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Acetone ( propanone) is the organic compound with the formula (CH3)2CO.

It is a
colorless, volatile, flammable liquid, and is the simplest ketone.Acetone is a colorless
liquid used as a solvent and an antiseptic. It is one of the ketone bodies produced
during ketoacidosis.Acetone occurs naturally in plants, trees, forest fires, vehicle
exhaust and as a breakdown product of animal fat metabolism. This agent may be
normally present in very small quantities in urine and blood; larger amounts may be
found in the urine and blood of diabetics. Acetone is toxic in high doses.

Acetone
Uses of acetone
Acetone is used for following purposes.

1. Adhesives and sealant chemicals


2. Agricultural chemicals (non-pesticidal)
3. Intermediates
4. Ion exchange agents
5. Laboratory chemicals
6. Processing aids, not otherwise listed
7. Processing aids, specific to petroleum production
8. Solvents (for cleaning or degreasing)
9. Solvents (which become part of product formulation or mixture)
10. Viscosity adjustors
Properties of Acetone:

L.No Properties Values


1. Density 784.5 kg/cm3

2. Melting point -91.6℃

3. Boiling point 56.11℃ at 760 mm Hg


4. Vapour pressure 180 mm Hg at 20℃ ; 270
mm Hg at 30℃
5. Viscosity 0.34 mm²/s at 40°C
6. Solubility greater than or equal to 100
mg/mL at 22.2℃,
Miscible with water

7. Surface tension
0 ℃: 26.2 mN/m;
20 ℃: 23.7 mN/m;
40℃: 21.2 mN/m

8. Heat of vaporization 31 kJ/kmol,25℃

9. Dissociation constant(pKa) 20

10. Heat of combustion -1789 kJ/kmol

11 Flash point -18℃


Health effects:
Acetone has been studied extensively and is generally recognized to have low acute
and chronic toxicity if ingested and/or inhaled.Acetone is not currently regarded as
a carcinogen, a mutagenic chemical or a concern for chronic neurotoxicity effects.
Acetone can be found as an ingredient in a variety of consumer products ranging from
cosmetics to processed and unprocessed foods. Acetone has been rated as a generally
recognized as safe (GRAS) substance when present in beverages, baked foods,
desserts, and preserves at concentrations ranging from 5 to 8 mg/L.

Global supply and demand:


About 97% of the world's acetone production is as a by-product of phenol production.
Therefore, a lot of the trends in the phenol industry also apply to acetone. The global
acetone industry is driven by the solvents sector, which represents 34% of global
demand, and in 2016, 42% of the global demand for solvents came from Northeast
Asia. Global solvent demand from acetone will continue to maintain a healthy growth
rate of 3.7% to 2021. Methyl methacrylate (MMA) is the second-largest end use for
acetone. In 2016, global demand for MMA resin accounted for 26% of total acetone
consumption. Bis phenol A is the third-largest demand sector. However, by the end of
the forecast period, bis phenol A demand will exceed that of MMA, growing at 3.3%
per year over the next five years to 2021.
In 2016, worldwide demand for acetone is led by China (23%), the United States
(21%), and Western Europe (20%). Solvents are the largest end use, and are used in
products such as nail polish removers, cement, lacquers and finishes, cleaners, paint,
coatings, films, and adhesives. Pharmaceuticals are also an important consumer of
acetone solvent, with large quantities being used in glass-reinforced plastics, rubber
chemicals, and household, cosmetic, and personal care products. The solvents sector
is usually the last place acetone ends up, and then only if it cannot be sold into the
other higher-value applications. Solvents are expected to be one of the faster growing
markets, increasing at an average rate of 3.7% per year over the next five years.

Objective and scope:


The project aims at a designing a project for production of acetone using
dehydrogenation of ISO-propel alcohol(IPA).this method provides 99% purity of
acetone and also this method of production is cost effective compared with others.the
objective of design project as follows.

 Detailed literature survey.


 Draw the process flow sheet for the selected process.
 To check thermodynamic feasibility of process.
 To carry out material and energy balance for the process.
 To carry out equipment design for the major units in the process.
 To do the detailed plant layout and the economics of the project.

Methods of manufacturing:
There are mainly 3 processes for the production of acetone and they are commercially
acceptable are given below.

 Oxidation of cumene.
 Dehydrogenation of IPA over a catalyst and in the absence of catalyst
 Vapor-phase oxidation of butane.

Oxidation of cumene:The overall process for the production


of acetone from benzene and propene consists of two major steps. In the first
step cumene is produced from benzene and propene in the cumene process by Friedel-
Crafts alkylation.

