Improve Safety Level Urea Plant of Shiraz Petrochemical

Company by Lowering Passivation Air

Authors
J an van der Werf, J o Eijkenboom, Alex Scheerder, Stamicarbon bv, The Netherlands
A. Reza Foolad, Shiraz Petrochemical Company, I.R. Iran




ABSTRACT
Shiraz Petrochemical Company (SPC) operates a Stamicarbon CO
2
stripping urea plant
since 1983 with a design plant capacity of 1500 mtpd near Shiraz in I.R. Iran. Early
2003 SPC installed the first Safurex

stripper in the world after experience was gained

with Safurex

high efficiency trays in the urea reactor.

As the high pressure carbamate condenser was made of BC.05 stainless steel, SPC
offered the first opportunity to reduce the oxygen content in the CO
2
from normally 0.6
vol.-% to 0.3 vol.-%. Stamicarbon and SPC agreed to perform a low oxygen test.
The only reason to add oxygen is to passivate the stainless steels in the HP synthesis
section in contact with the process medium. Having a Safurex

HP Stripper and BC.05

HPCC less oxygen is needed for passivation.
Lowering the oxygen level in a urea plant leads to an improvement of the safety level.
The ultimate goal is to operate an urea plant oxygen free, which is intrinsically safe. A
pre-requisite is that all equipment must be in Safurex

.
Lowering the oxygen level also leads to numerous other benefits such as lower energy
consumption and lower investment figures. The low oxygen test at SPC is a milestone
to realize an oxygen free and thus intrinsically safe urea plant.
This paper presents the results of the low oxygen test at SPC both from process as well
as from corrosion point of view.

The low oxygen test demonstrated no increase in corrosion in the HP synthesis section.
Process benefits were evident; increased reactor conversion, lower steam consumption
in HP Stripper and lower ammonia emission.
There are no limitations for the SPC plant to run the plant at 0.3 vol.-% oxygen.

Based on this result, Stamicarbon specifies an oxygen content of 0.3 vol.-% in the CO
2

feedstock in a Stamicarbon stripping plant when following pre-requisites are met:
HP Stripper in Safurex

material quality
HPCC / HP Poolcondenser in BC.05 material quality


1.
LIST OF CONTENTS


1. Introduction

2. Low Oxygen Test Procedure

3. Risk analysis

4. Process consequences

5. Corrosion consequences

6. Process safety

7. Conclusions
2.
1. Introduction

In the high pressure synthesis section (140 bar) of a Stamicarbon CO
2
stripping urea
plant, the prevailing process conditions are highly corrosive. Carbamate is the corrosive
component. To protect the carbon steel pressure vessels these are lined or overlay
welded with austenitic stainless steel at process side. Materials such as a 316L Urea
Grade (Stamicarbon designation: BC.01) and X1CrNiMoN25-22-2 (Stamicarbon
designation: BC.05) are used. Application of these stainless steels is only possible when
oxygen is supplied to the synthesis. Stamicarbon recommends 0.6 vol % oxygen. Not
withstanding this, still one has to account for passive corrosion rates varying between
0.05 to 0.1 mm/year, which is acceptable (corrosion allowance). However, a shortage
on oxygen supply to the synthesis can result in a catastrophic increase in corrosion
rates (>30 mm/ year).
Besides the risk for active corrosion, the presence of oxygen in the synthesis is not
beneficial from process and safety point of view.

Operating a Stamicarbon urea plant without oxygen therefore gives great technological
benefits. The process scheme can be simplified by the deletion of several equipment
items such as, amongst others, the HP scrubber and the 4 bar absorber. Besides a
lower investment figure and longer lifetime also a lower energy consumption figure as
well as higher plant output will be realized. Furthermore a urea plant without oxygen will
be intrinsically safe.
The requirement for an oxygen free urea plant is that all materials in the synthesis
section, which are exposed to the process, are Safurex

.
Safurex

is a duplex stainless steel (Stamicarbon designation: BE.06) which has

excellent corrosion resistance under urea synthesis conditions without the need for
passivating air (oxygen).

When the alloy protection of the HP Carbamate Condenser is made from BC.05
material and the HP Stripper is made in Safurex

, one can already reduce the oxygen

content that is needed for passivation. Stamicarbon expects that in this case the oxygen
concentration can be reduced to 0.3 vol.-% instead of the typical 0.6 vol.-%.

