Professional Documents
Culture Documents
1.
Introduction
2.
Application trends
3.
4.
5.
6.
7.
8.
9.
Creep properties
10.
Conclusion
Low alloy CrMo(V) steel plates for petrochemical reactors
Verfasser/Dokument
Content
Introduction
Wherever high temperatures and/or high hydrogen partial pressures in the
processes are required, CrMo steels have been used for more than 50 years.
Due to changing process parameters in chemical and petrochemical processes
these steel grades have been developed to enhanced properties.
conventional CrMo steels:
Verfasser/Dokument
1Cr Mo
2Cr 1Mo
ASTM/ASME
A/SA 387-12-1/2
EN 10028-2: 1992
13CrMo4-5
EN 10028-2: 2003
13CrMo4-5
ASTM/ASME
A/SA 387-11-1/2
EN 10028-2: 2003
13CrMoSi5-5
ASTM/ASME
A/SA 387-22-1/2
A/SA 542-A/B-3/4/4a
EN 10028-2: 1992
10CrMo9-10
11CrMo9-10
EN 10028-2: 2003
10CrMo9-10
12CrMo9-10
2Cr 1Mo V
ASTM/ASME
A/SA832-22V
3Cr 1Mo V
EN 10028-2: 2003
13CrMoV9-10
ASTM/ASME
A/SA832-23V
Verfasser/Dokument
A/SA 542-D-4/4a
A/SA 542-E-4/4a
EN 10028-2: 2003
12CrMoV12-10
Nelson-curves
800
700
6%Cr, 0,5%Mo
3%Cr, 0,5%Mo V
500
2,25%Cr, 1%Mo, V
1%Cr, 0,5%Mo
2,25%Cr, 1%Mo
400
1,25%Cr, 0,5%Mo
1%Cr, 0,5%Mo
300
Verfasser/Dokument
Temperature [C]
600
Carbon steel
200
0
50
100
150
200
250
acc. API 941, 1997
ever bigger and heavier reactors (already more than 1000t per unit)
Verfasser/Dokument
Verfasser/Dokument
fast rising and only few manufacturers are able to meet the very
high quality standards requested
up
on
up agr
t o ee m
42 e
t nt
225
200
N + AC + T
150
( Q + T)
125
N+T
up to 37 t
up to 37 t
100
75
50
up to 28 t
25
0
1.500
1.750
2.000
2.250
2.500
2.750
3.000
3.250
3.500
3.750
4.000
4.250
4.500
4.750
5.000
5.250
width [mm]
Maximum thickness is often limited by requirements from specifications
Low alloy CrMo(V) steel plates for petrochemical reactors
Verfasser/Dokument
thickness [mm]
175
J- / X-Factor
Ch-V + PWHT
20%
Hardness
Verfasser/Dokument
1Cr Mo
1Cr Mo
2Cr 1Mo
2Cr 1Mo V
Step Cooling
10
11
Kc
cooling rate
[C/h]
Kh
heating rate
[C/h]
t
Holding time
[h]*
Verfasser/Dokument
Temperature [C]
T
Holding
Temperature
[C]
Time [h]
heating
HP = T (+ 273) log
T (+ 273)
2,3 * Kh ( 20 - log Kh )
holding
+ t+
cooling
T (+ 273)
2,3 * Kc ( 20 -log Kc )
) + 20 ] * 10
-3
12
PWHT
670C/180Min.
680C/600Min.
690C/300Min.+700C/90Min.
675C/600Min.+680C/300Min.
HP
20.15
20.15
20.15
20.15
20.15
Verfasser/Dokument
Tempering
700C/300Min.
700C/250Min.
680C/250Min.
680C/60Min.
680C/60Min.
13
HB before
Before
PWHT
Verfasser/Dokument
HB after
After
PWHT
Hollomon parameter
14
1000
3CrMoV, t/4
3CrMoV, t/2
12CrMo 910
HP 20,8: Tempering
+705 C/10h
800
HP 21,11: Tempering
+705 C/30h
700
CrMoV: acc.
