Engineering Failure Analysis 14 (2007) 164–169

www.elsevier.com/locate/engfailanal

Embrittlement evaluation and lifetime assessment of

hydrocracking pressure vessel made of
3Cr–1Mo low-alloy steel
S.A. Jenabali Jahromi *, M. Najmi
Department of Materials Science and Engineering, School of Engineering, Shiraz University, Shiraz, Iran

Received 4 May 2005; accepted 5 November 2005

Available online 29 March 2006

Abstract

The Cr–Mo steels which are widely used for pressure vessels in refineries and petrochemical plants, have a potential for
hydrogen and temper embrittlement. During long-time service the embrittlement leads to decrease of the critical flaw size
of brittle fracture and/or to the reduction of the remaining life of a pressure vessel. In this investigation the effect of high
temperature and high pressure hydrogen on a vessel, made of 3Cr–1Mo low-alloy steel is studied. Inspections show that the
only detected crack in the base metal is originally formed by welding defects and calculations show that it will not grow up.
Therefore, it is predicted that the operation of the pressure vessel in normal condition and under regular supervision can be
continued.
 2006 Elsevier Ltd. All rights reserved.

Keywords: Hydrocracking pressure vessel; 3Cr–1Mo Low-alloy steel; Temper embrittlement; Crack growth

1. Introduction

In the past, concern in the petroleum industry regarding selection of materials for pressure vessels has
focused largely on safety and economic issues, which dictate against unexpected equipment failures. More
recently, however, the need for extension of the lives of current plants well beyond their originally anticipated
durations has also become an important issue [1].
With respect to the fact that many of the world’s refinery and process plants reaching and exceeding their
design life, there is a growing importance being attached to the assessment of the integrity of welded pressure
vessels in which hydrogen or hydrogen containing fluids are processed at elevated temperatures [2].
Low-carbon, low-alloy steels are often used in these situations in the petrochemical industries and refiner-
ies. These steels mainly contain Cr, Mo, or V as significant alloying elements [3].

*
Corresponding author. Tel.: +98 711 230 7293; fax: +98 711 628 7294.
E-mail address: jahromi@shirazu.ac.ir (S.A. Jenabali Jahromi).

1350-6307/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.engfailanal.2005.11.009
 S.A. Jenabali Jahromi, M. Najmi / Engineering Failure Analysis 14 (2007) 164–169 165

More and more fitness for service (FFS) evaluation is used in the petrochemical industry, together with an
improvement of the safely of workers and plant integrity. FFS assessment can save a lot of money by increas-
ing inspection intervals, avoiding necessary repairs or increasing the life of pressure vessels [4].
The Cr–Mo pressure vessel steels have a potential for temper embrittlement that leads to toughness degra-
dation and decrease of the critical flaw size for brittle fracture [5,6]. The safety of the reactor vessels must be
assured by in-service inspections, such as ultrasonic testing, and the analysis of the test results to assess the
remaining life of the vessels [6].
Temper embrittlement shifts the ductile-to-brittle transition temperature to higher values, resulting in cor-
responding reduction in fracture toughness. In this situation the risk of failure occurs not under operating con-
ditions but during start-up and shut down conditions.
Temper embrittlement occurs due to segregation of impurities such as As, Sb, Sn, S and P, to grain bound-
aries during heat-treatment or high temperature service [7]. Hippsley and Lewandowski [8] indicated that
intergranular sulfur enrichment was detected before fracture nucleation. Watanabe et al. [1] proposed an
embrittlement factor ‘‘J’’ which relates impurity elements to temper embrittlement which defined as
J ¼ ðSi þ MnÞ  ðP þ SnÞ  104 ;
where concentration of various elements are expressed in weight percent.
Other degradation in the presence of hydrogen or hydrogen-containing compounds is hydrogen embrittle-
ment. The principal effects of this embrittlement are manifested as reduced ductility and as reduced threshold
stress intensity for crack propagation [1,9]. It is generally felt that elements causing temper embrittlement,
enhances the hydrogen embrittlement susceptibility [7].
This investigation has been carried out on a thick wall hydrocracking pressure vessel to evaluate the embrit-
tlement and estimation of the remaining life.

