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Group # 5
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1. Acetone Introduction
Acetone belongs to ketone family
(dimethyl ketone) with scientific name 2Propanone.
In 2010, the worldwide production capacity
for acetone was estimated at 6.7 million
tons per year.
The United States had the highest
production capacity with 1.56 million tons
per year (2010)
The second largest production is in Taiwan
and followed by China (2010).
It is a common building block in organic chemistry.
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Project Demand
(million Tones)
2010
6.7
2011
7.2
2012
7.9
2013
8.4
2014
9.0
2015
9.63
2016
10.3
2017
11.02
1.5 Capacity:
The capacity of the desired plant to produce acetone is 45000 tons per year. The capacity data of
some previous years is:
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Year
Quantity (Tones)
Year
Quantity (Tones)
2004
31000
2008
39000
2005
32000
2009
40000
2006
34000
2010
42000
2007
36000
2011
45000
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The term stems from isopropyl benzene or cumene (C6H5-CH(CH3)2), the intermediate
material during the process.
2.2 By the direct oxidation of propylene using air:
Acetone can also be produced by the direct oxidation of propylene using air. In this process
the catalysis consists of a solution of copper chloride containing small quantities of
palladium chloride. The reaction takes place under a moderate pressure and at 100C. It is
exothermic by 61 kcal/mole of acetone produced. The overall reaction is as follows:
Propylene
Oxygen
Acetone
Isopropyl alcohol
acetone
hydrogen
The primary advantage of this process is that the acetone produced is free from trace aromatic
compounds, particularly benzene. For this reason, acetone produced from IPA is favored by the
pharmaceutical industry.
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Isopropyl alcohol
dehydrogenation process
Primary product is phenol
Acetone is the primary
Acetone is the primary
Acetone is by product
product
product
Purity of acetone is low
Purity is high
Purity is high
--Propylene used should be 99% Aqueous solution of the
pure
isopropyl alcohol can be used
Conversion to acetone is low
Conversion to acetone is low
Conversion to acetone is high
Worldwide production method Not used worldwide
Worldwide production method
Unconverted benzene present Not a dangerous compound
Not a dangerous compound
along with acetone is
present along with acetone
present along with acetone
dangerous to some process
To purify acetone large
Less separation process
Less separation process
number of separation
required and production cost is required and production cost is
processes are required which
low
low
increase the production cost
Major disadvantage of the production of acetone from cumene process is that some
amount of reactant benzene is present along with desired product which is toxic.
The disadvantage of production of acetone from propylene oxidation process is that
propylene required for the process should be 99 % pure.
So our process for the production of acetone is dehydrogenation of isopropyl alcohol.
Isopropyl alcohol
( )
Acetone
( )
Hydrogen
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( )
Isopropyl alcohol
Di-isopropyl ether
()
Water
At the higher temperature (>350 C), dehydration reaction is expected to be significant and
propylene is formed.
( )
Isopropyl alcohol
( )
( )
Propylene
Water
So the suitable temperature conditions for the reaction is between 325 C to 350 C
4.3 Selection of catalyst:
Trial and error experimentation and scientific analysis provide guidance for the selection of the
catalyst. There are some categories of the catalyst which are suitable for some purpose. For
example platinum, copper and related metals elements such as palladium are known to catalyze
hydrocarbon oxidation and dehydrogenation. Since our desired reaction is the dehydrogenation
reaction of hydrocarbon (isopropyl alcohol), so the catalyst used for the process belong to this
category.
One of the factors considered in the selection of catalyst is their turn over frequency (TOF).
4.3.1 Turn over frequency: Turn over frequency of the catalyst is defined as the amount of
reactant converted into product by the catalyst in the unit time. For most relevant industrial
applications, the turnover frequency is in the range of 102 - 102 s1
The turnover frequency of cu chromites catalyst is 0.026 per second
The TOF of carbon supported copper is 0.052 per second double than that of the cu
chromites catalyst.
Platinum (with a turnover frequency of 0.66 per second) metal has the high TOF for this
process but it is expensive.
So the suitable catalyst for this process is carbon supported copper.