Propane and other hydrocarbons contained in the propene feed stock are separated as
low-boiling components in the cumene distillation unit. High-boiling components,
mainly polypropylene, are separated as a residue. There is only a little amount of
process water, which is generated from water dissolved in
the benzene and propenefeed stocks. In the second step (cumene oxidation, Hock
process), cumene is first oxidized with atmospheric oxygento cumene
hydroperoxide (CHP). CHP is then cleaved to phenol and acetone by using a strong
mineral acid as catalyst. Ketones, mainly byproducts from acetone, are separated as
low-boiling components in the distillation. High-boiling components, which are
mainly formed in the oxidation and cleavage unit, are separated as a residue. A certain
amount of process water is generated in the phenol-acetone process and must be
further treated in a biological waste water treatment plant. The overall reaction can be
considered as a dual oxidation: benzene is oxidized to phenol and propene is oxidized
to acetone.

Dehydrogenation of IPA: At the beginning of the process, feed including i-propyl


alcohol and water, and recycle stream are mixed in feed drum.
(CH3)2CHOH→(CH3)3CO + H2

From here, this mixture is send to vaporizer to changestream’s phase as vapour. After
vaporizer, mixture is heated to reaction temperature in the heater. Reactor used is a
tubular flow reactor. Acetone, hydrogen gas (H2) are produced and water and i-propyl-
alcohol are discharged. The mixture with acetone, hydrogen, water, i- propyl-alcohol
are sent to cooler and then to condenser. After condenser the mixture is sent to flash
unit. Hydrogen, acetone, i-propyl-alcohol and water are obtained as top product. This
top product is sent to scrubber to remove hydrogen. The bottom product of flash unit
which is formed by acetone, water, i-propyl-alcohol are mixed with the bottom
product of scrubber before acetone column. In acetone column, acetone is obtained
from top product with 99 wt%.
I-propyl alcohol and water and also 0,1% of acetone is sent to i-propyl-alcohol
column from bottom product. The top product of this column is sent to feed drum and
bottom product is thrown away as waste water.

Vapour phase oxidation of butane:Butane was partially oxidized in a flow reactor at


325–425°C and 0.25–6.5 atm. The study was directed toward the effects of numerous
variables on product distribution, rather than on factors influencing the overall
reaction rate. Emphasis was placed on the direct products—those formed directly
from either the butyl peroxide radical or the butyl radical. Increasing the surface area
or changing the surface area from glass to stainless steel reduced the reaction rate, and
at the higher temperatures increased the yield of cracking products; however, in
general such changes did not affect the distribution of other direct products.
Increasing the partial pressure of butane, oxygen, or inert gas increased the ratio of
direct oxygenated products to butene, the only exception being the butene oxides.
Increasing the temperature had the opposite effect.

The results indicate that the direct oxygenated products and the butenes are produced
almost entirely by a homogeneous reaction, and suggest that the association of the
butyl radical and oxygen is a termolecular reaction involving the deactivation of the
nascent, excited butyl peroxy radical. The direct oxygenated products are believed to
be formed from the deactivated butyl peroxy radical; the butenes probably are formed
directly from the reaction of butyl radical and oxygen. Cracking products are
produced homogeneously at 325°C, but primarily heterogeneously at 425°C.
Heterogeneous cracking is catalyzed by stainless steel and does not occur when only
glass is present. Secondary oxidation of butene does not occur to a measurable extent.

Process selection:

The main reason behind choosing second method for the production of acetone ,as
this is commercially accepted one,highly economical and gives maximum yield of
production compared to other manufacturing methods.

Process description:
Feed drum is a kind of tank used for the mixing of the recycle stream and feed
stream.Recycle stream concentration was assumed to be same with the feed stream.
The temperature of the feed stream is assumed to be 25℃ at 2 bar pressure, which is
assumed to be constant.The temperature of recycle stream was calculated as 111.5℃
The temperature of the leaving stream was calculated as 32.89℃, by the energy
balance around feed drum.In the vaporizer molten salt was used for heating. The
temperature at the entrance of the unit is the temperature of the mixture leaving the
feed drum, which is 32.89℃. And the leaving temperature is the bubble point
temperature of the mixture, which is 109.5℃. The pressure is 2 bars, and assumed to
be constant.Since the temperature leaving the vaporizer is not enough for the reaction
a pre-heaterwas used.

