & Sons. Inc.
13. B.E. Pouling, J.M. Pransnitz, J.P. OConnell Properties of Gases and Liquids , 5th edition
(2000), McGraw-Hill.
14.J.M.Smith, H.C.Van Ness, M.M. Abbott, Chemical Engineering Thermodynamics, 6th
Edition, Tata-McGraw-Hill Edition.
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