SA 542-D-4a
600
12CrMo 910 acc. EN 10028-2:2003
Verfasser/Dokument
R m [MPa]
900
500
thickness: 200 mm
condition: N+AC+T
400
19,00 19,20 19,40 19,60 19,80 20,00 20,20 20,40 20,60 20,80 21,00 21,20 21,40
HP
15
900
2CrMoV, t/4
2 CrMoV, t/2
3CrMoV, t/4
3CrMoV, t/2
12CrMo 910 (2CrMo)
700
HP 20,8: Tempering
+705 C/10h
HP 21,11: Tempering
+705 C/30h
600
500
CrMoV acc. SA 542-D-4a
Verfasser/Dokument
R p02 [MPa]
800
400
12CrMo 910 acc. EN10028-2:2003
300
19
19,2
19,4
19,6
19,8
20
20,2
HP
20,4
20,6
20,8
21
21,2
21,4
16
350
thickness: 200 mm
condition: N+AC+T
3CrMoV, t/4
300
250
200
150
100
Verfasser/Dokument
50
0
19,00
19,20
19,40
19,60
19,80
20,00
20,20
20,40
20,60
20,80
21,00
21,20
21,40
HP
17
Verfasser/Dokument
18
N+AC+T
(Q + T)
0 C
-29 C
-18 C
N+T
-18 C
0 C
200 HB
Hollomon parameter
Hollomon parameter
N+AC+T
(Q + T)
205 HB
210 HB
215 HB
220 HB
N+T
225 HB
20
40
60
80
20
60
195 HB
200 HB
205 HB
40
Verfasser/Dokument
210 HB
220 HB
-29 C
80
19
N+AC+T (Q + T)
Hollomon parameter
N+AC+T
(Q + T)
N+T
- 40 C
- 29 C
- 18 C & -29 C
- 18 C
- 10 C
Hollomon parameter
200 HB
190 HB
200 HB
195 HB
205 HB
N+T
205 HB
210 HB
210 HB
Verfasser/Dokument
215 HB
215 HB
20
40
60
80
20
40
60
80
20
Offset in hardness between 2CrMo and 2CrMoV steels in dependence of delivery condition
250
240
Q+T
Q+T
220
210
200
190
10h @ 705 C
Q+T
N + AC + T
(Q + T)
30h @ 705 C
Q+T
5h @ 700 C
Verfasser/Dokument
hardness [HB]
230
180
2CrMo
2CrMoV
21
-40 C
-29 C
-29 C
-29 C
2Cr N+T
2Cr Q+T
1Cr N+T
1Cr Q+T
Verfasser/Dokument
Hollomon Parameter
22
700
Tempering
PWHT-Min
PWHT-Max
740 C/30
690 C/8h
690 C/24h
12CrMo9-10
600
Rm
12CrMo9-10
500
Rp0.2
400
Verfasser/Dokument
900
12CrMo9-10
300
19,8
20,0
20,2
20,4
HP-Factor
20,6
20,8
21,0
21,2
23
700
+ 0,25% V
Rm V-m
odified
600
Rm
enhanced
Rp0.2
enhanced
500
400
Verfasser/Dokument
900
300
19,8
20,0
20,2
20,4
HP-Factor
20,6
20,8
21,0
21,2
24
700
Rp0.2 V-m
odified
500
Rp0.2
400
enhanced
Verfasser/Dokument
600
Rm V-m
odified
+ 0,25% V
900
300
19,8
20,0
20,2
20,4
HP-Factor
20,6
20,8
21,0
21,2
25
PWHT-Min
PWHT-Max
715 C/250
705 C/8h
705 C/24h
800
A542-D-4a
700
600
Rm V-m
odified
A542-D-4a
Rp0.2 V-m
odified
500
400
A542-D-4a
Verfasser/Dokument
900
300
19,8
20,0
20,2
20,4
HP-Factor
20,6
20,8
21,0
21,2
26
Verfasser/Dokument
27
600
700
- plate thickness: 200 mm
- heat treatment: N+AC+T
2,25CrMoV, Rp02
3CrMoV, Rp02
12CrMo 910, Rp02, HP=21,0
3CrMoV, Rm
12CrMo 910, Rm, HP=21,0
600
400
500
300
Rm [MPa]
400
12CrMo 910 acc. EN 10028
part 2
200
0
50
100 150 200 250 300 350 400 450 500 550 600 650
Testing temperature [C]
300
0
50 100 150 200 250 300 350 400 450 500 550 600 650
Testing temperature [C]
28
Verfasser/Dokument
Rp0,2 [MPa]
500
2,25CrMoV, Rm
2CrMoV, Rm
3CrMoV, Rm
2CrMo, Rm ,HP=21.0
550
2CrMoV, Rp0.2
2CrMo, Rp0.2 ,HP=21.0
500
450
400
350
plate thickness: 200mm
heat treatment: N+AC+T
300
0
50
Verfasser/Dokument
3CrMoV, Rp0.2
