4.

3 PROSES SELECTION

Figure 2.1 : PFD for Oxidation of Propylene

Equipment Summary for Figure 2.1

C-101 Air compressor
C-102 Off-gas-recycle compressor
E-101 Propylene reactor preheater
E-102 Acrolein reactor precooler
E-103 Product gas cooler
E-109 Molten salt cooler
E-110 Molten salt cooler
R-101 Propylene reactor
R-102 Acrolein reactor
T-101 Refluxed gas absorber column
T-102 Liquid extraction column
4.3.1 Input Streams to Reactor 101
The input to the first reactor, R-101, consists of three feed streams and a recycle stream
from the off gas absorber, T-1-1. The three feed streams are air (1), steam (2), and propylene
(3). The propylene feed has a purity of at least 95%, with the balance being propane. The
purpose of the recycle stream is to add carbon dioxide to the reactor feed stock, which along
with steam will reduce the risk of explosion of the propylene and acrolein during the
oxidation stage. The feed that going on the reactor is 10.21 mol% of water, 0.01 mol% of
carbon dioxide, 17.02 mol% of oxygen, 64.01 mol% of nitrogen and 8.75 mol% of
propylene

4.3.2 The Reactions

The pathway to Acrylic Acid requires the reaction of the feedstock and then the separation
and purification of the acrylic acid via liquid extraction and distillation. The gaseous phase
oxidation of propylene is undertaken in two separated fixed-bed reactors of identical
capacity. The difference between those reactors is the temperature of the cooling fluid and
the catalyst type.

Propylene Reactor: R-101

The first reactor operates more efficiently when the temperature is kept between 300oC and
450oC. It is in this temperature range that the catalyst's activity is at its maximum, and
subsequently both the single-pass conversion of propylene and the selectivity of propylene
to acrolein are at their maximum. A catalyst of molybdenum, vanadium and niobium is
used in the first reactor. Such a catalyst is highly selective for oxidising propylene to
acrolein and water as shown in the following exothermic reaction:

C3H6 + O2 → C3H4O +H2O

However, the propylene is still oxidised in three undesirable exothermic reactions

producing acetic acid, acrylic acid, carbon dioxide and water by-products.

Because the reaction is exothermic, large amounts of heat are produced. Consequently, an
efficient cooling system is required to ensure that the reactor operates within the optimum
temperature range. The recommended reaction temperature is 409oC. The propylene reactor
operates at 465 kPa. The fractional conversion of this reactor is 84%
Acrolein Reactor: R-102
This reactor operates more efficiently when the temperature is kept between 200oC and
350oC. It is in this temperature range that the catalyst's activity is at its maximum.
Consequently, the conversion of acrolein and selectivity of acrolein to acrylic acid are both
maximised. The same catalyst used in R-101 is also used here. The difference is only on
the composition of the main active elements. The reaction to obtain acrylic acid from
acrolein is as follows:

1
C3H4O + O2 → C3H4O2
2

The reaction is also exothermic and the cooling fluid is the same as that used in R-101. The
recommended reaction temperature is 300oC. The acrolein reactor operates at 350 kPa. The
fractional conversion of this reactor is 76%

Refluxed Gas Absorber: T-101

The product from the acrolein reactor, stream 9, is piped directly to the refluxed gas
absorber, T-101. The product from R-102 is here simultaneously cooled and separated by
a water stream entering the top of the tower. The water is used to "scrub" the gas and remove
all the gases that are immiscible in water (nitrogen, carbon dioxide, oxygen, acrolein and
propylene). Small amounts of both acetic acid and acrylic acid are absorbed into the water.
The gaseous distillate waste stream, stream 10, containing water and undesirable gases, is
passed through a splitter, where 85 mole % is recycled as a feed to the propylene reactor,
and the remaining 15 mole % is piped to the incinerator. The bottoms product of water and
the two acids, stream 15, is piped to the acid extraction tower, T-102.