2. Materials and experimental procedures

The hydrocracking pressure vessel is made of a 3Cr–1Mo steel and operating for about 28 years. The range
of normal operating temperature is from 380 to 455 C and the hydrogen pressure is 16.94 MPa.
The pressure vessel is overlayed internally with a 3–5 mm thick weld metal of type 347 stainless steel.
Table 1 lists other important characteristics of pressure vessel.
The pulse-echo short wavelength ultrasonic testing (SWUT), magnetic particles and dye-penetration meth-
ods are used to detect any failure or crack. Also the hardness of several points along axis of the vessel mea-
sured with a portable device, which includes weld, heat affected zone (HAZ) and base metal. Some powder
samples were taken from different parts of pressure vessel, by grinding, to evaluate the chemical analysis.
Experimental procedures and calculation flow chart is shown in Fig. 1.

3. Results

The chemical composition of the vessel is analyzed by atomic absorption method and the results are shown
in Table 2. Table 3 lists the average Brinell hardness number in different zones of the pressure vessel.
The only remarkable detected crack which was found by ultrasonic technique was in the middle of a cir-
cumferential weld and it’s dimensions was 50 mm M 42 mm M 12 mm. Fig. 2 shows the schematic shape
and position of the crack.
Table 1
Characteristics of the pressure vessel
Maximum operating temperature 455 C
Design yield strength (room temperature) 516.8 MPa
Design yield strength (470 C) 414.3 MPa
Design Charpy energy (10 C) 47.45 J
Thickness of base metal 186 mm
Thickness of overlay 3–5 mm
External radius of vessel 2.81 m
166 S.A. Jenabali Jahromi, M. Najmi / Engineering Failure Analysis 14 (2007) 164–169

Inspection Stresses J-factor CVN

KIC-US
Crack size KI

KIH KIC

a cr
KI>KIH

Crack growth

Leak Remaining life Fracture

Fig. 1. Flow chart of experimental procedures and calculation.

Table 2
Chemical analysis of the vessel (wt %)
Element C Cr Ni Mn Mo Sn Sb Si Cu P S
wt% 0.35 3.0 0.20 0.50 1.10 0.025 0.055 0.20 0.10 0.02 0.025

Table 3
Average hardness number of different zones of the vessel
Zone Base metal Weld metal HAZ
Hardness (BHN) 201.3 217.0 233.0

4. Calculations and embrittleness evaluation

To evaluate the pressure vessel condition, embrittleness factors and fracture mechanics approach are used.
In the calculations the information of 2.25Cr–1Mo low alloy steel is used wherever, there is not enough infor-
mation about 3Cr–1Mo pressure vessel alloy steel.
Eq. (1) shows the fracture criterion based on fracture mechanics, in terms of half crack length, a [6]
a P acr ; ð1Þ
acr is critical crack size for brittle fracture. Eq. (2) calculates the critical crack size for embedded cracks
K 2IC Q
acr ¼ ; ð2Þ
pr2
where KIC is fracture toughness, Q is a flaw shape parameter and r is the applied stress.
With respect to the hardness measurements, the yield strength is about 430 MPa [10].
According to Table 2 J-factor can be calculated.
 S.A. Jenabali Jahromi, M. Najmi / Engineering Failure Analysis 14 (2007) 164–169 167

Fig. 2. Schematic views of pressure vessel and the detected crack.

J -factor ¼ ðSi% þ Mn%Þ  ðP% þ Sn%Þ  104

ð3Þ
J -factor ¼ ð0:2 þ 0:5Þ  ð0:02 þ 0:025Þ  104 ¼ 315
This factor reveals the amount of temper embrittleness of pressure vessel [1], which its value for an unused
and advanced reactor materials is around 100.
According to the J-factor the fracture appearance transition temperature (FATT), is calculated for
3 · 105 h as below [6];
FAAT ¼ 79:3 log t  253 ¼ 181  C ð4Þ
Two stress sources can be available in this case. The first one is the applied stress due to the internal pres-
sure of the vessel and the other one is the residual stress in the weld area.
Based on the shape and position of the detected crack, the hoop stress is the most important component of
the applied stress which can develop the crack. This stress can be calculated by the following equation [11]
 