4.4 Reaction kinetics:
The reaction to form acetone from isopropyl alcohol is endothermic with a standard heat of
reaction 62.9 kJ/mol. The reaction is kinetically controlled and occurs in the vapor phase over a
catalyst. The reaction kinetics for this reaction is first order with respect to the concentration of
alcohol and can be estimated from the following equation:
[
With Ea = 72.38 MJ/Kmol and
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Water
Acetone
Isopropyl
alcohol
Hydrogen
Molecular
Weight(kg/kmol)
18
58
60
Freezing Point(C)
-95
-88.5
- 259.2
Boling Point(C)
100
56.2
82.2
-252.8
Critical
Temperature (C)
647.3
508.1
508.3
33.2
Critical Pressure
(bar)
220.5
47
47.6
13
Critical Volume
(m3/min)
0.056
0.209
0.220
0.065
Liquid
Density(kg/m3)
998
790
786
71
Heat of
Vaporization(J/mol)
40683
29140
39858
904
Standard Enthalpy
of Formation
at 298K(kJ/kmol)
-242.0
20.43
-272.60
Standard Gibbs
Energy of
Formation at 298K
(kJ/kmol)
-228.77
62.76
-173.5
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Conversion %
46.3
55.4
64.6
73.4
83.5
90.0
7. Flow sheet:
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7.1.3 Heater: Since the temperature leaving the vaporizer is not enough for the reaction to carry
out. Due to which a pre-heater is used to maintain the temperature of the feed stream to the
reaction temperature of 350 C which is the reaction temperature. The unit is working at 2 bars,
and assumed to be constant. The entrance and leaving temperatures are 109.50C and 350 C.
7.1.4 Reactor: The reactor is the starting point for the calculations. The temperature values for
the entering and leaving streams is 350 C, (i-e the process is isothermal). The reaction takes
place inside is endothermic, for this reason the reactor has to be heated. For heating, molten salt
is used from the furnace.
7.1.5 Cooler: The entrance temperature of the cooler is 350 C and leaving temperature is 94.70
C. (Temperature is calculated by using energy balance). For cooling purpose water is used. By
using refrigerant better results may be obtained. But since it costs too much, due to which it isnt
chosen as the cooling material. From the temperature values its easily seen that the load is on
the cooler not on the condenser, for this process. But in reality the unit cannot cool that much,
and the load is mostly on the condenser. In this process, the mixture cooled down to its dew
point. The pressure is 1.5 bars, and assumed to be constant.
7.1.6 Condenser: The temperature of the entering stream is the dew point and the leaving
temperature is the bubble point of the mixture. In the condenser water is used as cooling
material.
7.1.7 Flash unit: Flash unit is operating isothermally, for this reason temperature is not changed.
It is 81 C in the entrance and exit. From trial and error method, (V / F) value is found to be 0.2.
The entrance temperature of the unit is the bubble point of the mixture, but if it is its dew point
the (V/F) value should be much higher. In the flash unit the hydrogen is flashed out from the
mixture of isopropyl alcohol, water and acetone. Along with hydrogen some amount of acetone
and isopropyl alcohol is also flashed out. In order to recover these, a scrubber unit is used.
7.1.8 Scrubber: Scrubber operated adiabatically. Water entering the unit is at atmospheric
temperature (i-e 25 C). The temperature of the off gas, including hydrogen and a very little
amount of acetone, is between 40-50 C. The temperature of the leaving stream (containing
water, acetone and isopropyl alcohol) is found to be 28.10 C from the energy balance around the
scrubber.
The streams leaving the scrubber and flash unit are mixed together before entering the acetone
column. The temperature leaving the flash unit and scrubber are 81 C and 28.10 C
respectively. The temperature of the mixture is found to be 45.0 C. This result is obtained by
using energy balance around the mixing point.
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7.1.9 Acetone distillation column: The acetone column is used to separate the acetone from the
mixture. The entrance temperature is 45 C. The leaving temperatures for the top and bottom
product are 102.3 C and 105 C, respectively, which are the bubble and dew points. Top
product of the unit includes acetone (99wt% of acetone which is desired). From the bottom
isopropyl alcohol, water and a very little amount of, 0.1 %, acetone is discharged.
7.1.10 Isopropyl alcohol column: In this distillation column, isopropyl alcohol and water are
separated. The entrance temperature is 105 C. The leaving temperatures of the top and bottom
products are both111.50 C. The top product is recycled to the feed drum. For this reason its
assumed to have the same concentration with the feed stream. The bottom product is pure water
and its thrown away. Since its temperature is very high it cannot be recycled to the scrubber.
But if a cooler is used, a recycle can be used.
7.2 Description f the process in the reactor
The reaction occurring in the reactor is in vapor phase. So the isopropyl alcohol is first vaporized
and then passed from the reactor. The process is continuous. Since the dehydrogenation of the
isopropyl alcohol is the endothermic reaction, so heat has o be supplied to the reactor to maintain
the temperature at 350 C. For heating purpose the molten salt is used. The molten salt is
circulated through the small scale furnace where it is heated and its temperature is raised above
the 350 C and this heated molten salt is used to provide the heat to the reaction during the
process. In order to heat the molten salt in the furnace, natural gas is burned in the furnace in the
limited amount and this amount of heat is used to heat the molten salt which in turn provides the
heat to the reaction.