Shiraz Petrochemical Company is the first urea plant, which meets these requirements:
The HP Carbamate Condenser is made in BC.05 material and the new HP Stripper is
made in Safurex

.
In the period of J uly 31 till September 18 2005, SPC in presence of Stamicarbon
reduced the oxygen content to 0.3 vol.-%.

3.
2. Low Oxygen Test procedure

SPC operated the urea plant already at 0.45 vol.-% oxygen before the low oxygen test
started. In order to judge the effect of lower oxygen content, base line readings were
taken from J uly 31 till August 6:
- Nickel content in the end product to monitor any increase in corrosion.
- Essential process parameters to evaluate the effects on process conditions.
Amongst others: temperature in top of Urea reactor and steam consumption in
HP Stripper.
On August 7 the oxygen was reduced to 0.3 vol.-% and the plant operated at this low
oxygen level till September 9 and was stopped for a planned turnaround. Due to
mechanical problems in the compressor the CO
2
was kept constant (compressor speed
and capacity did not change after reducing the oxygen content).
In the TA a corrosion inspection was done in the HP synthesis section.

First the base line of the Nickel content in the end product at higher oxygen content
(0.45 vol.-%) was established: 0.2 ppm. In case of active overall corrosion the Nickel
content will increase significantly by a factor 5 and thus readily detectable.

After monitoring the Nickel content for 6 days, the oxygen content was reduced to 0.3
vol.-%. The Nickel content did not change during the test, see figure 1. The Nickel
content of about 0.2 ppm is constant throughout the test.



















[Ni] content end product (ppm)
Laboratory analysis
0.00
0.10
0.20
0.30
0.40
0.50
0.60
3
1
/
7
4
/
8
8
/
8
1
2
/
8
1
6
/
8
2
0
/
8
2
4
/
8
2
8
/
8
1
/
9
5
/
9
9
/
9
Date
o
x
y
g
e
n

c
o
n
t
e
n
t

(
v
o
l

%
)
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
[
N
i
]

c
o
n
t
e
n
t

(
p
p
m
)
oxygen (vol %)
[Ni] content (ppm)
Low Oxygen test
baseline
Figure 1: Nickel content in end product (0.2 ppm). No change during Low Oxygen Test

4.
3. Risk analysis

As the proposed low oxygen test (0.3 vol%) is for the first time executed in a
Stamicarbon CO
2
stripping urea plant, the execution of a risk analysis before starting the
test seems appropriate.

3.1. Risk analysis for Safurex

The risk to operate Safurex

with an oxygen content of 0.3 vol% can be qualified as non

existing based on the following facts:

3.1.1. Zero oxygen tests on laboratory scale
Stamicarbon did perform numerous corrosion tests at nearly zero oxygen levels in
laboratory.



>30 mm / yr 75 days 183C 25.22.2
? mm / yr 75 days 183C 316L-UG
0,05 mm / yr
75 days 183C SAFUREX

SAFUREX

BC.01
BC.05
disappeared
>30 mm / yr 75 days 183C 25.22.2
? mm / yr 75 days 183C 316L-UG
0,05 mm / yr
75 days 183C SAFUREX

SAFUREX

BC.01
BC.05
disappeared
Figure 2: Stamicarbon laboratory tests in oxygen free carbamate

From Figure 2 one can conclude that Safurex

can withstand very low oxygen contents

contrary to the normal austenitic stainless steels.

3.1.2. Flange face leakage of SPC's Safurex

stripper
Another evidence and experience was gained by incidence. In October 2003 as well as
September 2005 a flange face leak occurred in the Safurex

stripper. Such a leak

occurs in case the gasket in heavily damaged. Such an occurrence normally results in
heavy corrosion of the gasket serrated ring (BC.03 material quality) and flange faces
(BC.05 material quality) due to crevice corrosion (oxygen depletion in the crevice), see
figure 3.
In SPC's case the severeness of the corrosion could only be observed by the damage
of the BC.03 serrated ring, see figure 4a. However the flange faces were intact, see
5.
figure 4b and after cleaning and gasket replacement the operation could directly restart
again. Not even machining was needed.

Figure 3: Flange faces after a leakage of the man way gasket in case of a BC.05 and Safurex

flange face. In the picture left the heavily corroded flange face (BC.05) is shown due to crevice
corrosion. On the right hand side a Safurex

flange face is presented having no corrosion at all

after a gasket leak


Figure 4a: (Sept. 2005): heavily corroded Figure 4b: no corrosion of Safurex

BC.03 gasket ring flange face


Not corroded
Safurex
flange face











BC.05
Safurex

BC.05
Safurex

PTFE
envelope
BC.03
serrated
gasket ring
Corroded BC.05
flange face
Not corroded Safurex
flange face
Not corroded


3.1.3. Experiences in NH
3
stripping plant
No corrosion occurred in a plant test of Safurex

parts in a NH
3
stripping plant at 0.25 to
0.30 vol% oxygen levels and elevated temperatures around 200
o
C.





