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5.4.1 INTRODUCTION
In this process, acetylated castor oil (ACO) which is also known as palmatic acid or
hexadecanoic acid (C15H31COOH), undergoes thermal cracking to produce 1-tetradecene
(C14H28), which is referred to as drying oil (DO); and acetic acid (CH3COOH). However, there
is an undesired reaction that produces 1-octacosene (C28H56), which is referred as gum, from
the drying oil dimers. The chemical reactions and reaction kinetics for the thermal cracking
process are as follows (Grummit & Fleming, 1945):
Chemical Reactions
2C14 H 28 (l )
k2
C28 H 56 ( s)
DO gum (5.4.2)
There are two chemical reactions that occur in the thermal cracking of ACO. The first
(equation 5.4.1) is the main reaction where 1 mole of ACO (palmatic acid) reacts under high
temperature to produce 1 mole each of Acetic Acid & Drying Oil (1-tetradecene). The second
reaction (equation 5.4.2) is an undesired side reaction that produces 1 mole of Gum (1-
octacosene) from 2 moles of Drying oil (DO).
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5.4.1.1 Process Description
Figure 5.4.1 shows the process flow diagram for this plant. This process begins with
the raw material, ACO, being fed from a holding tank where it is mixed with recycled ACO.
The mixed feed would then heated to reaction temperature. Since the reaction occurs at high
temperatures, there is no need for a catalyst. The heated feed then flows into a plug flow
reactor. The reactor is simply a vessel to promote radial mixing. Then, process fluid is feed to
the distillation column (T-101) to separate the gum from the product. Another stream from
first distillation column (T-101) is fed to a distillation column (T-102) where the ACO is
separated and recycled. The non-recycled stream again goes through another distillation
column (T-103) where the DO is purified from the acetic acid. The contents of Streams 18
(acetic acid) and 19 (DO) are cooled and sent to storage. Drying oil (DO) is the main product
for sale, while the acetic acid is sold as a by-product (Grummit & Fleming, 1945).
5-104
5.4.1.2 Process Flow Diagram
5-105
5.4.2 OBJECTIVE OF THE DESIGN
The objective of this chapter is to determine detail design parameter for distillation
column T-102. The purpose of this distillation column is to separate the recycled stream
(Stream 16), which consists of hexadecanoic acid (ACO) and tetradecene (DO), from stream
14. Hexadecanoic acid and tetradecene are then recycled back to the reactor to obtain
higher conversion in reactor 101 and 102. The non-recycled stream again goes through
another distillation column (T-103) where the DO is purified from the acetic acid.
Distillation is by far the most important separation process in the petroleum and
chemical industries. It is the separation of key components in a mixture by the difference in
their relative volatility or boiling points. In most cases, distillation is the most economical
separating method for liquid mixtures (Sinnott, 2005). In this process, the feed in stream 10
contains more than two components which are hexadecanoic acid, tetradecene, acetic acid
and octacosene. It is commonly referred to as multi-component distillation. Figure 5.4.2
below shows the schematic diagram of the distillation column unit (T-102).