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best choice.
Since our reaction is the gaseous phase and endothermic reaction so the choice is the plug flow
reactor.
8.2 Choice of the bed (Fixed, fluidized or moving)
Use of the catalyst requires modifications to basic reactor design to fixed bed reactors, moving
bed reactors or fluidized bed reactors.
8.2.1 Fixed bed reactors: These are used in the heterogeneous catalyst reactions and pressure
drop across the bed is small. The design of the fixed bed reactor is very easy as compared to the
moving bed and fluidized bed reactors. Their size is also compact as compared to other fluidized
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bed and moving bed reactors. The energy requirement is also small because no amount of energy
is needed as in fluidized bed and moving bed required to fluidize or move the bed.
8.2.2 Fluidized bed reactors: These are the reactors with a gas phase working fluid that requires
gas flow around and across the fine particles at a rate sufficient to fluidize the particles
suspended within the reactor. Since the catalyst bed has to be fluidized so the energy requirement
in these reactors is large. Pressure drop is also large as compared to the fixed bed reactors
because the pressure is dissipated to fluidize the bed. The volume of the reactor required is also
large as compared to fixed bed reactor, because the void spaces between the fluidized beds
occupy the more volume.
8.2.3 Moving bed reactor: These units are fluid reactors used where the fluid contain solid
particles that can be separated from the suspension fluid. Mostly suitable for liquid phase
reactions or where the slurry travels through the reactor. Moving bed reactors are not preferred
for the gas phase reactions. In these reactors the pressure drop is the greater among all.
From above points we see that the suitable reactor for our process is fixed bed plug flow
reactor, with the reaction occurring in the tubes and the heat exchanging material flowing
outside the tubes.
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Chemical factors:
The design must provide sufficient residence time for the desired reaction to proceed to the
required degree of conversion.
ii.
For example with heterogeneous reactions the reaction rate may be controlled by the rates of
diffusion of the reacting species; rather than the chemical kinetics.
iii.
Safety factors
The confinement of hazardous reactants and products, and the control of the reaction and the
process conditions.
Anhydrous
87% by weight.
Due to which we are using the 87 weight percent solution of isopropyl alcohol.
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Acetone
Hydrogen
Water
Isopropyl alcohol
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Mass out
Mass of water in + Mass of IPA in = Mass of water out + Mass of IPA out +
Mass of acetone out + Mass of hydrogen out
6000 + 896.5
6896.5 kg/hr
6896.5 kg/hr
Component
Acetone
Hydrogen
IPA
Water
Number of
moles entering
in reactor
100 kgmol/hr
49.8 kgmol/hr
Mass of
component
entering in reactor
6000 kg/hr
896.5 kg/hr
Number of
moles leaving
from reactor
90 kgmol/hr
90 kgmol/hr
10 kgmol/hr
49.8 kgmol/hr
Mass of component
leaving from
reactor
5220 kg/hr
180 kg/hr
600 kg/hr
896.5 kg/hr
From the 100 kmol/hr of the isopropyl alcohol entering in the reactor the amount of the acetone
produced per year is 45700 tons, which is very close to the desired amount of the product. So we
are not applying the material balance again, but using these calculations in the process.
So,
By using 100 moles of the isopropyl alcohol per hour the amount of acetone produced is 45700
ton per year.
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Temperature at outlet =
350 C
Component
Acetone
Hydrogen
IPA
Water
Number of moles
entering in reactor
100 kgmol/hr
49.8 kgmol/hr
Number of moles
leaving from reactor
90 kgmol/hr
90 kgmol/hr
10 kgmol/hr
49.8 kgmol/hr
Heat of formation of
components
-216.685 KJ/gmol
0
-272.290 KJ/gmol
-241.826 KJ/gmol
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Components
In
IPA
Water
Moles In
ni
Standard
heat of
formation
kgmol
100
49.8
Heat of
Sensible
phase change heats
(
)
KJ/gmol
-272.290
-241.826
KJ/gmol
39.858
40.65
KJ/gmol
20.014
10.476
KJ
(
)
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Acetone
IPA
Hydrogen
Water
kgmol
90
10
90
49.8
Standard
heat of
formation
KJ/gmol
-216.69
-272.290
0
-241.826
Heat of
Sensible
phase change heats
(
)
KJ/gmol
30.2
39.858
40.65
KJ/gmol
33.940
22.6
9.466
11.388
KJ
) ]
Here kinetic and potential energies are neglect able with no work done and no accumulation of
heat.
