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Faculty of Engineering
Chemical Engineering Dept.
4th Year Graduation Project
ESTERIFICATION REACTOR
SPECIAL DESIGN
Poly Ethylene Terephthalate Project PET
Abstract
Polyethylene Terephthalate PET is one of the most important types of
polyesters which is produced worldwide. PET can be produced via direct
esterification of Terephthalic acid TPA or Transesterification of Dimethyl
Terephthalate DMT. The main route used now is direct esterification of TPA with
Monoethylene Glycol MEG.
This report will include the detailed design of the Esterification reactor by
direct esterification process. This design includes basic design of the reactor giving its
all dimensions (diameter, height, mixer power and heating media type and its flow
rate). The mechanical design of the reactor also is included.
I|
1.
Introduction
The reactor is the core of any chemical industry as it is the step where reaction
occurs and all the units of the plant are designed either to prepare the feed for the
reaction or to purify the product. So the choice of the reactor affects the whole flow
diagram of the plant and affects also the cost of the plant.
PET production by using TPA and ethylene glycol can be performed by two
different schemes. The first one is monomer production which is called BHET then
polymerization of this monomer to give the polymer PET. While the second scheme is
direct polyesterification of both TPA and MEG to give the polymer. The chosen
process for our project CTIEI process follows the second scheme in which the first
reaction occurs in a CSTR reactor to give the monomer while the polyesterification of
the monomer occurs in two stages prepolymerization and final polymerization.
Modern polyester (1)
Esterification reaction is usually reversible reaction but when the products of
the reaction are removed continuously removed from the reaction medium it can
enhance the reaction in the forward direction. The reaction conditions have to be
adapted with this purpose to give the desired product with desired specifications.
The feed of the reactor is terephthalic acid and ethylene glycol mixtures at 160
C as slurry where the molar ratio of the fresh ethylene glycol to the fresh TPA within
the range 1.05 to 3. After the reaction proceeds the formed monomer BHET and the
unreacted TPA is removed from the bottom of the reactor as slurry with small
amounts of ethylene glycol while the vapour phase consists of water vapour and
excess ethylene glycol which is processed to two distillation columns to recover the
ethylene glycol and to be recycled to the process. (2,3)
2.
Reactor conditions:
The reactor temperature is 260 C and it is somehow constant, and the pressure
is ranged from 1 atm to 2 atm, and in another one from 1 to 3 atm. The selected
pressure for the reactor is 1.5 atm to be within the range of whole literatures. The
reaction can be catalytic or non catalytic. Both are available and industrially
performed. When the reaction is non catalytic it becomes self catalyzed by TPA. This
study proceeds by non catalytic esterification. The effluent from this reactor is
directed to the polymerization reactors which performed in melt phase so usually the
polymerization catalysts and side reactions inhibitors are entered in this reactor but
have no effect on the reaction kinetics or the reactor volume since they are in low
quantities ppm ranges. (2,3)
3.
Reaction Kinetics
Firstly the reaction kinetic scheme in which the reaction occurs must be at the
same conditions of the reactor of this study because the rate depends on the process
variables like temperature and pressure and reactant concentrations. The reactions of
the scheme are
K1
TPA + MEG
MHET + H 2 O
(I )
K2
MHET + MEG
BHET + H 2 O
( II )
These two reactions are the main reactions but actually monohydroxyethyl
terephthalate MHET is an intermediate in the reaction medium and the reaction is
represented by the overall reaction of the form
( III )
TPA + MHET
Dimer2 + H 2 O
( IV )
The reactions (I-II) are of importance kinetically but the other two reactions
(III-IV) are in equilibrium and can be neglected.
There is another side reaction in the kinetic form is the formation of diethylene
glycol DEG from the ethylene glycol.
eq
2 MEG
DEG + H 2 O
R = 3KJ / mol
This reaction is important because the DEG content in the final PET product is very
limited especially for bottle grade application. So the reaction must be minimized as
much as possible for that reason stabilizer have to be added in the reaction medium to
work as inhibitors for this reaction and any formed amounts of DEG would vaporized
and directed to the distillation system to be removed.