100 150 200 250 300 350 400 450 500 550 600 650
testing temperature [C]
29
30
Verfasser/Dokument
450
400
HP 20,63
HP 20,81
SA 387-22-2, measured
SA 387-22-2, measured
Rm min20 C
300
0
100
200
300
400
500
600
T emperature [C]
31
Verfasser/Dokument
500
Verfasser/Dokument
32
550
500
450
400
350
300
200
150
100
150
200
250
300
350
400
450
500
550
600
33
Verfasser/Dokument
250
550
500
450
SA 387-22-2
SA 542 D4a
400
SA 542 C4a
test data
350
test data
test data
300
0
100
200
300
400
500
Verfasser/Dokument
600
600
Temperature [C]
34
Verfasser/Dokument
35
Verfasser/Dokument
Intergranular crack
36
high safety
peration of installation
Operation
(~30 years) 400 C
without danger of
grain-boundary
embrittlement!
Crack
Conclusion:
Temper Embrittlement
Verfasser/Dokument
37
normal production
special production
0,011
Sn
0,005
0,005
As
0,007
0,007
Sb
0,001
0,001
* depending on Cr-content
special production
J-factor
X-factor
J-factor
X-factor
1Cr Mo
120
13
100
1Cr Mo
165
13
120
2Cr 1Mo
130
13
100 **
Verfasser/Dokument
normal production
** 80 for 2CrMoV
38
[Si]
[Mn]
0.13 %
0.25 %
0.60 %
[Tliq]
[Mo]
1.00 % ~1560C
A conventional process
B conventional process with heating in VD units
C special converter process
200
150
A
100
B
C
50
Verfasser/Dokument
250
[C]
0
0
0.5
1.5
2.5
3.5
Cr-content [%]
Low alloy CrMo(V) steel plates for petrochemical reactors
39
80
EAF with 70 % alloyed-rejects srap + ferrous alloys
EAF with sheet-metal scrap + ferrous alloys
LD-steel BOF process
60
50
40
30
20
Verfasser/Dokument
70
10
0
Arsenic (As)
Tin (Sn)
Antimony (Sb)
40
Ductility and Charpy-values taken from randomly picked Dillinger orders in SA 387-22-2 at different temperatures. Plate thickness 134 &
208 (G&B) mm
400
350
300
250
Av [J]
0 C
-20 C
-30 C
-40 C
-60 C
-80 C
-100 C
200
150
100
50
0
10
20
30
40
50
60
70
80
90
100
Verfasser/Dokument
Ductility [%]
41
Verfasser/Dokument
42
Verfasser/Dokument
43
Development of [O]tot during production for continous casting and without special converter treatment
60
50
Otot in ppm
40
[O]tot in ppm
50
40
30
20
10
30
20
10
time in min
15
Verfasser/Dokument
10
0
after
vacuum
treatment
after
CaSiafter
after
inclusion
addition
cleanness shape
control
stirring
tundish
mould
plate
Steps after vacuum treatment are still very important to bring total
oxygen further down
Low alloy CrMo(V) steel plates for petrochemical reactors
44
impact
energy
initial
after step
cooling
after service
54 J
TSC
Verfasser/Dokument
Ttot
Ttot = 2.5 x TSC
test temperature
Low alloy CrMo(V) steel plates for petrochemical reactors
45
s te p-cooling-tre atm e nt in
accordance to EN 10028-2
5 9 3 C
600
550
55,6C/ h
5 3 8 C
5 2 4 C
4 9 6 C
500
2 ,8 C/ h
4 6 8 C
2 ,8 C/ h
450
400
350
15 h
3 15 C
60 h
24 h
100 h
1h
300
3 15 C
cooling in
Verfasser/Dokument
temperature [C]
5,6 C/ h
still air
250
10
11
12
tim e [d]
Low alloy CrMo(V) steel plates for petrochemical reactors