The refluxed gas absorber operates at a pressure of 550 kPa and temperatures between 60oC
and 300oC.
Acid Extraction Tower: T-102
The dilute aqueous stream, stream 16, from the refluxed gas absorber, T-101, enters the top
of the acid extraction unit, T-102. The acid fraction of the stream is removed by an organic
solvent. The solvent must have a high solubility for acrylic acid and a low solubility for
water. One solvent with these characteristics is n-pentane, which has a high affinity for
both acetic and acrylic acid and a boiling point of 36oC. The n-pentane stream enters the
bottom of T-102, and leaves the top of the unit with most of the acrylic and acetic acids.
The waste stream, stream 18, containing water and small amounts of n-pentane and the two
acids, is removed from the bottom of T-102 and piped to the wastewater treatment facility.

The acid extraction tower operates at 200 kPa and temperatures between 40oC and 50oC.

Figure 2.2 : PFD for Oxidation of Propylene

 Equipment Summary for Figure 2.2
E-104 Solvent-recycle cooler
E-105 Solvent-free acid cooler
E-106 Acrylic acid product cooler
E-107 Acetic acid product cooler
E-108 Acrylic acid product cooler
T-103 Solvent recovery cooler
T-104 Acrylic acid column
T-105 Acetic acid column
V-101 Solvent-recycle storage tank
V-102 Acrylic acid product storage tank
V-103 Acetic acid product storage tank

Solvent Tower: T-103

The top product from T-102, stream 17, goes directly to the solvent tower, T-103, for the
separation of the n-pentane solvent from the two acids. Since n-pentane has the lowest k
value (vapour/liquid ratio), it will be predominantly recovered in the distillate, with only
trace amounts in the bottoms product. Both acrylic acid and acetic acid are removed as
bottoms product and fed to T-104. The solvent tower distillate, stream 20, containing 99.9
mole% of n-pentane is recycled to the acid extraction tower, T-102.

Acrylic Acid Tower: T-104

The acrylic acid tower, T-104, separates the bottoms product from T-103 into an acrylic
acid bottoms product, stream 26, and an acetic/acrylic acid distillate, stream 25, which is
fed to T-105 for further purification.

The acrylic acid tower operates at a pressure of 250 kPa and temperatures between 150 oC
and 175oC.
Acetic Acid Tower: T-105
The acetic acid tower, T-105, separates the bottom product from T-104 into an acrylic acid
bottoms product, stream 27, and an acetic distillate product, stream 31.

The acetic acid tower operates at a pressure of 200 kPa and temperatures between 130oC
and 160oC.

4.3.3 Output Streams

The production of acrylic acid via the oxidation of propylene generates four output streams

 The acrylic acid product, stream 34, containing 99.8 mol% acrylic acid,
receives combined bottoms products from both the acrylic acid and acetic
acid towers, T-104 and T-105.
 The acetic acid product, stream 29, containing 98.5 mol% acetic acid, comes
from the acetic acid tower, T-105, distillate product.
 The wastewater, stream 18, containing 99.1 mol% water and the balance n-
pentane, acrylic acid and acetic acid comes from the acid extraction tower,
T-102.
 The off gas, stream 12, containing 79.1 mol% nitrogen, with the balance
being propylene, acrolein, oxygen, carbon dioxide and water vapour, is only
21.9 mol% of the stream originated from the refluxed gas absorber, T-101.
5.0 MATERIAL BALANCE