Through this study the considered reactions would be I and II only and the
related rate equations. Although TPA is solid and the reaction proceeds in the liquid
phase and so the diffusion should have a role, it was found that the chemical reaction
is the limiting step in this model since the increase in the homogeneous volume can be
neglected.
The rate equations of the two reactions are below, it can be observed that first
reaction is second order reaction for TPA which acts as the catalyst of this reaction
beside its role as reactant while the order of ethylene glycol is zero as a solvent. For
the second reaction again TPA is the catalyst because its acid properties are more
potent than those of the MHET and it remains permanently in the reaction zone and
also zero order for MEG.
2
r1 = k1CTPA
dis
r2 = K 2 C MHET
The values of rate constants K1 and K2 are calculated at the reaction temperature and
give the values of 24.5 (Kg/mol min) and 8.73 (min-1).
Because of existence of solids in the reaction mixture the solubilities of both reactant
and product must be specified. Here the solubility of TPA in the reactant MEG and
solubility of TPA in the product BHET can be calculated from the equations below
(
dissolvedTPA mol
MEG (
) = 9062 exp
1kg MEG
BHET (
(
dissolvedTPA mol
) = 374 exp
1kg BHET
4877
)
T
3831
)
T
after substituting with reaction temperature 260 C in these equations the value of MEG
is 0.96 and hence it can be assumed that the reaction is liquid phase reaction and this
31
phase stands for the reactants phase. In case of solubility of TPA in BHET its value is
0.2 and it means that BHET formed is insoluble in the reaction phase that ensures the
forward direction of the reaction. (4, 5)
4.
I.
MHETout
TPAout
MHETout
K 2
V
= MHETin + K1
Total mixture mass
Total mixture mass
MHETout
V
BHETout = BHETin + K 2
Total mixture mass
II.
Assume an overall conversion and enter other data required for the simulation
process like reactor conditions inlet flow rates....etc
42
II.
Run the simulation and take the results from the program like BHETout total
mixture mass and mixture density.
III.
IV.
Repeat the calculations above for several selected conversions and draw the
conversion Vs the reactor volume.
210
190
170
150
130
110
90
70
50
0.4
0.5
0.6
0.7
0.8
0.9
Overall Conversion
III.
Mixer calculations:
As stated above it is required to install high efficient mixing tool to make the
reaction mixture homogeneous. The mixing operation depends on many variables like
type of mixture to be mixed, the existence of heating or cooling and the dimensions of
the equipment where the mixer equipped. Firstly all these variables must be clearly
specified before the mixer design.
52
P=NpD5N3
Where
Np: the power number which obtained from graphs by knowing Reynolds number
D: diameter of the stirrer which assumed to 3be 0.5 times tank diameter
N: speed of the of the stirrer in rps
: the reaction mixture density either from literature or simulation
To get Np we must calculate Re firstly
Re =
D 2 N
After calculating Re a graph for getting the power number but these graphs valid only
for vessels of H/D=1 so this value of Np (1.2 from Jeankoplis) can be assumed to be
valid here because the distance between the two stirrers is equal to the tank diameter.
This calculated power for the single stirrer, to get the power for double stirrer
multiply the resultant power by 1.2 to get the power for the double stage pitched blade
turbine stirrer of the value 122 KW. The stirrer dimensions are illustrated in the
equipment design drawing. (6, 12)
IV.
