Preventing Stress Corrosion

Cracking in the Carbon Dioxide

Absorber of Ammonia Plants

Through field tests and experience, the threshold below which SSC
does not occur is estimated at 100 MPa. A new local stress relief
technique can lower residual welding stresses in that level.

Hiroshi Ishimaru and Tetsuya Takegawa

ABSTRACT field tests with precracked C-T

specimen to decide threshold stress
After nine year operation of CC>2 level below which S.C.C. does not
removal tower using Vetrocoke process, occur,
stress corrosion crackings (S.C.C.)
were found in 19?6 only on its locally The suitable local stress relief was
stress relieved circumferential butt applied to 101-E tower successfully,
welds. Though there was no difference and no S.C.C. took place for the
in hardness between locally and wholly following one year.
stress relieved welds, the residual
stresses of locally relieved welds
were far higher than that of wholly
relieved ones. By heating the limited 1. CC>2 removal tower
band width of shell, it bulged and
non-sustained bending moment was The 750 ton/day ammonia plant of
generated. This moment deformed the Sumitomo Chemical Company
heated portion of shell plastically, designed by M. W. Kellogg came on
and consequently, residual stresses stream in Niihama in May, 196?
were redistributed when cooled. To Potassium carbonate solution
lower that moment, the uniform temper- activated by arsenous oxide,
ature band width should be kept wide namely, Giammarco-Vetrocoke
and temperature gradient be minimized. solution, is used in CC>2 removal
process of this plant. It is
After carrying out intensive examina- reported that though carbon steel
tions with a large size model, we has a high corrosion resistance
determined the necessary uniform band against this solution to save
width and gradient of temperature to special alloy, it is susceptible
lower the residual stress below the to stress corrosion crackingl)2).
prescribed level. e also carried out
The C02 removal tower is made of
ASTM A212 Gr B and 45 m (148 ft)
in height, and consists of four
Sumitomo Chemical Company, Limited parts, each of which was wholly
Niihama, Ehime, Japan stress relieved in a closed
furnace before assembling in a
0149-3701-80-2959 $01.00 1980
American Institute of Chemical Engineers
170
vendor's shop. It has three
locally stress relieved circum-
ferential butt weld joints. e
call them C-7, C-13 and C-l8.
(Weld lines were designated from
C-l to C-23 from the top.)
The nominal composition of
Vetrocoke solution is 300 kg/m3
K2C03, 110 kg/m3 AS23 and the
ratio of C02 to K2 is in a range
from 1.7 to 0.9- Composition of
process gas at the inlet is 52%
H2, 21% C02 and 17% 2 The
temperature is about 110C in the
middle of the tower.
Details on stress corrosion
cracking
Stress corrosion crackings were
found only on the three locally
stress relieved welds, namely, C-71
C-13 and C-l8 after nine year
operation of the tower. Before
that time, these welds had not
been inspected.
The cracks, mainly branched
intergranular, are produced in the
deposit metal and propagated a
little into the base metal
longitudinally. The ratio of
crack length on the metal surface
to depth was small.
The Vickers hardness number of
cracked welds is from l80 to 190
and have no difference in hardness
from shop stress relieved ones.
To inspect these cracks from out-
side on streamly by angle beam
technique of ultra-sonic, the
depth of crack should be deeper
than 1/4 of wall thickness and
weld reinforcement of both surface
be ground off.
Measurement of residual stresses
of C02 removaltower by X-Ray
method
The occurrence of stress corrosion
cracking is limited to the locally
heat treated welds. This is
because, we suppose, there is a
difference in the degree of relief
of residual stress between wholly
and locally heat treated welds.
171
We measured the inner surface
residual stresses of the tower by
X-Ray method.
As shown in Figure 1, the residual
stresses of locally stress
relieved welds were over 20O MPa
(29.0 ksi) which were extremely
higher than those of wholly heat
treated ones.
After the cracks were ground off
and welded for repair, local
stress relief was done according
to the ASME code in 1976.
Repaired circumferential weld
lines were heated in uniform from
outer surface with wrapping heater
elements. Although the residual
stresses were still high and
stress corrosion crackings took
place again after a year opera-
tion.
In 1977, those cracks were
repaired again and local stress
relief was done with a longer
holding period and a higher hold-
ing temperature. Since more than
20O MPa (29 ksi) of residual
stresses still remained, occur-
rence of stress corrosion cracking
could not be prevented.
We measured residual stresses of
another C2 removal tower which
was made recently. The result
indicates that the levels of
residual stress in wholly stress
relieved welds are about 35 MPa
(5.1 ksi) while those of locally
stress relieved ones are in a
range from 100 to 200 MPa (l4.5 to
29 ksi). We concluded that under
the conditions that meet minimum
requirements of ASME code, the
local stress relief could not
lower residual stress to the level
below which stress corrosion
cracking does not occur. The
result quantitatively certifies
the notice by the British Standard
1515 Part 1 that local stress
relief is not effective to prevent
stress corrosion cracking.
On the other hand, it seems that
the metallurgical benefit of
softening the deposit metal and
the heat affected zone by temper-
ing hardened structure is produced.
Stress level for safe operation
The relation between value of
surface residual stresses of the
welds of our tower 101-E measured