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Flowrate Mole
Component (kmol/hr) Fraction
ACO 0.2653 0.00215
DO 61.4943 0.49889
AA 61.5026 0.49896
Gum 0.0001 0.00000
(S12)
123.26 kmol/hr
Flowrate Mole (S10)
Component (kmol/hr) Fraction
315.21 kmol/hr
ACO 191.4709 0.60744 T = 82.8 oC
DO 61.6862 0.19570 P = 11 kPa
T-102
AA 61.5026 0.19512 T = 125.5 C o
NO
YES
5-108
Figure 5.4.3: Algorithm for distillation column design
5-109
5.4.5 THEORETICAL BACKGROUND
(5.4.3)
(5.4.4)
The relative volatility of two components can be expressed as the ratio of their k
values. From the K-values, the relative volatility for each component can be determined and
more accurate. (Sinnott, 2005):
Ki
i j
Kj
(5.4.5)
Where, Ki = light components
Kj = heavy components
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5.4.5.2.1 Key Component
Key component is component whose volatility that is vapor pressure characteristics relatives
to each other make them adjacent in the listing of the component in the feed. These key
components are separate into two as follows (Geankoplis,2003) :
The Fenske equation (Fenske,1932) is used to estimate the minimum stages required at total
reflux (Sinnott, 2005):
(5.4.8)
Where,
D = subscript for distillate
B = subscript for bottom
Nm = minimum theoretical stages at total reflux
XHK = concentration of heavy key component
XLK = concentration of light key component
αavg= average relative volatility
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5.4.5.5 Minimum Reflux Ratio
The number of stages required for separation will be dependent on the reflux ratio
used. As the reflux ratio is reduced a pinch point will occur at which separation can only be
achieved with an infinite number of stages. Colburn (1941) and Underwood (1948) have
derived equations for estimating the minimum reflux ratio for multicomponent distillations. As
the Underwood equation is more widely used , the equation can be stated in the form
(Sinnott, 2005):
x i ,d
ii = Rm + 1 (5.4.9)
Where,
i = the relative volatility of component i with respect to some reference
component, usually the heavy key
Rm = the minimum reflux ratio
Xi,d = concentration of component i in the tops at minimum reflux
i xi , f
1 q
i (5.4.10)
Where xi,f = the concentration of component i in the feed, and q depends on the condition of
the feed.
Where,
μa = molar average viscosity,mNs/m2
αa = average volatility of the light key
The overall column efficiency is correlated with the product of the relative volatility of the light
key component and the molar average viscosity of the feed, estimated at the average column
temperature. The overall column efficiency is relatively high in the range 50-100% (Seader,
2004)
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5.4.5.7 Number of stages using Lewis Matheson method
Estimation of the actual physical number of plates required in the distillation column is
usually done by dividing the actual theoretical stages by the overall plate efficiency (Sinnott,
2005):
(5.4.12)
Besides that, Lewis Matheson method is using in calculation of number of ideal stages. Feed
point also can be determined from this method:
1. For Top-Down:
(5.4.13)
2. For Bottom-up:
(5.4.14)
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5.4.5.8 Approximate Column Sizing
A trial and error approach is necessary in plate design. Starting with a rough plate
layout, checking key performance and revising the design until a satisfactory design is
achieved (Sinnott, 2005). The design procedures are as follows:
1. Determination of the vapour and liquid rate, based on the reflux ratio and feed
condition.
2. Estimation of the system physical properties.
3. Selection on a trial plate spacing.
4. Based on the flooding condition, the column diameter is determined.
5. Try to make a plate layout with downcomer area, active area, hole diameter, hole
area, weir height, weir length, and plate thickness.
6. The weeping rate is checking.
7. The plate pressure drop is checking.
8. The down-comer backup is checking .
9. Determination of plate layout details
10. Confirmation on the percentage flooding based on the chosen column diameter.
11. Entrainment is checking.
12. Determination of the column wall thickness and column head selection.
13. The design is finalize with the drawing and data specification sheet.
The overall height of the column will depend on the plate spacing. Plate spacing from
0.15 m to 1m are normally used. In this distillation column, the plate spacing used is 0.50 m
as it is in the range of 0.15 m to 1 m (Sinnott, 2005).
The column diameter is computed to avoid flooding where the liquid begins to fill the
column and leave with vapor because it cannot flow downward at the required rate (Seader,
2004).The principle factor on determining the column diameter is the vapor flow rate. The
column diameter can be calculated by calculating the top and the bottom net area at its
maximum volumetric flow rate.
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The Liquid-vapor flow factor, FLV is given by:
0.5
Lw V
FLv =
Vw L (5.4.15)
Where:
Lw = liquid mass flowrate, kg/s
Vw = vapor mass flowrate, kg/s
The flooding condition fixes the upper limit of vapour velocity. A high vapour velocity
is needed for high plate efficiencies, and the velocity will normally be between 70 to 90 per
cent of that which would cause flooding. For design, a value of 80 to 85 per cent of the
flooding velocity should be used. The flooding velocity can be estimated from the correlation
given by Fair (1961,referred to Sinnott,2005):
(5.4.16)
Where,
Uf = flooding vapour velocity, m/s, based on the net column cross-sectional
area,An
K1 = a constant
2/3
Lw
how = 750
LxI w (5.4.17)
5-115
5.4.5.12 Weep Point
The vapor velocity at the weep point is the minimum value for stable operation.