i =1
j =1
62
Where;
m: total number of components in the feed stream
n: total number of components in the effluent stream
Cp: the average heat capacity of component at either inlet temperature or outlet
temperature
Tin: temperature difference between inlet temperature and reference one
Tout: temperature difference between outlet temperature and reference one
Hr: heat of reaction at the reactor temperature
First of all is calculating the heat of reaction at the reactor temperature, this can be
calculated according to Hess law as follow
TPA +
2 MEG
nC p (25 260)
TPA +
C
260
nC pv (183 260) +
n + nC (25 183)
pL
2 MEG
C
25
BHET +
2 H 2O
(nC
nC pL (100 25) +
n + nC (260 100)
pV
(260 25) )
BHET +
2 H 2O
or
So we must know Hro which also will be calculated from the heat of formations of
the reactants and products as follow
Hro=nprHfopr-nreactHforeact
After the value of Hro is calculated the value of Hr at reaction temperature
also would be calculated and finally substitute in the value of Q or net heat load to the
reactor. There is another easier way to perform energy balance for the reactor; it is
from Aspen plus model of the reactor which was used before to perform the mass
balance. By using this model the net heat load is included in the reactor results after
the simulation is run. The value of heat load required given by
Aspen is more accurate than the calculated manually value.
V.
Spiral Coils
72
used instead of jacket to provide the required heat. There are a lot of configurations
for the coil in the reactor the cheapest one of them is spiral coil. Because it has no
limitation to be used in the reactor, it is chosen for this reactor.(6)
Firstly about the heat transfer media used for heating, there are more than one
alternative. The first one is high pressure steam whose pressure exceeds 15 bar.
Beside HPS there are Dow Therm, Xcel Therm and Paratherm. In the case of this
reactor the pressure is 1.5 bar only so the alternative of HPS is totally rejected because
it would increase the process pressure and also increase the hazard for the process.
For the design procedure of the internal coil, the value of diameter of coil is
assumed to be 3 and the loop diameter is assumed to be 0.8 times the tank diameter
and only one coil is used. This assumptions is valid for the H/D=2 i.e. valid for this
reactor.
Number of loops can be calculated via the equation
N loops =
H vessel
2 Dcoil
Vcoil =
2
Dcoil
Lcoil
Vtotal = Vcoil + VR
Now new dimensions for the reactor are specified due to the increase in volume.
The area of heat transfer of the coil can be calculated by
Qcoil = UAcoil Tm
there are two unknowns Tm and the overall heat transfer coefficient U and Qcoil is the
same calculated Q before. To complete the design the value of U must be calculated.
There is an equation to determine outside heat transfer coefficient h
D 2 N
hDo
= 0.09 tirrer
k
0.65
Cp
0.333
Dstirrer
Dvessel
0.333
n
baffles
0.2
0.4
82
All the physical constants in the above equation are available either in the simulation
results or in the literatures except for the value of
one, nbaffle is the number of baffle equipped in the reactor which has been chosen
before as 4 baffles. This equation is valid for the use of blade turbine stirrer for the
ratio of H/D=2 and baffled vessels i.e. it is valid to be used in this case. In case of the
low thickness of the tube, the conduction resistance of the tube can be neglected. For
the case of choosing very efficient heating media in the coils its resistance also can be
neglected. Thats why in this case the calculated h can be assumed as U the overall
heat transfer coefficient.
Returning to the equation of heat transfer rate mentioned above the only unknown
now is logarithmic mean temperature difference Tm so it can be calculated easily. To
find the conditions of the heating medium like flow rate inlet and outlet
temperature, the following must be done.
Tm =
Tin Tout
where Tin = Toil in TR and Tout = Toilout TR
Tin
Ln
3
T
out
To get the reasonable Tin of the heating medium, trial and error should be used. The
first trial is assuming the temperature approach of 15 C; it means that outlet
temperature of the heating medium is 275 C. With substituting in the last equation the
value of inlet temperature of the heating medium is calculated as 472 C. It is found
that this temperature is very high to be the inlet temperature of a heating medium so
another trial is required.