46
40
not fulfilled
30
20
fulfilled
10
0
-10
-20
-140
-120
-100
-80
-60
-40
-20
Verfasser/Dokument
50
20
47
50
TT + 2.5 xT <= 10
40
not fulfilled
30
20
fulfilled
10
0
-10
-20
-140
-120
-100
-80
-60
-40
-20
Verfasser/Dokument
TT + 3 xT <= 10
20
48
Verfasser/Dokument
49
allow able
resulting
resulting w eight allow able
resulting
resulting w eight
stress
w all thickness
of the vessel
stress
w all thickness
of the vessel
[MPa]
[mm]
[t]
[MPa]
[mm]
[t]
2CrMo
Div. I
129
214
616
103
263
757
2CrMoV
Div. I
145
192
553
140
199
572
2CrMo
Div. II
151
185
533
117
234
674
2CrMoV
Div. II
169
167
480
163
172
497
2CrMo
Div. II
151
185
533
117
234
674
2CrMoV
Div. II
199
143
413
163
172
497
2007 Edition
Verfasser/Dokument
50
12CrMo9-10:
The tensile and toughness properties are satisfactory in a HP-range between 19.6 and 20.8
CrMoV-steels:
In spite the higher tensile requirements HP-values up to 21.1 are acceptable
CrMo(V)-steels:
Impact toughness increase by tempering effect until an optimum HP value is
Verfasser/Dokument
reached.
51
Verfasser/Dokument
( *after hot forming the parts will be heat treated as per the material standard)
52
Verfasser/Dokument
53
Verfasser/Dokument
54
Verfasser/Dokument
shape profiling
55
J-edge
Verfasser/Dokument
X-edge
56
Cold forming
Verfasser/Dokument
57
Forming
Cold Forming:
General trend of the influence of cold deformation on mechanical properties
Rp0,
2
Verfasser/Dokument
Rm
Av
(T=const.)
cold deformation
Low alloy CrMo(V) steel plates for petrochemical reactors
58
Verfasser/Dokument
59
750
700
650
600
550
Rp0.2
Rm
500
350
300
Verfasser/Dokument
400
Prftemperatur
-60-60C
C
Test Temperature
Prftemperatur
-80-80C
C
Test Temperature
250
200
Q 980 C/2h/W+
A 730 C/90'/L
Q 950 C/10'/W+
A 730 C/90'/L
HG 1100 C
/2,5h/L+
Q 950 C/10'/W+
A 730 C/90'/L
HG 1140 C
/2,5h/L+
Q 950 C/10'/W+
A 730 C/90'/L
HG 1170 C
/2,5h/L+
Q 950 C/10'/W+
A 730 C/90'/L
HG 1100 C
/5,0h/L+
Q 950 C/10'/W+
A 730 C/90'/L
HG 1140 C
/5,0h/L+
Q 950 C/10'/W+
A 730 C/90'/L
HG 1170 C
/5,0h/L+
Q 950 C/10'/W+
A 730 C/90'/L
HG 1100 C
/2,5h/L+
Q 980 C
/120'/W+
A 730 C/90'/L
HG 1170 C
/5,0h/L+
Q 980 C
/120'/W+
A 730 C/90'/L
60
Verfasser/Dokument
61
300
200
150
100
50
0
-100
-80
-60
-40
-20
20
40
60
80
Verfasser/Dokument
A v [J]
250
100
Test Temperature C]
62
250
200
150
100
50
0
-100
-80
-60
-40
-20
20
40
60
80
Verfasser/Dokument
Av [J]
100
Test Temperature [ C]
Low alloy CrMo(V) steel plates for petrochemical reactors
63
Delayed HICC
Toughness in the weld / step cooling
API RP- 934, ASME VIII-2, App. 26
Low alloy CrMo(V) steel plates for petrochemical reactors
64
Verfasser/Dokument
HAZ hardness
SA 542 D4a
Shell outside
Verfasser/Dokument
120mm
Shell inside
Low alloy CrMo(V) steel plates for petrochemical reactors
65
Fabrication aspects to be considered for the use of V modified steels vs. standard 2CrMo steels
Verfasser/Dokument
Personnel education.
