Challenges in 21/4Cr1Mo(V)

welding fabrication

Application
Application Technology,
Technology, Volker
Volker Gross
Gross
Böhler Schweisstechnik Deutschland
Böhler Schweisstechnik
Hamm,
Deutschland Hamm, Germany
Germany
5.2012, SBW

Agenda

basics of CrMo and CrMoV

strength/ toughness features

development of suitable filler metals

essential issues

strong recommendations
 Reactors in refinery
applications
C-Mn C-Mn/ inconel duplex

1200t 1500t

21/4Cr1MoV
21/4Cr1Mo
930t
800t
Behaviour of C in
Whymicro
ferritic CrMos are
structure suitable
Propeties: ferrite vs. austenite
- thermal expan.
Tendency to carbide formation
- thermal conductiv.
- diffusion coeff. C
- solubility for C
Strength at high temp.

- carbide formation

austenite
ferrite

effect of stable carbides

•less risk of CH4-formation > petrochemical (hydrotreating) reactors,
11/22/22V
•Application in the creep range > power plant equipment 4
production of base materials, plates

low N, H, O
General difference between base metal and weld metal
Base metal
-Structure defined by rolling/
forming processes, heat treatments
-Lowest contents in S, N, H, O by
vacuum metallurgy
but: (slow solidifcation)
Normalizing/ solution annealing
required
Weld metal
-Structure: as casted
.Welding under normal atmosphere
slag = pick up of N,H,O
but fortunately: fast solidifcation
leading to regular distribution of
elements,
therefore in general no solution
annealing to be applied
6
weld YS (MPa) TS (MPa) Elong. (%) CVN (J)
22 800 950 19 50
11 700 850 20 70
 CrMo(V) heat treatment essentials

General features of bainitic/ martensitic structure:

heat treatments required

DHT: dehydrogenation treatment (350°C/ min 4hrs )
removes Hydrogen! A MUST
H-sources: atmosphere/ coating/ flux)

ISR: intermediate stress relieving (620-680°C/ 6hrs)
for highly stressed joints (nozzles, build up rings, etc)

SR: stress relieving <min pwht> (660-705°C/8hrs min)
desired structure achieved (min reactor condition)
Influence on strength & toughness

Step Cooling / max pwht
Simulation of fabrication & refinery conditions
ranges-chemistries (wt-%) of CrMo-filler metals
x-factor
SAW, process, flux, polarity C Si Mn P/S Cr Mo
[ppm]

0,07 0,2 0,7 < ,01 2,4 1 5

DC+, single wire
UV 420 TTR
0,08 0,2 0,8 < ,01 2,4 1 7

0,1 0,2 0,8 < ,01 2,4 1 4

AC,single wire
UV 420 TTR-W
0,1 0,2 0,8 < ,01 2,4 1 7

0,1 0,2 0,8 < ,01 2,4 1 5

Tandem, DC+/AC
UV 420 TTR-W
0,11 0,2 0,8 < ,01 2,4 1 7

x-factor
C Si Mn P/S Cr Mo Ni
[ppm]

0,05 0,2 0,7 < ,01 2,4 1,1 0 05 7

SMAW, DC+
0,06 0,2 0,7 < ,01 2,4 1,1 0,05 6
 Main metallurgical
Metallurgical review ofdifference between
welding processes= OXYGEN
solidification conditions
Typical impact strength for B3 GTA / SM-SA weld metals
before / after step cooling

300
~50ppm O, GTAW (~base metal)
250

200 difference in oxygen ~400ppm O, SAW / SMAW

Kv [J]

150 before sc
after sc
before sc
100
after sc
54 J
50

0
-80 -70 -60 -50 -40 -30 -20 -10 0
Test temperature [°C]

Impact - temperature - curve

 formation of oxides, consequences

Oxygen in weld metal=

composed of different oxides

oxides formed during solidification

=nuclids
Fe2O3

the higher the formation temp. =

Cr2O3
MnO
early formation of nuclids
SiO2

More nuclids =
Al2O3
-faster solidification
-finer grains
-less seggregation
-less precipitations
Improvement in toughness in SMA welds; pos. 3 G up,
conv. CrMos, 21/4Cr1Mo,Properties after SR and step cooling