The second trial is in reverse way, the heating medium alternatives (Dow
Therm vapour phase, Xcel Therm vapour phase and Xcel Therm liquid phase) are
compared together by their characteristics and properties and it is found that the liquid
phase Xcel Therm is better than the others. Beside the phase of the media there is
another point of comparison is the flow rate required for the heating which is
calculated later. Hence the inlet temperature is 400 C and then substitute again to get
the outlet temperature of the oil is 293 C. (Xceltherm site and Dow Therm file)
Finally the flow rate of the heating medium is calculated from the equation
Fcoil =
Qcoil
C p (Tin Tout )
29
It results the value of 53 ton/hr; it is observed that this value id=s very high but
reasonable with respect to the volume of the reactor and inlet mass flow rate and heat
load of the reactor. (8, 9, 10)
5. Mechanical Design
I.
Material of construction
It was noticed that the reactor will be subjected to slurry with acidic medium at high
temperature of 260 C, so the material used must withstand these conditions and
Stainless steel 316 L was found to be suitable in such a reactor. Stainless steel 316L
contains 18% Cr + 8% Ni +0.03% C + 3% Mo. Carbon steel is also reasonable but
less used. (11)
II.
Calculations:
The reactor is a tall vessel under internal pressure and it will be designed at coastal
area. Design according to ASME code.
(1)Design of thickness of the shell
C = 1/16 ; E = 1
tsh = 4/16
(3) Design of neck
existing Necks
Type steel
M=2.75, y=3700
diameter
Assume Dig=Dineck=19.68
Di neck=19.68 assumed
Dog=19.75
tneck=2/16
Do neck=19.84
Donew=19.93
2 10
Ds=23.68
E=17/16
Dof=25.8
Qbf=33a34 ibf
Dmg=19.81003937
all bolts=12000 psi
c=0.0625
h=1.44
dib=1
Q'b=7231.261721bf
Q"b=14391.8609 bf
3
l=0.553474128
DF=22.57809111
tf=6/16"
(7) Design of Flat Cover
tF.C=7/16"
tR=19/16"
(9)Design of tall vessel
2 11
= 0
Pw=0.27
=
. = -
. = +
!!
"
!!
"
$%
&
= 0
'.' [ 0 ]
= -
.
. = -
. = +
In case of operation:
. = +
-
. = -
+
!!
"
$%
$%
&
&
Do sk=1.02 Do sh
L sk=2.5 m
tsk=(Do-Di)/2+c
mentioned above
assumed dimensions
Thickness of 1 is enough
6.
There are a lot of factors that affect the cost of the reactors. As being CSTR reactor it
is required to got vessel cost individually, the cost of mixer and the shaft and the
motor power and finally the cost of heating system of the reactor here it is the coil
212
system. That is all about fixed capital cost of the reactor. About the
variable cost of the of the reactor it is required to specify the power of the
mixer and the heating medium flow rate. Beside these accurate method of
the cost estimation, there are shortcut methods like estimation of the
reactor cost by its dimensions only and multiply this cost by a factor to
get the estimation of the mixer and the heating system. Attached below
the cost estimation of the process including the reactor. (13, 14)
ECONOMIC STUDY
1. Estimation Of Purchased Cost Of Equipment (PCE):
Table (1): Purchased Cost of Equipment for TPA production (Eastman)
Eastman TPA
Equipment
Cost At
2007 ($)
Compressors
Compressor1
181,500
3
Compressor2
197,700
Compressor3
128,400
Compressor4
383,000
Total Compressors Cost
Expanders
Expander1
130,000
Expander2
98,000
Total Expander Cost
Flash Separators
Over Flow Flash Drum
68,200
Vacuum Flash Drum
80,100
Total Flash Cost
WRC
Cost Of Top Trays