So the general energy balance equation becomes:
This shows that in order to carry out the reaction we have to supply the 6.3111 106 KJ of heat
on the basis of 100 kg-mol of isopropyl alcohol entering in the reactor.
12.3 Supply of the heat:
From the energy balance calculations, it is also seen that the reaction is endothermic and we have
to supply the heat to the process. This heat is supplied by the use of the molten salt:
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The mass flow rate and the temperature are selected and
optimized and that values of the flow rate and
temperature are selected which makes the process most
efficient at minimum cost.
From this relation we see that the inverse relation exist
between the mass flow rate of the salt and the inlet
temperature of the salt. By increasing the inlet
temperature of the salt, mass flow rate has to be
decreased to exchange 6.3111 106 KJ of heat.
Similarly if we decrease the inlet temperature of the salt
then mass flow rate has to be increased to exchange this
amount of heat. So a suitable value of both temperature
and mass flow rate has to be selected to make the
process optimum.
is the
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Where
[
By putting the values of conversion from 0 to 1 in rate equation we obtain the values of
.
From this we find the values of 1/
. Plot the graph between and 1/
, the weight of catalyst
can be calculated.
13.2 Table of and
and
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0.0061
163.9344
0.1
0.004990909
200.3643
0.2
0.004066667
245.9016
0.3
0.003284615
304.4496
0.4
0.002614286
382.5137
0.5
0.002033333
491.8033
0.6
0.001525
655.7377
0.7
0.001076471
928.9617
0.8
0.000677778
1475.41
0.9
0.000321053
3114.754
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and
and
3500
3000
2500
(1/-rA)
2000
1500
1000
500
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Conversion (XA)
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) ]
)(
( )
Where
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For the desired reactor the length to diameter ratio is 4.766 lies between the allowable limit. So
the design is satisfactory.
13.12.2 Pressure drop calculation
For the fixed bed reactor to operate economically the pressure drop along the length of the
reactor should be less than the 10% of the operating pressure.
The pressure drop along the length of the packed bed is calculated by using the Ergun equation.
The Ergun equation is:
(
Where
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This is greater than the reactor volume. So all the conditions are satisfied and design is accepted.
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1-2
2-2.5
2.5-3
10
3-3.5
12
Since the diameter of the vessel is 2.15 m, so from the above table the thickness of the shell is
9mm.
Thickness of the reactor shell = 9mm
14.2 Head selection and design
The ends of a cylindrical vessel are closed by heads of various shapes. The principal types used
are:
1. Flat plates and formed flat heads
2. Hemispherical head
3. Ellipsoidal head
4. Torispherical head
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Flat head
Applicable to low
pressure
Cheapest from all
types
Torispherical head
Used up to the
operating pressure of
15 bar
Above 10 bars their
cost should be
compared with that of
an equivalent
ellipsoidal head
Ellipsoidal head
Above 15 bars
ellipsoidal head is
used
Economical within
pressure limits
Hemispherical head
Used for very high
pressures
Capital cost is high
Where
)
(
So by putting the values of all the variables the value of thickness of head is:
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Bracket Support
15. Specification Sheet
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Equipment
Reactor
Type of reactor
Operating temperature
350 C
Operating pressure
2 bar
Volume of reactor
13.6 m3
Volume of catalyst
8.16 m3
Weight of catalyst
73000 Kg
Number of tubes
485
Shell height
10.248 m
Diameter of shell
2.15 m
Thickness of shell
9 mm
Head type
Torispherical head
Support type
Bracket support
(Ch.E-308) Chemical Reactor Design
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16. References
www.che.cemr.wvu.edu/publications/projects/acetone/acetone-a.PDF
http://www.owlnet.rice.edu/~ceng403/gr1998/acetone.html
http://www.scribd.com/doc/30134032/Isopropyl-Alcohol
www.annualreviews.org/doi/pdf/.../annurev.matsci.35.100303.12073
www.jbrwww.che.wisc.edu/home/jbraw/chemreacfun/.../slides-masswrxn.p
Gael D. Ulrich P. T. Vasudevan A Guide to Chemical Engineering Process Design
and Economics 2nd ed, Process publishing, 1993
Plant design and economics for chemical engineers by Timmerhaus 5th edition
Chemical engineering design by Coulson and Richardsons volume 6, 4th edition
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