SMAW : Phoenix SH Chromo 2 KS, ø: 4,0 mm SMAW : Phoenix SH Chromo 2 KS, ø: 4,0 mm
250 250
690°C/10 h (current) 690°C/10 h (previous) 690°C/10 h (current) 690°C/10 h (previous)
690°C/10 h + sc (current) 690°C/10 h + sc (previous) 690°C/10 h + sc (current) 690°C/10 h + sc (previous)
200 200
CVN [J]

150

CVN [J]
150

100 100

54 J 54 J
50 50
≈

0 0

≈
-50 -40 -29 20 30 -50 -40 -29 20 30
Test temperature [°C] Test temperature [°C]

SMAW : Phoenix SH Chromo 2 KS, ø: 4,0 mm SMAW : Phoenix SH Chromo 2 KS, ø: 4,0 mm
250 250
690°C/30 h (current) 690°C/30 h (previous) 690°C/30 h (current) 690°C/30 h (previous)
690°C/30 h + sc (current) 690°C/30 h + sc (previous) 690°C/30 h + sc (current) 690°C/30 h + sc (previous)
200 200
CVN [J]

CVN [J]
150 150

100 100

54 J 54 J
50 50

≈
0 0
≈

-50 -40 -29 20 30 -50 -40 -29 20 30

Test temperature [°C] Test temperature [°C]
Toughness properties of SAW single wire, AC

250
690°C/8 h (current)
690°C/8 h (previous)
200 690°C/8 h + step cooling (current)
690°C/8 h + step cooling (previous)

150
KV [J]

current previous

100

54 J
50

0
-90 -80 -70 -60 -50 -40 -30 -20
Test temperature [°C]

Impact - temperature - curve

 Enclosure to Inspection certificate no.
130012.1
Phoenix SH Chromo 2 KS, Ø 5,0 mm, heat-no. 1114566

300
691°C±14°C / 5hrs 691°C±14°C / 5hrs + sc 54 J

250

200
CVN [J]

150

100

50
(vTr54 + 2,5 x (∆vTr54sc)) = - 35,0°C
-54,8
-68,0

0
-80 -70 -60 -50 -40 -30 -20 -10 0 10 20 30 40 50
Temperature [°C]

05.052006 Autorized inspection representative

 Enclosure to Inspection certificate no.
130014.1
Union S 1 CrMo 2, Ø 4,0 mm, heat-no. 328556 / UV 420 TTR-W, heat-no. 1401278

300
691°C±14°C / 5hrs 691°C±14°C / 5hrs + sc 54 J

250

200
CVN [J]

150

100

50
(vTr54 + 3,0 x (∆vTr54sc)) = - 57,7°C
-54,5

-52,9

0
-80 -70 -60 -50 -40 -30 -20 -10 0 10 20 30 40 50
Temperature [°C]

05.052006 Autorized inspection representative

 Enclosure to Inspection certificate no.
130015.1
Union I CrMo 910 Spezial, 2,4 mm, heat-no. 293156

300
691°C±14°C / 5hrs 691°C±14°C / 5hrs + sc 54 J

250

200
CVN [J]

150

100

50
(vTr54 + 2,5 x (∆vTr54sc)) = - 82,3°C
-92,8

-88,6

0
-100 -90 -80 -70 -60 -50 -40 -30 -20 -10 0 10 20 30 40 50
Temperature [°C]

05.05.2006 Autorized inspection representative

„Old“ materials (grade 11/22) with limited strength

CrMo- grades
PWHT YS TS AWS filler
Type C Cr Mo V Nb
[°C] [MPa] [MPa] metal

11 0,15 1,3 0,5 660 275 485 - 660 B2

22 0,12 2,3 1 690 310 515 - 690 B3

B3 mod.
22 V 0,10 2,30 1 0,3 0,05 705 415 585 - 760 Code Case
2098

Service conditions and demand for bigger reactors increased

Consequence of increased service conditions:
• increase in wall thickness
increase in weight of the equipment
(limitations in transport to be considered)