Minimum vapor velocity through the holes based on the holes area, ûh (Sinnott, 2005):
0.9(25.4 dh)
ûh = k2
( v) 0.5 (5.4.18)
where
ûh = minimum vapour velocity through the holes(based on the hole area), m/s,
dh = hole diameter, mm,
K2 = a constant, dependent on the depth of clear liquid on the plate
ht hd hl (5.4.19)
Where
ht = total pressure drop per plate, mm of liquid
hd = friction loss for dry plate, mm of liquid
hl = equivalent head of liquid on plate, mm of liquid
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5.4.5.13.1 Dry plate drop
Pressure drop through the holes can be predicted from a modification of equation for
flow through an orifice (Sinnott, 2005):
2
U v
hd = 51 h
Co L (5.4.20)
The orifice coefficient is a function of the plate thickness, hole diameter and the hole of
perforated area ratio.
12.5 103
Residual head,hr = (5.4.21)
L
The liquid area and the plate spacing must be such that the level of the liquid and forth in the
down comer is well below the top of the outlet weir on the plate above. The backup of liquid
in the down comer is caused by the pressure drop over the plate and the resistance to flow in
the down comer itself.
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Head loss by Cicalese et al (1947, referred to Sinnott, 2005):
2
Lw
hdC = 166
LxA
ap
(5.4.23)
where hap is height of the bottom edge of the apron above the plate. This height is normally
set at 5 to 10 mm below the outlet weir height (Sinnott, 2005):
(5.4.27)
Where,
tr = residence time, s,
hbc = clear liquid back-up, m.
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5.4.5.16 Check Entrainment by Fair
Entrainment can be estimated from the correlation given by Fair (1961), Figure 5.4.13, which
gives the fractional entrainment (kg/kg gross liquid flow) as a function of the liquid-vapour
factor FLV, with the percentage approach to flooding as a parameter. The percentage flooding
is given by (Sinnott, 2005):
U V 100%
Flooding percentage = (5.4.28)
uF
The area available for perforation will be reduced by the obstruction caused by
structural members (the support rings and beams), and by the use of calming zones.
Calming zones are unperforated strips of plate at the inlet and outlet sides of the plate. The
width of the support ring for sectional plates will normally be 50 to 75mm: the support ring
should not extend into down comer area. A strip of imperforated plate will left round the edge
of cartridge-type trays to stiffen the plate. A cartridge type construction is used; allowing 50
mm unperforated strips round. Formula used is list below (Sinnott, 2005):
Mean length of calming zone, approx = weir length + width of unperforated strip (5.4.30)
Total area available for perforation, Ap = Active area – (Area of unperforated edge + Area of
calming zones) (5.4.31)
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5.4.6 CALCULATION FOR CHEMICAL DESIGN
Composition and flow rate at feed,F; distillate,D and bottom,W are obtained from figure 5.4.2.
From table 5.4.1, the average activity coeffients is calculated based on K-values. Therefore,
based on the value, it is show that the system is non-ideal system.
Table 5.4.2 shows the average relative volatility for each component. The average relative
volatility is based on light key. Acetic acid is chosen as light key. So the average relative
volatility, αavg is 497.26. It shows that the component is volatile as it has greater volatility. The
greater relative volatility, the mixture is easier to separate.