66
Weld metal and HAZ in the as welded condition are susceptible to hydrogen induced cold cracking
how to avoid this defect ?:
Verfasser/Dokument
67
Verfasser/Dokument
68
A
Z
0
-20C
-40C
Indiv 1
Indiv 2
-20C
Indiv 3
Average
50
H Zt
A /2
Z
3/
4
H
A
Z
H to
A p
Z
H t/
A 4
H Z t/
A 2
Z
w
3/
el
4
d
w m
el e
w d m tal
e
t
w ld eta op
el m l
d et t/4
m al
e t t/
al 2
w
el
3/
d
4t
w m
el e
w d m tal
e
t
w ld eta op
el m l
d et t/4
m al
e t t/
al 2
3/
4t
H to
A p
Z
H t/4
A
CHARPY-V (J)
350
300
250
200
150
100
-40C
69
2CrMoV
test temperature: -20C
250
200
150
100
PWHT 30hrs @ 710 C
PWHT 10hrs @ 680 C
PWHT 5hrs @ 680 C
50
0
0,5
top
1,5
t/4
2,5
t/2
weld metal
3,5
3/4t
4,5
top
5,5
t/4
6,5
t/2
7,5
3/4t
Verfasser/Dokument
Charpy-V [J]
300
8,5
HAZ
70
2 Cr-1Mo
2 Cr-1Mo
350C 4h
2 Cr-1Mo
620C 4h
54 J TT 38C
54 J TT -23C
2 Cr-1Mo-V
350C 4h
2 Cr-1Mo-V
620C 4h
2 Cr-1Mo-V
650C 4h
2 Cr-1Mo-V
650C 8h
2 Cr-1Mo-V
680C 4h
54 J TT 85C
54 J TT 120C
54 J TT 72C
Verfasser/Dokument
2 Cr-1Mo-V
54 J TT 15C
54 J TT -4C
71
Verfasser/Dokument
72
Verfasser/Dokument
73
PWHT limits:
680C, 5hours
680C, 10 hours
Verfasser/Dokument
710C, 30 hours
74
Verfasser/Dokument
75
Verfasser/Dokument
76
Influence of step-cooling test, PWHT: 705 C/8 hrs; Location : HAZ center
450
400
0 = with Step-Cooling-Test
0 = without Step-Cooling Test
Order-No
Ref.-No
Heat-No
Material
Thickness
HP:
Weld seam
Current
Position
350
250
200
X
AC
HAZ center
Test Criteria:
TTr + Faktor * TTr max. shift
150
100
50
0
-120
-100
-80
-60
-40
-20
20
40
60
80
100
Faktor:
max. Shift
Min Av
TTr without Step-Cooling:
TTrsc with Step-Cooling:
DTTr = TTr SC - TTr
test criteria fullfilled
2,5
10
54
-99,15
-80,40
18,75
Yes
Temperature [ C]
Low alloy CrMo(V) steel plates for petrochemical reactors
77
C
J
C
C
C
Verfasser/Dokument
A v [J]
300
674739
21250
55470
SA 542-D-4a
120
[mm]
300
0 = with Step-Cooling-Test
0 = without Step-Cooling Test
Order-No
Ref.-No
Heat-No
Material
Thickness
HP:
Weld seam
Current
Position
250
A v [J]
200
674739
21250
55470
SA 542-D-4a
120
[mm]
X
AC
WM center
100
Faktor:
max. Shift
Min Av
TT r without Step-Cooling:
TT rsc with Step-Cooling:
SC
DTT r = TT r - TT r
test criteria fullfilled
50
2,5
10
54
-61,19
-64,84
-3,65
Ye s
C
J
C
C
C
0
-120
-100
-80
-60
-40
-20
20
40
60
80
100
Temperature [ C]
Low alloy CrMo(V) steel plates for petrochemical reactors
78
Verfasser/Dokument
Test Criteria:
150
not fulfilled!