358mm F22
PC:
454 °C
215 bar

ATB
 CrMo- grades
PWHT YS TS AWS filler
Type C Cr Mo V Nb
[°C] [MPa] [MPa] metal

11 0,15 1,3 0,5 660 275 485 - 660 B2

22 0,12 2,3 1 690 310 515 - 690 B3

22 V 0,10 2,30 1 0,3 0,05 705 415 585 - 760 B3 mod.

Benefit of CrMo(V) materials for hydroprocessing reactors

• high (creep) strength conditions due to stable carbides
• higher resistance against hydrogen, disbonding
• high toughness level
 service conditions: Courtesy of ATB

454°C, 215 bar

ASME VIII F22 F22V
Ed.
2006 358mm 317mm
2007 267mm
ALLOWABLE STRESS

250 economical advantages:

allowable stress MPa

225
200
save in thickness
175 save in weight
150
125
100
ATB BUT:
350 378 406 434 462 490 21/4Cr1MoV has to be welded
temperature °C
Conventional 2¼Cr1Mo -ASME 2006 Conventional 2¼Cr1Mo -ASME 2007
2¼Cr1Mo V modified -ASME 2006 2¼Cr1Mo V modified -ASME 2007
Key property of CrMoV welds

Increased strength in the as welded condition to be considered

weld YS (MPa) TS (MPa) Elong. (%) CVN (J)

22V 880 1070 19 20
22 800 950 19 50
11 700 850 20 70
ISR of restrained joints, CrMoV SA welds

Tests on tandem DC/AC all weld metal,2x4mm

550/550 A, 29/ 32 V, 80 cm/min
Preheat.: 180 °C, interpass: max 230 °C

Strength,rt ISR As welded 620°C/ 4h 650°C/ 4h 680°C/ 4h 710°C/ 4h

Rp0.2, MPa 880 859 778 650 591
Rm, MPa 1070 956 858 735 682
A5, % 18,9 16,2 15,7 19,2 19,4
Z, % 51,2 60,4 62,9 69,9 70
CVN (J) at RT 17 19 20 8 14 11 17 26 40 127 123 132 152 153 156
Hardness HV10 345 333 295 252 232

Secondary hardening
Advantage of high toughness
 actual joint metal toughness

SAW Union S 1 CrMo 2 V/ UV 430TTR-W

tandem weld, 300mm wt

1/2t

min pwht 705-710°C/8hrs

C Si Mn P S Cr Mo Ni V Al Cu Nb Xf Kf
,09 ,11 1,19 ,005 ,004 2,45 1,03 ,03 ,25 <,01 ,03 ,013 6 0,7
 strength properties of CrMoV-welds

all weld metal, SAW, single wire, AC

PWHT T Rpo.2 Rm A5
°C/hrs °C MPa MPa %
Requ. >585
705/ 10 rt 569 667 23
705/ 8 rt 563 662 23
705/ 32 rt 491 610 26

Comment:
no comfortable safety margin for tensile strength.
Same properties in stick electrode welds
main issues in CrMoV-welding

Which properties are affected?

2 type of defects mainly, consequences are time and money consuming
due to repair, delay in deliveries

• cracks
 Hydrogen attack under control by rebaking, DHT
 Reheat cracking under control by Kf
• more frequent: toughness vs requirements
Facts on SRC

- SRC does occur on equipment only due to restrained

condition, not on qualification/pt coupons of same thickness

- SRC to be detected by high density UT only

- does not occur after DHT, but after ISR/pwht

- even after optimized ISR

 Reheat cracking issue
location of cracks (boat sample)

•Cracks occur in not refined areas in multi layer SA welds

•Arrested at the fine grain area
•No specific precipitations, seggregations, micro structure compared to
sound welds
 New Composition Factor to
Control reheat cracking
Proposed criterion in the Gleeble Test: (RoA>23%)
40
K factor = Pb + Bi + 0.03Sb < 1.5ppm
35 ]