by X-Ray method and occurrence of
stress corrosion cracking showed
that no stress corrosion cracking
takes place below the stress of
l60 MPa (23.2 ksi).
The threshold stress intensity
factor K value obtained through
field test with self loaded
compact tension specimens is shown
in Figure 2. The harder the
material is, the lower becomes the
KISCC value. Contact of the
material with zinc, a less noble
metal, gives effect to prevent the
precrack of the specimen from
propagating.
The threshold nominal stress level
can be calculated from these
results. The calculation accuracy
largely depends upon the estimated
size of initial flaw. The thresh-
old stress level necessary for
safe operation is decided to be
100 MPa (14.5 ksi) considering
those test results and field
experience (a stress corrosion
cracking has not been taken place
on wholly stress relieved welds.)
Comparison on methods for prevent-
ing stress corrosion cracking
(1) Shotpeening
This is a method to obtain
high compressive residual
stress most easily on the
steel surface. In this
method, however, it is
difficult to peen long weld
line uniformly and the ten-
sile residual stress comes
peak at the end of peened
parts .
(2) Vibrational residual stress
relief
For sufficient stress relief,
the vibrational stress is
required to exceed the yield
172
stress of material. There-
fore, this method is hardly
applied to the tower.
(3) Flame plastic spraying
Carbon steel strips whose
surface were sprayed with
epoxi or fluorine resin were
tested in the field. The
former was attacked by the
Vetrocoke solution, and the
latter was not damaged by
the same. The technology for
flame spraying of fluorine
resin in the field have not
been established.
(4) Type 304 stainless steel
strip lining
The results of field test
with U-Bended specimens show
that the type 304 stainless
steel does not have suscep-
tibility to stress corrosion
cracking. But the large
difference in coefficient of
thermal expansion between
carbon steel of shell and
stainless steel of lined
metal redistributes the
residual stress at the fillet
edge welds around all four
sides of lined metal during
the post weld heat treatment.
(5) Effect of hardness to the
occurrence of stress corro-
sion cracking
Bent-beam specimens with
various hardnesses controlled
by heat treatment were tested
in the field for five years
and checked by microscope
occurrence of stress corro-
sion cracking on their cross
sections. The threshold
hardness of normalized
ferritic-pearlitic structure
below which stress corrosion
cracking does not occur is
somewhat higher than that of
martensitic or tempered
martensitic structure. These
results indicate that the
carbon steel, the hardness of
which is below 20O Vickers,
immune to the stress corro-
 sion cracking. Although the
hardness of the tower is not
higher than l80 Vickers ,
stress corrosion cracking
takes place.
We also studied the repair
method in which the tower is
welded from inside while
cooling it from outside. It
seems difficult, however, to
apply the method to the plant.
Consequently, we began to
seek for the following new
techniques for field heat
treatment to relieve residual
stresses below the threshold
level .
Examination on holding time and
temperature
MX = -D ( d Wi
Holding time and temperature
necessary to relieve welding
stress below the threshold level
were studied with two types of
small specimens : the one is
circular grooved weld and the
other is weld overlayed by
electrodes to repaired C02 removal
tower .
Post weld heat treatment was made
in a muffle electric furnace, and
surface residual stresses were
measured by X-Ray method before
and after the heating. So it is
clearly indicated that almost all
welding stresses are relieved after
heat treatment for an hour at 500C
(l,040F). The effect of tempera-
ture to stress relief is not
improved over 580C (1,O76F). In
order to prevent lowering of
tensile strength, the material
temperature must not be high for a
long time.
The reason why residual stresses
are not relieved by local heat
treatment
We consider the residual stress is
not relieved by local heat treat-
ment under the conditions that meet
minimum requirements of ASME code
because of the following:
When circumferential band width of
cylindrical shell is heated, it
173
buldges locally and, as a result,
non-sustained force is generated
at the boundary between uniform
and not-uniform parts of longitu-
dinal temperature distribution.
As the simplest example, a
cylindrical shell with symmetrical
linear temperature distribution to
weld line is assumed (Refer
Figure 3) Then the maximum moment
value Mo is generated at point 0
and can be calculated as follows J"
(t0 -
Mo = -( (1)
The moment MX at the weld line
which is apart from point O by X
is given by the following equa-
tion :
o'
d X^
(2)
Where a: radius of shell
h: thickness of shell
D:
12(1 -
=
\j = Poison's ratio
E = Young's modulus
As yield strength of material
drops at high temperature, moment
MX deforms weld line plastically
and reproduces and/or redistrib-
utes residual stresses. On the
other hand, Figure 11 given by
S. T. Timoshenko indicates that
the moment MX comes to almost 0 if
distance x is over 3/- This
means if uniform temperature width
is 6/, external force is not
applied to the weld line. It is
impracticable to heat uniformly
the band width of 6/ of actual
tower with a large radius, and
reproducing of stress at point 0
can not be avoided. So, we have
 carried out several experiments
with large size cylindrical shell
model to find applicable condi-
tions for successful local stress
relief to the tower.
8. Local stress relief heat treatment
test with a large size cylindrical
shell model