-25
T T5 4
-50
x
2,5
+
J
10
T <=
C x
x
fulfilled
-75
-100
Verfasser/Dokument
25
-125
-100
-80
-60
-40
-20
20
79
250
235
650C-10h
2CrMoV
as welded
675C-10h
2CrMo
as welded
650C-10h
700C-10h
725C-10h
675C-10h
Verfasser/Dokument
hardness [HV10]
400
700C-10h
usual range
80
HAZ hardness vs. cooling time t8/5 and PWHT (bead on plate)
450
2.25CrMoV as welded
2.25CrMoV 705 C / 10 h
2.25CrMoV 705 C / 30 h
3CrMoV as welded
3CrMoV 705 C / 10 h
3CrMoV 705 C / 30 h
12CrMo9-10 as welded
12CrMo9-10 690 C / 10 h
12CrMo9-10 690 C / 30 h
350
300
250
Verfasser/Dokument
hardness HV10
400
200
1
10
20
30
40
81
250
230
210
190
170
150
2CrMoV
top 1mm
centre
bottom 1mm
top 1mm
centre
bottom 1mm
82
Verfasser/Dokument
B
as
e
B Me
as
t
e al
B Me
as
t
e al
M
et
al
H
A
Z
H
A
Z
H
W
A
el
Z
d
M
W
el eta
d
l
M
W
el eta
d
l
M
et
al
H
A
Z
H
A
Z
H
B
as AZ
e
B Me
as
t
e al
B Me
as
t
e al
M
et
al
Hardness HV10
220
210
200
190
180
se
Ba Me
se t al
Ba Me
se t al
M
et
al
H
AZ
H
AZ
W
H
AZ
el
d
W Me
el
t
d al
W Me
el
t
d al
M
et
al
H
AZ
H
AZ
Ba H
se AZ
Ba Me
se t al
Ba Me
se t al
M
et
al
170
Top
PWHT 705C, 8hrs
Bottom
Top
Bottom
Verfasser/Dokument
Ba
Brinell Hardness HB
(10mm Ball)
83
0,5m
As welded
no carbides
620C - 15
M3C few M23C6
TEM micrographs on carbon extraction replica 21/4CrMoV
Ref.: Lundin,C.D. and K.K.Khan, WRC Bulletin 409
0,5m
730C - 8h
M7C3, M23C6,
fine V4C3, M2C
84
Verfasser/Dokument
0,5m
Verfasser/Dokument
85
Creep properties
In case of reactor design in creep regime: if creep strength values on welded joints
are verified to be within a 20%-scatter band of the base material
welding consumable and base metal from the material manufacturer duly
approved by tests within the creep regime can be used for fully stressed welds
using a joint efficiency factor of 1 instead of 0.8 (design according to German
AD-Merkblatt, in future also according to EN 13445)
Verfasser/Dokument
86
Verfasser/Dokument
temperature of PWHT
87
Verfasser/Dokument
Source JSW
88
200
100
90
80
70
60
50
100
12CrMo9-10
2.25CrMoV
3CrMoV
VdTV 404/1
VdTV 525
VdTV 491
1000
10000
Verfasser/Dokument
300
100000
Time [h]
Low alloy CrMo(V) steel plates for petrochemical reactors
89
Conclusion
CrMo steels with % V offer improved performance for petrochemical reactors
compared to enhanced 2Cr1Mo steels. Plates are commercially available up to
about 250 mm thickness.
optimized welding consumables have to be used with respect to low hydrogen input
and very low impurity level to limit in service embrittlement.
screening tests of the weld metal before production starts, e.g. as per API RP 934,
are recommended.
the steels tolerate very high temperatures 690 - 710 C for post weld heat
DH-GTS is a long term supplier with plenty of know how for high sophisticated steels
a wide range of dimensions can be supplied.
more and more vessels will be designed from CrMoV steels to take advantage of
improved process possibilities and improved properties.
Low alloy CrMo(V) steel plates for petrochemical reactors
90
Verfasser/Dokument
Verfasser/Dokument
91