87,913.8
Cost Of Bottom Trays
36,414
Top Shell
124,100
Bottom Shell
32,700
Total WRC Cost
Heat Exchangers
Inter-Stage Cooler1
1,405,300
Inter-Stage Cooler2
1,303,000
WRC Condenser
265,600
Flash Condenser
2,437,400
Rankine Condenser
328,000
Solvent Vaporizer
82,800
Total Costs
($)
890,600
228000
148,300
281127.8
13
2
353,900
202,500
511,700
6,890,200
479,700
576,300
558900
470800
1,029,700
Eastman TPA
Equipment
Static Mixer
Centrifuge
Rotary Vacuum Filter
Rotary Vacuum Filter
RVF Vacuum System
Total RVF Cost
3
Vacuum Flash Drum Vacuum System
Crystallizer
Post Oxidizer
Shell
Impeller
Cost of 1 stage
Total Post Oxidizer Cost
Bubble Column Oxidizer
Titanium lining
Carbon steel shell
Total Bubble Column Cost
Total Fixed Cost 2007 USD$
2007 Cost Index
2010 Cost Index
Cost At 2007
($)
Total Costs
($)
8,500
203,500
346,500
13,800
360,300
10,300
1,184,000
306,300
134,300
440,600
881,200
4,778,100
5,032,300
9,810,400
22,982,127.8
525.4
555.2
24,285,643.99
CTIEI
Equipment
Cost At 2007
($)
Total Costs
($)
14
2
First Column
38,600
First Column Condenser
47,300
First Column Trays
5,357
Total First Distillation Cost
91,257
Second Distillation Column
Second Column
69,800
Second Column Condenser
35,400
Second Column Reboiler
91,800
Second Column Trays
3,689
Packing
22,406
Total Second Distillation Cost
223,095
Vacuum Unit
20,700
Table (2 contd.): Purchased Cost of Equipment for Intermediate PET
production (CTIEI)
Pre-Polymerization Reactor
Pre-Polymerizer
786,500
Agitator
247,000
Total Pre-Polymerizer Cost
1,033,500
Esterification Reactor
Esterifier
1,117,700
Agitator
45,200
3
Total Esterifier Cost
1,162,900
Mixer
Agitator
36,200
Vessel
43,200
Total Mixer Cost
79,400
Disk Ring Reactor
1,676,550
Total Purchasing Cost CTIEI 2007 ($)
2007 Cost Index
2010 Cost Index
4,287,402
525.4
555.2
4,530,577.827
Table (3): Purchased Cost of Equipment for Product PET production (Buhler)
Buhler
Equipment
Total purchasing cost Buhler 2007
2007 Cost Index
2010 Cost Index
Cost At 2007
($)
Total Costs
($)
6,431,103
525.4
555.2
6,795,866.741
35,612,088.56
15
2
FCI
Factor*PCE
35,004,148.99
15,751,867.05
15,751,867.05
5,250,622.349
3,500,414.899
3,500,414.899
13,126,555.87
7,000,829.798
1,750,207.45
7,875,933.523
1,0851,2861.9
27,128,215.47
5,425,643.093
1,0851,286.19
43,405,144.75
151,918,006.6
22,787,700.99
174,705,707.6
16
2
Cost
301,468,800
92,500,000
525,000,000
288
70,400,000
Utilities
Type
Steam
Cooling
Price ($)
0.355
0.251
Electricity
Fuel
96
500
Cost
6,833,750
8,785,000
6,048,000
1,400,000
12,581,864
3
Table (7): Calculation of Net Profit/year and Payback time
Manufacturing Cost
Direct Cost
A- Variable Cost
Raw Materials
Miscellaneous
Utilities
Shipping And Packing
Total Variable Cost
B- Fixed Cost
Labor
Supervision
Plant Overhead
Depreciation
Interest
Insurance
Rent
Royalties
Maintenance
Total Fixed Cost
Calculation Equation
0.1 Maintenance
$ 14per Ton
Value ($)
371,869,088.00
1,519,180.07
12,581,863.64
4,900,000.00
390,870,131.70
1,800,000.00
360,000.00
900,000.00
22,787,700.99
1,519,180.07
1,519,180.07
1,519,180.07
1,519,180.07
15,191,800.66
47,116,221.92
437,986,353.62
217
Manufacturing Cost
Indirect Cost
Calculation Equation
Value
109,496,588.41
Manufacturing Cost
547,482,942.03
Sales
617,500,000.00
Gross Profit
Net Profit Per Year
70,017,057.97
56,013,646.38
3.12
18
2
References:
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
19
2