The shell used in the test is
1.5 m (4.9 ft) in diameter, 3 m
(9.8 ft) in length, 32 mm (1-1/4
in) in wall thickness of ASTM
SA516 Gr 7O and has three circum-
ferential butt welds which are not
stress relieved. The residual
stresses were measured by X-Ray
method. Each of three circum-
ferential butt weld lines were
heated from outside by wrapping
heater elements. The longitudinal
temperature distributions are
given in Figure 4.
The residual stress values after
local stress relief by the conven-
tional temperature distribution
CASE A which meets the ASME codes
are still high as experienced in
the field tower. Use of low
strength welding rod as overlaying
metal is effective to decrease
welded residual stresses, but it
gives no effect to the residual
stress after stress relief.
Figure 5 shows the longitudinal
residual stress distributions
before and after stress relief by
CASE B with more gradual tempera-
ture distribution than CASE A.
And results of CASE C with flat
temperature distribution which has
concave region at its center are
shown in Figure 6. The width of
uniform temperature region is
2.3/- The residual stresses are
relieved satisfactory. So minimum
requirement of uniform temperature
band width is determined. Since
the tower has many holes, nozzles
and other devices, it is difficult
to add sufficient heating elements
thereto to keep wide and uniform
temperature band width. We tested
the Bulk Head Method. In this
method, the shell is partitioned
off with bulk heads which face
each other across the weld line,
174
and heated from inside with space
heater units installed therein.
Its outside is only insulated with
asbestos clothes. The temperature
of inner surface is somewhat
higher than that of outer one, but
as shown in Figure 7, the residual
stresses are relieved sufficiently.
This method is concluded to be
most practical in the field.
Judging from these results, it
becomes clear that if the uniform
temperature band width is kept
over 3/ it is possible to lower
the residual stresses in the weld
below 100 MPa (14.5 ksi). And if
the distance .between the weld line
and the point where the tempera-
ture comes a half of the maximum
value is larger than 3/i the
residual stresses reproduced at
the discontinuous point 0 of the
temperature distribution do not
come to the harmful level.
9- Results of field heat treatment
f0rCO2 removaltower
We found out the method for field
stress relief that can bring
satisfactory result.
In March, 1978, we applied it to
the locally repair welded 101-E
C02 removal tower. The tower was
heated by Bulk Head method. The
longitudinal distribution of
temperature and the residual
stresses after heating at C-l8
weld line are shown in Figure 8.
The residual stresses in weld line
were relieved sufficiently below
the prescribed level to prevent
stress corrosion cracking. There
was no difference in stress
distribution circumferentially.
The reproduced stress at the
discontinuous point of longitu-
dinal temperature distribution
also did not exceed that level.
After a year operation, inner
surface of the tower was inspected
by magnaflux and microscopic
replica method in March, 1979-
No crack was found at the welds
of tower. It is still in a sound
state at present.
Conclusion
(1) Stress corrosion crackings
were found only in the locally
stress relieved welds of C(>2
removal tower operated for
nearly nine years. The
Vetrocoke process was used,
but inhibitor for stress
corrosion cracking was not
used.
(2) As a whole, the residual
stresses at the welds
relieved in a closed furnace
are low enough, but they
exceed 200 MPa (29.0 ksi) at
the locally stress relieved
ones. The residual stresses
were measured by X-Ray method.
(3) Residual stresses at the
locally heat treated welds
were not relieved. This is
caused by the moment
generated at the discontinu-
ous point of longitudinal
temperature distribution. By
keeping the uniform tempera-
ture band width across the
weld line over 3/i residual
stress can be lowered below
the threshold level.
(4) The threshold stress below
which stress corrosion crack-
ing does not occur is esti-
mated to be 100 MPa (l4.5 ksi)
through field tests and
experience. Materials with
hardness higher than 200
Vickers have susceptivity to
stress corrosion cracking.
(5) Local stress relief which
meets above mentioned
requirements was conducted on
C2 removal tower 101-E, and
residual stresses were
confirmed to be below the
threshold level.
After a year operation, its
inner surface was inspected
and no stress corrosion
cracking was found at the
locally stress relieved
welds.
175
Acknowledgement
We wish to express our thanks to
Mr. Kamohara, Hitachi Research
Laboratory, Mr. Fukujouji, Mr. Matsuo
and Mr. Morita, Kasado Works of
Hitachi, LTD. for their informative
suggestion and work for experiments
with large sized model and also to
Messrs, the Kasado Works and Hitachi
Research Laboratory of Hitachi, Ltd.,
and Sumitomo Chemical Company for
giving us permission to publish this
article.
Literature cited
1. Atkins, K,T,G., Fyfe, D. and
Rankin, J,D
Corrosion in C2 removal plant
towers.
Presented at AICHE symposium on
safety in ammonia plants and
related facilities, Vancouver,
Sept. 1973-
2. Naito, K., Hashimoto, T. and
Kihara, T
Stress corrosion cracking of mild
steel in gas treating plants.
J. Japan Petrol. Inst. 14 , 762
(1971)
3- Timoshenko, S,P. and Krieger, S.
Woinowsky
Theory of plates and shells,
chap. 15, second edition, McGRAW-
HILL
4. Burdekin, F,M
Local stress relief of circum-
ferential butt welds in cylinders.
Brit, welding journal. Sept. 1963,
483-490.
T* P
ISHIMARU, H. TAKEGAWA, T.
 Weld (In* Residual tress (MPa) TOO,
40 80 120 160 200 "D MXM CASE A