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Table 5.4.2: average relative volatility
No.of trays α(ACO) α(DO) α(Acetic) α(Gum)
Tray1 1 85.6000 1053.3788 0.6599
Tray2 1 47.4561 728.3269 0.6112
Tray3 1 39.3427 650.7129 0.5953
Tray4 1 62.0185 638.1988 0.5921
Tray5 1 75.0035 635.8290 0.5911
Tray6 1 66.2164 438.9700 0.5189
Tray7 1 111.5893 372.6323 0.4967
Tray8 1 20.6083 229.8526 0.4347
Tray9 1 14.2100 124.8799 0.3613
Tray10 1 12.3553 99.7943 0.3373
AVERAGE 1 53.4400 497.2576 0.5199
STD 0 31.0754 285.0185 0.1050
The system is a non-ideal system and the bubble point and dew point is calculated
based on the relationship between K-values at each tray and temperature that are plotted
into graph and equation forms. Figure 5.4.4 to 5.4.7 shows variation of K-values with
temperature for all components.
5-121
Figure 5.4.5: graph of K value for Tetradecene
5-122
Figure 5.4.7: graph of K value for Octacosene
Based on equation 5.4.7 for dew point, value close to 1.0, therefore dew temperature
355.93 K is accepted.
Table 5.4.3: Method to find dew temperature at the top of the column
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5.4.6.4.2 Bubble Point (Bottom Column)
Based on equation 5.4.6 for bubble point, k xi i value should close to 1.0. This is trial and
error method as k xi i value is not 1 at temperature 541.21 K. Therefore, using goal and
Table 5.4.4: Method to find bubble temperature at the bottom of the column
Based on equation 5.4.6 for bubble point, k xi i value should close to 1.0. This is trial and
error method as k xi i value is not 1 at temperature 398.62 K. Therefore, using goal and
5-124
5.4.6.5 Step 5: Calculate minimum theoretical stages using Fenske equation
Minimum number of stages is calculated using Equation 5.4.8:
i xi , f
1 q
i
i xi , f
=1 – 1 = 0
i
θ
Component Xif αi αi Xif 2.51
ACO 0.60744 1.0000 0.6074 -0.4013
DO 0.19570 53.4400 10.4581 0.2054
Acetic Acid 0.19512 497.2576 97.0224 0.1961
Gum 0.00175 0.5199 0.0009 -0.0005
Total 0.0003
This is trial and error method, so, the value of = 2.51 which is close to 0.
ixi,
Therefore for the equation 5.9: i d = R m + 1, Rm +1 can be determine using θ= 2.51.
Table 5.4.7 shows the summary calculation to determine Rm +1 and also based on mole
fraction and relative volatilities at top tray.
5-125
Table 5.4.7: Summary calculation for the equation to determine Rm +1
Component Xid αi αi Xid αi-θ αi Xid / αi-θ
ACO 0.00215 1.000 0.00215 -1.51362 -0.0014
DO 0.49889 53.440 26.66069 50.92640 0.5235
Acetic Acid 0.49896 497.258 248.11020 494.74394 0.5015
Total 1.0236
Rm + 1 = 1.0236
Therefore, the minimum reflux ratio, Rm = 0.0236
Rm
= 0.0230
Rm 1
5-126
Figure 5.4.8 is a Erbar-Maddox correlation. From Erbar- Maddox correlation, value Nm/N can
be determined. Therefore,
Nm
= 0.20
N
Nm/N = 0.20
N =23stages
However, iteration needs to be performed to obtain optimum reflux ratio. For other reflux
ratio, the summary is in table 5.4.8:
R 2 3 4 5 6
Nm/N 0.2 0.25 0.28 0.35 0.42
N 23 18.776 16.764 14.412 11.176
Deviation 4.6940 2.0117 3.3529 2.2353
Table 5.4.8 shows iteration between reflux ratio and stages in order to determine optimum
reflux ratio. Value for Nm/N is from figure 5.4.8. The optimum reflux ratio is near this value
which is 5. Therefore, the required number of stages is 14 stages.
At average temperature,
T avg = (5.4.32)
= 448.57 K
5-127
Table 5.4.9: Viscosity data
Using equation 5.4.33, viscosity at average temperature for each component can be
determined as summarize in table 5.4.9 above. Therefore,
= 5.8844 mNs/m2
Constant molar overflow is assumed and the material balance and equilibrium
relationship equations are solved stage by stage starting at the top and bottom of the
column. The procedure is to start the calculation at the top and bottom of the column and
proceed toward the feed point. The initial estimates of the component distributions in the
products are then revised and the calculations repeated until the iteration stop when ratio of
Light key/ Heavy key at top down and bottom up is close to ratio of light key / heavy key at
feed. Table 5.4.10 to 5.4.12 shows summarization of top down, bottom up and results
obtained after iteration performed. Summarize table for stage by stage is shown in Appendix
A4.