30
RoA % at 650°C

25

20

15

10

5
Presented by Industeel, API 934 meeting Denver 2009
0
0 1 2 3 4 5 6 7 8 9 10 11 12
K factor = Pb+Bi+0,03Sb
Bohler approach to resolve reheat cracking

low K-factor + fine grain

because cracks are arrested at fine grain area
applicable for all joints

40

35

30
RoA % at 650°C

25
applied for circseams
20

15

10

0
0 1 2 3 4 5 6 7 8 9 10 11 12
GDMS-method only
K factor = Pb+Bi+0,03Sb (ppm)

Competitor „Bohler“ data

values
 HYDROGEN issue

Kind attention to the rebaking of SAW flux


~60°C
300°C
large volumen

heating sticks ~300°C Flux to be dryed on plates,

on bottom only 5cm height max !
Colds Cracks in build up welds (support rings) caused
by Hydrogen
Observations in 22V SA welds

failed
-min pwht
-min pwht+sc
Not acceptable,why?
Main reasons for toughness (step cooling) issues

• high X-bar >15ppm;

-not available with actual suppliers (<12ppm)
-not allowed by specifications

• trace elements influencing nucleation (under control)

• welding and all temperature parameters

•Why the weld failed in the step cooling test then???

 „small“ sized coupon for PQ
• Reason for overheating:
– Interpass temp. (recom. max 230°C) was measured on top side.
– loss in temp. from actual weld location to top side not considered

measured 230°C

actual
Temp. gradient! ~400°C

Not an issue for reactor welds (except nozzle welds) due to massive
qty., but to maintain preheating temp. becomes essential!
 Temp. range of pwht equipment

•record by thermocouple in the furnace: 705°C

•actual: 740 -760°C

!!!! thermocouple to be attached to the coupon !!!!

770

765 Kanal 1
Kanal 2
Kanal 3
Kanal 4
Kanal 5
760 Kanal 6
Kanal 7
Kanal 8
-low cost for equipment
Kanal 9
Temperatur in °C

755 Kanal 10
Kanal 11
Kanal 12
Kanal 13
-far cheaper than repeat test
750 Kanal 14
Kanal 15
Kanal 16
Kanal 17
Kanal 18
-online control on PC possible
745 Kanal 19
Kanal 20
Kanal 21
Kanal 22
LESS RISKS
740 Kanal 23
Kanal 24
Kanal 25
Kanal 27
735

730
14,0 14,2 14,4 14,6 14,8 15,0 15,2 15,4 15,6 15,8 16,0
Zeit in Stunden
toughness issue in 22V SA welds

fracture surface of impact specimens (-30°C/ 705°C/ 8hrs)

from same lots, but different „temperature conditions“

brittle fracture along grain bounderies ductile fracture

21-30J 160-200J
structure of 22V SAW impact specimen at -30°C/ 705 °C/ 8hrs

observations

21-30J 21-30J •large grains

•carbide precipitations on
grain boundery

excessive interpass
temp.
200µm 50µm

•smaller grains
160-200J 160-200J
•less carbide precipita-
tions on grain boundery

200µm 50µm
 cross section of SAW impact specimen

-brittle fracture -ductile surface

-Crack along grain boundery,
-precipitations !

cross section of impact specimen

21J 190J

21-30J 160-200J
 Narrow gap 22V SA welds
flat thin beads mandatory (~max 3.5 mm)
sufficient refinement by subsequent beads !!!!

flat thin beads achieved by

by suitable joint opening + suitable parameters

sketch for same weld metal volume

325 mm but different joint opening

16mm 22mm

AC, 500 A, 30 V; 45 cm/min

Different bead formation in SMA welds

-sufficient refinement
Phoenix Chromo 2 V, Ø 4,0 mm, 3G up -less precipitations
-smaller grains
toughness
low high

thick beads thin, weaved beads

ATTENTION: Conventional equation to calculate heat input not applicable.
Weaving width to be included.
Typical preheating arrangements for circumferrential seams
recommendations for smooth CrMoV welds

fine grain to be maintained by

flat beads (see API 934B too), controlled bead height
 weaved beads for SMAW, bead height: max 2,5mm
 SAW: bead height: max 3,5mm

controlled temperatures
preheating, interpass temp., DHT, ISR, PWHT

welding-parameters to be controlled

Quality of the equipment to be controlled

Welders to be trained!!!!!!!!!!!!!!!!!!

consequence: strict limitations in welding

Why do (did) these problems occur(ed) ?
• Material has been underestimated
• 21/4Cr1MoV asks for specific considerations including costs in
terms of:
– in welding, equipment, handling
– evaluations of acceptance criteria
- to rely on experiences in the conventional CrMo only is not sufficient at all.