C- 7 Deoo o MM CASC a
MM CASt C
HAZ .
Q
"V ^ 101 t 1*77
o 101 E 1*71 C-7
A
X ^X."'l E I97SC-C3
> C-13 Depo A

A
o
k. -^ ~ - - - - - -^p
- - - "

se
*
* e
^
A
j^ 200
:::::":::-:::::::::::::A l/ft Z/O 3/tt 4/fl s/a
il Another nflw
HAZ

-o
Length from

Figure 4. Longitudinal distribution of temperature at the

weld line

Dpo
101 E lower o
iC- o holding period of local stress relief heat
= C-22
JE ": Another new
HAZ :::::...<> treatment.
S IOIE fower D*po :~7A
O Stress relieved at Tenders shop.
-0 Stress relieved in 1976 in the field.
& Stress relieved In 1977 in the field. C-I weld line
Figure 1. Surface residual stresses of CO2 removal towers -6000
IO-E after local and whole stress relief heat
treatment.
IOO -500

(ksi) o>
-400
^ 60 60 100
80 Q.
E
N 50
-300
50-
40- O
O

28"
-100
I 20- Va 0 Vfl 2/fc SP 4//T
Length from C-l weld line
10- Figure 5. Distribution of residual stresses along the
longitudinal direction of large-sized model,
after local stress relief by Case B.
500 600 TOO
Tensile strength (MPa)
Figure 2. Relations between KjgCC *n G-V solution and C-3 W.U

tensile strength of carbon steels.

Temperature
0

-co-
2/rt l/f 0 l/f 2/f3 3/fl 4/13 *>/(*
Length from C-2 weld line

Figure 6. Distribution of residual stresses after local stress

Figure 3. Simple model of causing of bending moment by relief by Case C.
local heating of shell.

176
 -Weld line Bottom -weld line Top

M O \/ft 2/a V/9 5/a

Length from weld line

Figure 7. Distribution of residual stresses after local stress 3/rt 2/a 1/4 O 2/0 3//3
Length from weld line
relief by Bulk Head method.
Figure 8. Longitudinal distribution of outer surface
temperature and inner surface residual
stresses of Tower 101-E.

177