5-128
Top down Equation:
Lo 616.31 kmol/ hr
D 123.26 kmol/ hr
R 5
V1 739.57 kmol/ hr
Lo/V1 0.83
y2 = 0.83 (x1-xo) + y1
Bottom up Equation:
V’ = Vo 739.57 kmol/ hr
F 315.21 kmol/ hr
B 191.95 kmol/ hr
B / L’ 0.206
V’ / L’ 0.794
5-129
Table 5.4.12: Results after Iteration
Summary:
1. At Top-down: 3 stages
2. At Bottom-up: 11 stages
= 14 stages
E0
= (14-1) / 0.62
= 21 stages
= 4 trays
=17 trays
5-130
5.4.6.9 Step 9: Calculation for density and relative molar mass (RMM)
Table 5.4.13 shows properties of component at feed, distillate and bottom. The properties
are then used to calculate relative molar mass and density at top and bottom product. The
formulas used are listed as below (Sinnott, 2005):
MW TSTP POP
3. Mean Vapor density, V = V x x
TOP PSTP
(5.4.37)
STP
5-131
Calculation for density :
1. Top product
Using equation 5.4.36:
Liquid density, L = x D ,i i
= 2.1522x10-3 (881.5780) + 0.49889 (774.0980) + 0.4989571
(1051.50)
= 912.74 kg / m3
= 0.4840 kg / m3
2. Bottom product
Using equation 5.4.36:
Liquid density, L = x B ,i i
= 0.99612 (881.5780) + 0.00100 (774.098) + 2.88x10-3
(804.593)
= 881 kg / m3
5-132
5.4.6.10 Step 10: Flow rate Calculation
The liquid and vapor mass flow rate above and below feed point is calculated and then used
to obtain Liquid-vapor flow factor, FLV.
5-133
Table 5.4.14 below shows summary of physical properties at distillate and bottom
product.
The Liquid-vapor flow factor, FLV at top product can be obtained from equation 5.4.15:
0.5
Lw V
FLv =
Vw L
= 0.0172
5-134
The Liquid-vapor flow factor, FLV at bottom product can be obtained from equation 5.4.15:
0.5
Lw V
FLv =
Vw L
= 0.10
Take plate spacing as 0. 50 m, from figure 5.4.9 below (Sinnott, 2005), value for k1 can be
obtained.
Hence, from figure 5.4.9 value of K1 for top and bottom are:
Top k1 = 0.09
Bottom k1 = 0.07
5-135
Correction for surface tension:
k1 = ( / 0.02)0.2 (5.4.38)
which liquid surface tension is 0.02 N/m (Sinnott, 2005).
Value of surface tension, at top is 0.03117 N/m and 0.0268 N/m at bottom. Surface tension
is obtained as calculation in Appendix A4. Hence:
1. = 0.098
2. = 0.075
1. = 4.2692 m/s
2. = 1.3514 m/s
5-136
Therefore, Maximum volumetric flow rate at top (Using equation 5.4.39):
Vm
Q = (5.4.39)
V
17.60
Q = = 36.36 m3/s
0.4840
Vn
Q =
V (5.4.40)
17.60
Q = = 6.45m3/s
2.7269
In order to calculate the column diameter, an estimate of the net area is required:
36.36
An = = 10.02 m2
3.6288
6.45
An = = 5.62 m2
1.1487
5-137
Column cross area sectional, As
Take down comer area as 12% of total net area, An (Sinnott, 2005).