The unit is working at 2 bars, and assumed to be constant. The entrance and leaving
temperatures are 109.5℃and 325℃.The reactor was the starting point for the
calculations. The temperature values for the entering and leaving streams were found
from literature, which are 325℃and 350℃,respectively. The reaction taken place
inside is endothermic, for this reason the reactor has tobe heated. For heating, molten
salt was used. The pressure is 1,8 bar, and assumed to be constant.
The entrance temperature of the cooler is 350℃and leaving is 94.7℃. For
cooling,water was used. Instead of water a refrigerant may be used. Better results may
get. But since it costs too much, it wasn’t chosen as the cooling material. From the
temperature values it’seasily 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 bar, and assumed to be constant.
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 was used as cooling
material. In the calculation of the dew and bubble points Antoine Equation was used.
Trial and error was used with the help of Excel. The mixture includes acetone, i-
propyl-alcohol, water and hydrogen.But hydrogen was not taken into consideration in
the calculations. Since the condensation temperature of hydrogen is very low, it is not
condense in the condenser. It stays in the for this reasons it has no affect on bubble
and dew point calculations. Also since it does not affect the temperature calculations
it’s not taken into consideration on mole and mass fraction calculations. The leaving
and entering temperatures are 94.7℃and 81℃, respectively. The pressure is 1,5 bar,
and assumed to be constant.Flash unit was assumed to be isothermal, for this reason
temperature was not changed.It is 81℃ in the entrance and exit. The pressure is 1,5
bar, and assumed to be constant. By trial and error method, (V / F) value was found to
be 0,2. The entrance temperature of the unit is the bubble point of the mixture, but if it
was its dew point the (V/F) value would be much higher.Scrubber was assumed to be
adiabatic. The temperature of water entering the unit was assumed to be 25℃. The
temperature of the off gas, including hydrogen and a very little amount of acetone,
was assumed to 70℃. But this assumption is too high, a lower temperature should
have been assumed, since a lot of water is used in the unit. It should have been around
40℃- 50℃. The temperature of the leaving stream was found to be 28.1℃.The
pressure of the unit is 1,5 bar, and assumed to be constant.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℃and 28.1℃,respectively. The
temperature of the mixture was found to be 45℃. This result was getting by using
energy balance around the mixing point.
The acetone column is used to separate the acetone from the mixture. The entrance
temperature is 45℃. The leaving temperatures for the top and bottom product are
102.3 and105, respectively, which are the bubble and dew points. Top product of the
unit includes acetone i-propyl-alcohol and 99wt% of the product is acetone. This
amount is assumed to be the desired acetone production rate, which is 115000
ton/year. From the bottom i-propyl-alcohol, water and a very little amount of, 0,1 %,
acetone is discharged. The pressure is 1,1bar, and assumed to be constant.In the
distillation column, i-propyl-alcohol and water are separated. The entrance
temperature is 105℃. The leaving temperatures of the top and bottom products are
both111.5℃. The top product is recycled to the feed drum. For this reason it’s
assumed to have the same concentration with the feed stream. But in reality a very
little amount of acetone exists in the stream. It’s calculated but neglected on the
recycle stream calculations. The bottom product is assumed to be pure water and it’s
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.The pressure is 1,1 bar, and assumed to
be constant.In the calculations one year is assumed to be 360 working day and 8600
hours. If it was 300 working day and 7200 hours, the results may be higher.Since
approximated values are used in the calculations, some errors may occur. The values
were taken in three decimal digits. If four or more decimal digits were taken, more
accurate results would get. Also during the calculations of the specific heats,
approximated values used.

Thermodynamic feasibility:

CHEMICAL REACTION

(CH₃)₂CHOH → (CH₃)₂CO + H₂

compound Heat of formation (KJ/Kmol) Free energy formation (KJ/Kmol)


IPA -272.60 -173.5
hydrogen 0 0
acetone 20.43 62.76

Specific heat co-efficients from Literatue

compounds IPA Acetone hydrogen


a 32.427 71.96 28.84*
b 1.886* 20.1*10 0.00765
c 6.405*10-2 -12.78*10-8 0.3288*10-8

Calculations:

Δα=[(n*Δα)p - (n*Δα)r]
=[28.54*10-3+71.96 - 32.427]
Δα= 39.561
Δβ = [(n*Δβ)p - (n*Δβ)r]
=(0.00765*10-5-12.78*10-5) - 1.886*10-1)
Δβ = -0.18872
Δϒ=[(n*Δϒp - (n*Δϒ)r]
=(34.76*10-9+0.3288*10-8 -6.405*10-5)
Δϒ=-6.4811*10-5

ΔH˚T = ΔH’ + ΔαT+ΔβT2/2 + Δϒ*T3/3


=293.03-(39.561*298.1)-0.1872*298*298/2-6.401*10-5
ΔH˚T= -3681.25 KJ/Kmol

ΔG˚= ΔH’ + ΔαTlnT+ΔβT2/2 + Δϒ*T3/6-ART


-236.26 = -3681.25-39.561*298ln(298)+0.1887*298*298/2 + 6.4011*10-
5*298*298*298/6-A*8.314*298

A=-25.11
lnk= ΔH’/RT + ΔαTlnT/R+ΔβT/2R + Δϒ*T2/6R + A
=-(3681.25/(8.314*623)+(39.561*ln623/8.314) -(-0.18772*623)/(2*8.314 ) -
( 6.4811*10-5*623*623)/6*8.31 -25.11
lnK= 4.2921

ΔG˚= -RTlnK
=-(8.314*623*4.2921)
ΔG˚623k= -22.23149 KJ/Kmol,
Therefore,reaction is feasible.