• So far ~10 fabricators know about safe fabrication since introduction

in ~1995!!!
– WHY only ~10 major fabricators worldwide????
– Above mentioned items were simply not considered by other fabricators
 Beginning
Typical ofexperience
development of journey in fabrication
of Cr-Mo-V Reactors
Project Customer Shell No of Year of Mfg.
No. Thickness Circ.
Seams
45030 67 12 2000
45345 138 9 2007
45353 168 5 2008
45376 161 7 2008
45377 161 7 2008
45379 161 9 2008
45380 161 9 2008
Typical development of experience in fabrication
of Cr-Mo-V Reactors

Running Cr-Mo-V Reactors

Expected
No. of Shell No of Circ.
Project Customer Year of
Projects Thickness Seams
No. Dispatch
45514/
8 290 64
45522
45515/
8 287 72
45523
2010 -
45516/ 2011
4 229 8
45524
45517 1 303 9
45518 1 299.5 11
Typical development of experience in fabrication
of Cr-Mo-V Reactors

Running Cr-Mo-V Reactors

Shell Expected
No. of No of Circ.
Project Customer Thicknes Year of
Projects Seams
No. s Dispatch

45526 1 136 14
45527 1 168 10 2010
45528 1 165 9

45536/
4 153 8
1-4
45537/ 2010-
4 149 9 2011
1-4
45538 2 123 5
Typical development of experience in fabrication
of Cr-Mo-V Reactors

Running Cr-Mo-V Reactors

Expected
Project No. of Shell No of Circ.
Customer Year of
No. Projects Thickness Seams
Dispatch

45546 1 101 9
2011
45547 1 96 9

45548 1 101 9
2011
45549 1 96 9

45551 1 96 11

45556 1 91 15 2010-2011

45557 1 91 15
 DHDS Reactor – Essar Refinery, India

Largest Dia. Cr-Mo-V

DHDS Reactor

2007

Weight: 930 MT, Process: Axens; Material: 2.25Cr-1Mo-0.25V + SS347 O/L

Dimension: Ø 6.4 m x 31.1 m L x 138 mm Thk
Hydrocracking Reactor- I – Helpe, Greece

2009

Weight: 870 MT; Process: UOP; Material : 2.25Cr-1Mo-0.25V + SS347 O/L

Dimension: Ø 5 m x 26.1 m L x 297 mm Thk,
 Hydrocracking Reactor- II – Helpe, Greece

2009

Weight: 970 MT; Process: UOP; Material : 2.25Cr-1Mo-0.25V+ SS347 O/L

Dimension: Ø 5 m x 29.5 m L x 292 mm Thk,
 HDT Reactors – IOCL, Panipat INDIA

2008

Weight: 487 MT, Process: Axens; Material: 2.25Cr-1M0-0.25V + SS347 O/L

Dim.: Ø 4.2 m X 19 m L X 161 mm Thk
 DHDT Reactors – BRPL, INDIA

2008

Weight: 397 MT, Process: Axens; Material: 2.25Cr-1Mo-0.25V + SS347 O/L

Dimension: Ø 3.3 m X 22.9 m L X 146 mm Thk
 THE petrochemical success story worldwide

• a Middle East Refinery

• 22 heavy walled reactors in grade „22V“ by L&T, HZW

Process filler metals Boehler Qty.

SAW wire: Union S 1 CrMo 2 V 800 mt
Flux: UV 430 TTR-W
SMAW Phoenix Chromo 2 V 100 mt

Nos WT (mm) Weight (mt)

4 229 255
8 287 975
8 290 750
1 299 1240
1 303 1046