An 10.02
As = = = 11.39 m2
0.88 0.88
An 5.62
As = = = 6.38 m2
0.88 0.88
Column diameter,Dc
For plate design, down comer area, active area, holes area, hole size and weir height are
calculated first. The equation involve for calculation are shown below (Sinnott, 2005):
(5.4.42)
5-138
5.4.6.12.1 Column Area, Ac
D 2
Column Area, Ac=
4
= π (2.8511)2 / 4
= 6.38 m2
= 0.12 x 6.38
=0.766 m2
An = Ac – Ad
= 6.38 - 0.766
= 5.614 m2
Aa = Ac-2Ad
= 6.38 - 2(0.766)
= 4.851 m2
5-139
5.4.6.12.5 Hole area, Ah
Ah = 10% x Aa
=0.1 x 4.851
= 0.4851 m2
Iw = 0.77 x 2.8511
= 2.195 m
5-140
Table 5.4.15 shows the summary for Provisional Plate Design.
5-141
5.4.6.14 Step 14: Weir Liquid Crest
2/3
Lw
2/3
31.29
How = 750 = 750 = 47.31 mm liquid
LxI w 881X 2.195
At minimum rate,
Clear liquid depth, Hw + How = 50 + 37.25 = 87.25 mm
Therefore, from figure 5.4.11, K2 = 30.8
5-142
5.4.6.15 Step 15: Weep Point
The vapor velocity at the weep point is calculated Using equation 5.4.18,
Minimum vapor velocity through the holes based on the holes area,Uh:
0.9(25.4 dh)
Uh = k2
( v) 0.5
0.9(25.4 5.0)
= 30.8
(2.7269) 0.5
= 7.53 m/s
Figure 5.4.12: Relation between per cent perforated area with orifice (Sinnott, 2005)
5-143
For plate thickness/hole diameter = 5/5 =1
2
13.30 2.7266
= 51
0.84 881
= 39.57 mm liquid
Residual Head, hr
12.5 103
Residual head,hr =
L
12.5 10 3
=
881
=14.20 mm liquid
5-144
5.4.6.17 Step 17: Downcomer Liquid Back Up
The height of the bottom edge of the apron above the plate,Hap
From equation 5.4.25:
The height of the bottom edge of the apron above the plate,Hap
= Hw - 10
= 50 – 10
= 40 mm
= 0.04 m
down comer
2
Lw
hdC = 166
LxA
ap
2
31.29
= 166
881x0.0878
= 27.14 mm
= 5.51 s
Q 6.453
Uv= = = 1.149 m/s
An 5.62
5-146
From Figure 5.4.13, Value = 0.035. Value is below 0.1 so the column diameter proposed
earlier is acceptable (Sinnott, 2005).
5-147
5.4.6.19 Step 19: Perforated Area
At Iw/Dc = 0.77
= 99 0
5-148
Area of unperforated edge strips, Aes
= (50 x 10-3) m x Ls
= 0.198 m2
= 2.245 m
= 2 x 0.05 x 2.245
= 0.225 m2
Total area available for perforation, Ap = Active area – (Area of unperforated edge + Area of
calming zones)
= 4.429 m2
5-149
The ratio of Ah / Ap = 0.485/ 4.429 = 0.11
DH 2 (0.005) 2
Area of one hole,A1 = = = 1.9635 x 10–5 m2
4 4
Ah 0.485
Number of holes = = = 24,700 holes
A1 1.9635 10 5
5-150
5.4.6.21 Step 21: Column Height
=0.5 x 21
=11 m
Actual height:
= 11 m + 2 m
= 13 m
5-151
Table 5.4.16: Chemical Design Sheet for Distillation Column
Item No : T-102
Function: To obtaine higher conversion in reactor 101 and 102
Operating Condition
5-152
Hole Design Plate pressure Drop
Area of one hole (m2) 1.963 x 10-5 Total Pressure drop (mm 141
Number of holes 24,711 liquid)
References:
Sinnott, R.K., 2005. Chemical Engineering Design. 4th edition: Vol 6. Coulson &
Richardson’s.
Perry, R.H. and Green, D.W. (1997). “Perry’s Chemical Engineering Handbook.” 7th ed.
USA: McGraw-Hill, Inc
Seader J.D & Henley E. (1998), Separation Process Principles, John Wiley & Sons, New
Jersey.
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