Overall material balance

SCRUBBER:

T=81 OC, PRESSURE=1.48atm


Assume :1/100 of neet acetone is in off-gas

nacetone12=0.02418 kmol/hr
nacetone10=24.148-0.04148=24.124kmol/hr

ntotal = nacetone + nH2o8 +nh208 + nIPA8


= 24.148+90+3.731+0.776
=118.65 kmol/h
ntotal = nacetone12 + nH212
=0.024148+90 = 90.024 kmol/h
Yacetone12 = naectone /ntotal = 0.02418 / 90.024 = 2.68*10-4
similarly ,yacetone8 =0.203

nH2o10 = nh2o8 +nh211


=3.731+604..11 = 607.772 kmol/h

ntotal10 = naectone10 + nH2o10 +nIPA10


= 24.124+607.772+ .776 = 632.672 kmol/h

ACETONE COLUMN:

naectone13 = naectone9 + naectone10


=65.789 +24.124 = 89.91 kmol/h
nIPA = nIPA9 + nIPA10
=9.194 +0.776 = 9.97 kmol/h
nh2o = nh2o9 + nh2o10
= 45.491 +601.772
= 653.263 kmol/h
ntotal13 = naectone13 + nh2o13 + nIPA13
=753.146 kmol/h
Assume that 1/1000 of acetone is in bottom product
naectone15 = 89.913/1000 =0.089 kmol/h
naectone14 = 89.913- 0.089 = 89.824 kmol/h
since purity is 99%
nIPA 14 = (89.824 * 0.01)/0.99 = 0.907 kmol/h
nIPA15 = nIPA 13 – nIPA14
=9.043 kmol/h
nh2o15 = nh2o13 =653.26 kmol/h

IPA COLUMN:

since all the IPA is not the top product


nIPA17 = nIPA15 = 9.063 kmol/h
nacetone17 = nacetone15 = 0.089 kmol/h

assume the compostion of recycle stream is same as feed stream


YH2o = 0.33 , YIPA = 0.67

nwater17 = (9.063*0.33)/0.67 = 4.464 kmol/h


nwater16 = nwater15 – nwater17 = 653.263 – 4.464 =648.799 kmol/h

FEED DRUM:
input = output

nIPA2 = nIPA1 + nIPA17


= 100-9.063
=90.937 kmol/h

nIwater2 = -nwater17 + nwater1


= 49.25-4.464
=49.786 kmol/h

amount = 89.824kg/h*58.08*876.h/year*1ton/1000kg
= 45700.726 ton/year

Flash Unit

It is assumed that there is no change at temperature and pressure


Ki=Pi*/PT=yi/xi
At bubble point (T=81°C)
For acetone
Log Pacetone=7.02447-1161/224+81
Pacetone=1651.6mmHg
Kacetone=1651.6/(1.5/1.013)*760=1.467
For i-propyl-alcohol
Log PIPA=8.37895-1788.02/227.438+81
PIPA=369.89mmhg
KIPA=369.89/1125.092=0.328
For Water
Log PH2O=7.96681-1668.21/228+81
PH2O=369.89mmHg
KH2O=369.89/1125.092=0.328
From Trial Error(V/F)=0.2
F=nacetone7+nH2O7+nIPA=149.25kmol/hr
F=V+L
0.2=V/F
Yv=K*Xl
F*Zf=V*yV+L*xL
For acetone
yV=1.467*xL
90=29.85*yV+119.4*xL
xL=0.077
yV=0.026
For Water
yV=0.328*xL
49.25=29.85*yV+119.4*xL
xL=0.381
yV=0.125
At stream 8
V=29.85kmol/hr
Yacetone=0.809
nacetone8=0.809*29.85=24.148kmol/hr
yi-propylalcohol=0.026
ni-propylalcohol8=0.026*29.85=0.766kmol/hr
yH2O=0.125
nH2O8=.125*29.85=3.731kmol/hr
At stream 9
L=199.4kmol/hr
Xacetone=0.551
Nacetone=0.551*119.4=65.789kmol/hr
x i-proplyalcohol=.077
ni-proplyalcohol9=0.077*119.4=9.194kmol/hr
xH2O=.381
NH2O=0.381*119.4=45.491kmol/hr