6.
3.2. Risk analysis for Austenitic Stainless Steels

3.2.1. Conventional Urea plants
Evidence that the oxygen content can be reduced safely to 0.3 vol.-% is the fact that in
the old days conventional urea plants operated at oxygen levels of 0.3 vol.-%. The
synthesis section of the conventional plants consisted of a reactor and mixer in BC.01
quality. Process conditions were even more severe from corrosion point of view: 190 C
and 200 bar.

3.2.2. HP carbamate condenser in BC.05
At SPC the HP carbamate condenser is made from BC.05.
After the HP stripper the HP carbamate condenser is the most critical when reducing the
oxygen content. In general corrosion is more critical at higher temperatures and low
oxygen contents.

Figure 5: Temperature and partial oxygen content in the synthesis section
O
x
y
g
e
n

p
r
e
s
s
u
r
e
T
e
m
p
e
r
a
t
u
r
e
Stripper Reactor
HP Carbamate
Condenser
Top
Bottom
Bottom
Top
Temperature
Reactor
HP Scrubber
HP CC
Stri pper
O
x
y
g
e
n

p
r
e
s
s
u
r
e
T
e
m
p
e
r
a
t
u
r
e
Stripper Reactor
HP Carbamate
Condenser
Top
Bottom
Bottom
Top
Temperature
Reactor
HP Scrubber
HP CC
Stri pper
Figure 5 shows the temperature (red line) and partial oxygen content in the CO
2
stream
through the HP synthesis section. In the top of the Stripper the highest temperatures in
combination with the lowest partial oxygen content prevails, indicating the worse
corrosion conditions. In SPC the original stripper is replaced by a Safurex

stripper,
making it no longer sensitive to corrosion anymore even at low partial oxygen
pressures. Milder corrosion conditions prevail in the other equipment. The top of the
HPCC is the second worse location in the synthesis form corrosion point of view. In
SPC the original BC.01 HP carbamate condenser is replaced by a new HP carbamate
condenser made from BC.05, a more corrosion resistant material quality. This means
that also the HP carbamate condenser allows for a lower oxygen level for passivation.

7.
4. Process consequences

The reduction of the oxygen content first of all leads to more urea capacity as the air
added in the CO
2
compressor feed can now be replaced by CO
2
. Some 2% additional
CO
2
in this way is sent to the synthesis section at constant speed of the CO
2

compressor.

The reduction of the oxygen content resulted in
Increase in reactor top temperature (see figure 6) resulting in an increase in
reactor conversion
This leads to a lower steam consumption in HP Stripper, see figure 7
These results are obtained at a synthesis pressure of 140 142 Bar.


Figure 6: Increase in reactor top temperature


















Reactor Top Temperature (Deg C)
TAG-number: T141202
0.00
0.10
0.20
0.30
0.40
0.50
0.60

3
1

/
7
4
/
8
8
/
8
1
2
/
8
1
6
/
8
2
0
/
8
2
4
/
8
2
8
/
8
1
/
9
5
/
9
9
/
9
Date
O
x
y
g
e
n

c
o
n
t
e
n
t

(
V
o
l

%
)
180
180.5
181
181.5
182
182.5
183
183.5
184
184.5
185
T
e
m
p
e
r
a
t
u
r
e

(
D
e
g

C
)
oxygen (vol %)
Temperature (Deg C) Low Oxygen Test baseline











8.
Figure 7: Reduction of steam consumption in HP Stripper


Steam Consumption Stripper (Tons/hr)
TAG-number: FR41094



















Reduced steam consumption per ton of end product of 40 kg was obtained.



4.1. Emission figures
When less air is introduced in the HP synthesis the ammonia emission from the 4 bar
absorber is reduced.
In the SPC plant the throughput of the vent valve position of the 4 bar absorber was
reduced from 50 % to 30 %.