Stream 6 7 9 10 11 15 17
Temperature (°C) 191 409 300 - - 180 -
Pressure (Kpa) 430 465 350 - - 550 -
Molar Flow (Kmol/hr) 3233.236 9509.34 9370.744 9335.204 5672.73 5737.19 5357.267
Chemical
Component
Properties
Water H20 0.1021 0.112 0.112 0.125 1 0.9257 0.991
Carbon
CO2 0.0001 0.039 0.039 0.045 - - -
dioxide
Oxygen O2 0.1702 0.049 0.045 0.039 - - -
Nitrogen N2 0.6401 0.788 0.788 0.791 - - -
Propene C3H6 0.0875 - - - - - -
n-pentane C5H12 - - - - - - -
Acorlein C3H4O - 0.012 - - - - -
Acrylic Acid C3H4O2 - - 0.013 - - 0.0694 0.008
Acetic Acid C2H4O2 - - 0.003 - - 0.0049 0.001
Total 1 1 1 1 1 1 1
 Stream 18 20 21 24 29 34
Temperature (°C) 45 - - - 130 163
Pressure (Kpa) 200 - - - 200 250
Molar Flow (Kmol/hr) 1394.169 323.231 379.831 1014.338 61.933 316.834
Chemical
Component
Properties
Water H20 0.002 0.001 0.0056 0.001 - -
Carbon
CO2 - - - - - -
dioxide
Oxygen O2 - - - - - -
Nitrogen N2 - - - - - -
Propene C3H6 - - - - - -
n-pentane C5H12 0.727 0.999 - 0.999 - -
Acorlein C3H4O - - - - - -
Acrylic Acid C3H4O2 0.255 - 0.9353 - 0.015 0.998
Acetic Acid C2H4O2 0.016 - 0.0591 - 0.985 0.002
Total 1 1 1 1 1 1
Propylene Reactor : R-101

Stream
Component
Input Output
H20 0.1021 0.112
CO2 0.0001 0.039
O2 0.1702 0.049
N2 0.6041 0.788
C3H6 0.0875 -
C5H12 - -
C3H4O - 0.012
C3H4O2 - -
C2H4O2 - -
Molar Flow
3233.236 9509.34
(Kmol/hr)

Acrolein Reactor : R-102

Stream
Component
Input Output
H20 0.112 0.045
CO2 0.039 0.039
O2 0.049 0.045
N2 0.788 0.788
C3H6 - -
C5H12 - -
C3H4O 0.012 -
C3H4O2 - 0.013
C2H4O2 - 0.003
Molar
Flow 9509.34 9370.744
(Kmol/hr)
Refluxed Gas Absorber : T-101

Stream
Component Input Output
1 2 3 4
H20 1 0.045 0.125 0.9257
CO2 - 0.039 0.045 -
O2 - 0.045 0.039 -
N2 - 0.788 0.791 -
C3H6 - - - -
C5H12 - - - -
C3H4O - - - -
C3H4O2 - 0.013 - 0.0694
C2H4O2 - 0.003 - 0.0049
Molar
Flow 5672.73 9370.744 9335.204 5737.19
(Kmol/hr)

Acid Extraction Tower : T-102

Stream
Component Input Output
1 2 3 4
H20 0.9257 0.001 0.991 0.002
CO2 - - - -
O2 - - - -
N2 - - - -
C3H6 - - - -
C5H12 - 0.999 - 0.727
C3H4O - - - -
C3H4O2 0.0694 - 0.008 0.255
C2H4O2 0.0049 - 0.001 0.016
Molar
Flow 5737.19 1014.338 5357.359 1394.169
(Kmol/hr)
Solvent Tower : T-103

Stream
Component Input Output
1 2 3
H20 0.002 0.0056 0.001
CO2 - - -
O2 - - -
N2 - - -
C3H6 - - -
C5H12 0.727 - 0.999
C3H4O - - -
C3H4O2 0.255 0.9353 -
C2H4O2 0.016 0.0591 -
Molar
Flow 1394.169 379.831 1014.338
(Kmol/hr)

Acrylic Acid Tower : T-104

Stream
Component Input Output
1 2 3
H20 0.0056 - -
CO2 - - -
O2 - - -
N2 - - -
C3H6 - - -
C5H12 - - -
C3H4O - - -
C3H4O2 0.9353 0.015 0.998
C2H4O2 0.0591 0.985 0.002
Molar
Flow 379.831 61.933 316.834
(Kmol/hr)