pi r2o ro
rh ¼ 2 1 þ 2 ; k ¼ ¼ 1:153;
k 1 ri ri
 2
ð5Þ
16:94 1405
rh ¼ 1þ ¼ 119:74 ðMPaÞ;
1:1532  1 12192
where rh is the hoop stress, pi is the internal pressure, ro and ri are outside and inside radius, respectively.
With respect to American Petroleum Institute (API), the residual stress at the weld area should be consid-
ered for the FFS assessment of component containing a crack-like flaw [12]. Equation (6) shows how the resid-
ual stress in the weld should be calculated
rr ðxÞ ¼ 0:3rrys ¼ 0:3ðrys þ 69 MPaÞ ð6Þ
168 S.A. Jenabali Jahromi, M. Najmi / Engineering Failure Analysis 14 (2007) 164–169

which rys is design yield stress and rrys is actual yield stress. But Schlögl and Giessen [13] indicate that the resid-
ual stresses will disappear after a few years of operation. So after such a long years of operation, the weld
residual stress is not expectable and it has been released.
The crack shape parameter (Q) is 2.93 according to formula (7) [14,15]
1:65 2
Q ¼ 1 þ 1:464ða=cÞ  0:212ðr=ry Þ ¼ 2:93;
r=ry ¼ 120=430 ¼ 0:3; ð7Þ
2a ¼ 50 mm; 2c ¼ 42 mm; a=c ¼ 1:19;
The stress intensity factor KI for the detected crack is calculated by
rffiffiffiffiffiffi rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
pa p  0:025
KI ¼ r ¼ 120 ¼ 19:6 MPa; ð8Þ
Q 2:93
where, r is the applied stress, and a is half of the internal crack length. According to the Fick’s law, the hydro-
gen content at inner side of the crack is about 2 ppm [1], so the KIH is calculated by [6]
pffiffiffiffi
K IH ¼ 0:0014FAAT2  0:421FATT þ 57 ¼ 26:7 MPa m. ð9Þ
Since KI < KIH, the crack would not grow. To calculate the critical crack length, KIC should be found from
charpy energy. The upper-shelf CVN for pressure vessels has a correlation with KIC–US as below [1] and it
is considered that the value of Charpy v-notch energy (CVN) has decreased and became half after 28 years
of operation [16]
 2    2  
K IC–US CVN K IC–US 23:73
¼ 0:6478  0:0098 ) ¼ 0:6478  0:0098
r0 r0 430 430
pffiffiffiffi
) K IC–US ¼ 73 MPa m; ð10Þ
where r0 is the actual yield stress. And the relationship between KIC and KIC–US is [1]
K IC
¼ 0:623 þ 0:406 exp½0:00286ðT  FATTÞ
K IC–US
pffiffiffiffi
) K IC ¼ 73  ð0:623 þ 0:406 exp½0:00286ð455  181ÞÞ ) K IC ¼ 59 MPa m. ð11Þ
So the internal critical crack length acr is calculated:

k 2IC Q 592  2:93

acr ¼ ¼ ¼ 0:225 m ¼ 22:5 cm ) 2a ¼ 45 cm;
r2 p 1202  p
Since (acr > =thickness), the pressure vessel failure expected to be based on a leak before break criterion.
As KIÆKIH,then the crack will not grow, but if it grew the growth rate would be [6].
da pffiffiffiffi da
¼ 2:4  1024  K 11:7
I ; K I ¼ 19:6 MPa m ) ¼ 3:2  109 m=h; ð12Þ
dt dt
Therefore, the crack growth rate is very limited and the operation of the pressure vessel with respect to the
above fracture mechanics approach is expected to be safe.

5. Discussion and conclusion

The origin of the detected crack cannot be revealed because there is no access to it however, with respect to
its position (in the middle of the weld bead) it is predicted to form as a hot cracking during welding. According
to the fracture mechanics approach and despite of the temper and hydrogen embrittlement which have
occurred, the detected crack length a = 5 cm is very far from the critical crack length acr = 22.5 cm. Also
its growth rate is very low and if sometime the pressure vessel fails, it will leak before any break. Therefore,
under regular supervision the pressure vessel can operate in normal operating condition. But on the other
hand the important points related to the temper embrittlement should be considered. This means the
 S.A. Jenabali Jahromi, M. Najmi / Engineering Failure Analysis 14 (2007) 164–169 169

start-up and shut-down of the process should be done with respect to the calculated FAAT, which is about
180–200 C. In other words, in start-up and shut-down under 180 C the internal pressure of the reactor
should not be exceeded more than 30% of its design pressure [1].

Acknowledgements

The authors thank Engineer F. Baizaei the chief manager of Fars refinery for making this research effort
possible and Engineers M. Shadravan and J. Mehraban for their technical support.

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