0.00
0.10
20
30
40
50
60
3
1
/
7
4
/
8
8
/
8
1
2
/
8
1
6
/
8
2
0
/
8
2
4
/
8
2
8
/
8
1
/
9
5
/
9
9
/
9
Date
O
x
y
g
e
n

c
o
n
t
e
n
t

(
v
o
l

%
)
49
50
51
52
53
54
55
56
57
58
59
S
t
e
a
m

(
T
o
n
s
/
h
r
)
0.
0.
0.
0.
0.
oxygen (vol %)
Steam (Tons/hr)
Low Oxygen test baseline
9.
5. Corrosion consequences

The Nickel content during the low oxygen test did not change, indicating that there is no
increase of corrosion.

During the turnaround of the SPC plant, this observation was confirmed in the corrosion
inspection of the HP equipment.

The SPC plant was also inspected by Stamicarbon in 2000. The findings during this
inspection can thus be compared. Based on the inspection in 2000 and 2005 the
condition of the HP equipment is excellent taking into account the on-stream time of the
equipment.

5.1. HP Stripper (Safurex

)
The Safurex

stripper, installed in 2002 has an effective on-stream time of 1097 days (3

years). The average corrosion rate measured in the heat exchanger tubes of 0.05 mm/y
was far better than the corrosion rate of the former BC.05 stripper; 0.09 mm/y.
The lining and overlay welding in both top and bottom channels showed no corrosion.
This was confirmed by UT thickness measurements.

5.2. HPCC (BC.05)
The HPCC was replaced in 1996 and has an effective on-stream time of 1956 days (5,4
years). The corrosion rate of the heat exchanger tubes in the HPCC did not change
before and after the low oxygen test. During the inspection in 2000 as well in 2005 the
corrosion rate in the heat exchanger tubes nears to zero. Also the liners and overlay
welding in top and bottom channels showed no corrosion, as was confirmed by UT
thickness measurements. This is a normal corrosion behavior for BC.05 carbamate
condenser in Stamicarbon stripping plants.

5.3. HP Reactor (BC.01)
The HP reactor is still original, having a total effective on-stream time of 5277 days (14.5
years). Typical in the top of the reactor the highest corrosion will take place. Based on
UT measurements a corrosion rate in the top part is 0.06 mm/y and also the corrosion
rate did not change due to the low oxygen test. A corrosion rate of 0.06 mm/y is low;
normally a corrosion rate of 0.1 mm/y is found.

5.4. HP Scrubber (BC.01)
The HP Scrubber is still the original, except for the tube bundle, which was replaced in
1999. Effective on-stream time of the heat exchanger tubes mounts up to 1744 days
(4.8 years). The corrosion rate measured in the tubes is 0.02 mm/y. This was also
measured in 2000. Again there is no change in corrosion rate observed before and after
the low oxygen test.

5.5. HP Piping (BC.01)
At random UT wall thickness measurements on all HP pipelines showed no significant
corrosion from process side.
10.
6. Process safety

The vapor stream in the synthesis with the highest risk with respect to flammability is the
HP purge stream from the HP scrubber (highest hydrogen and oxygen concentration
under high pressure and temperature).

When reducing the oxygen content in the synthesis section, the composition of the HP
purge stream will change (less oxygen), but also the total purge stream will reduce
(ammonia purge will be lower).

Both effects will result in a situation (at 0.3 vol % oxygen) in which the composition of
the HP purge stream is moved away from the explosion limits of the O
2
H
2
NH
3

mixture at the given circumstances. Thus the risk for explosions is reduced.


11.
7. Conclusions

The low oxygen test showed that the SPC plant can run safely with 0.3 vol.-% oxygen in
the CO
2
feedstock without any risk for higher corrosion rates in the synthesis section.
Process benefits were clearly demonstrated; the reactor conversion increases, steam
consumption in the HP Stripper reduces and ammonia losses decreases.
There became more room to increase the compressor capacity for higher plant
production. The SPC compressor speed however was limited for mechanical reasons.
Finally the plant runs safer at lower oxygen levels, since the composition of the HP
purge system moves away from the explosion limits. The ultimate goal is to have zero
oxygen for an intrinsically safe plant. This can only be realized by having all equipment
in the synthesis section in Safurex

.

However for existing urea plants Stamicarbon decided to set the oxygen content in the
CO
2
feedstock at 0.3 vol.-% when following pre-requisites are met:
HP Stripper in Safurex

(BE.06)
HPCC / HP Poolcondenser in BC.05 material quality

Thus, all urea plants having a Safurex

stripper and a BC.05 HP carbamate condenser

or Poolcondenser have the possibility to increase the safety level and benefit from
process advantages by lowering the oxygen content to 0.3 vol.%.
















12.