High Wet CO2 + H2S Gas

Vs Latest NACE 1075-2003

A. Kobori

Copyright 2004

at
Customer seminar Nov. 13 2006

Agenda
1.

NACE Old Vs New

2.

Material selection by NACE Vs DR

3.

High CO2 + H2S Gas Vs Latest NACE

4.

Conclusion for material selection for High

CO2 +H2S

H2S Stress Cracking Corrosion( SSC)

Depth of Sulfide Stress Cracks

Intergranular H2S Cracking,

SEM, x1000 magnification
3

H2S Crack test -1972 in Japan

Stress to crack-ksi

190
170

AISI 4330

150
130

17-4PH
Material
AISI-4140

110
90
70
0.001

0.01

0.1

H2S partial pressure-psi

Remark: 0.05psi=0.3kPA,
We made 100KSI YP with AISI4330 and
105-115KSI YP with 17-4PH in old day
4

NACE -97 Vs NACE-2003

Title

NACE MR-0175-97 NACE MR0175/ISO 151563-2003EO

Wet Sour Gas

H2S

H2S, H2S+CO2
H2S+Others

Object

SSC by H2S

SSC by H2S,
SSC& CRA by (H2S+CO2)

Fig.1 for SSC by H2S pH2S Vs Pressure

pH2S Vs pH

Fig.D.1

(pCO2+pH2S) Vs pH

N/A

Fig 1 for H2S SSC by NACE -97

Note: 0.05psia= 0.3 kPA)

6

Fig.1 of NACE 2003, H2S partial pressure

Vs in situ pH for H2S SSC
Figure 1- NACE 2003
6.5

Region 1
5.5

in situ pH

Region 0
Region 2
4.5

Region 3

3.5

2.5
0.01

0.1

0.3

10

100

1000

H2S Partial Pressure kPa

Note: Region 0,pH2S <0.3kPA, No precaution is required for

selection of steels per para 7.2.1.3
7

SSC Region by Fig .1 of NACE-2003

SSC Region 0: pH2S < 0.3kPa (0.05psi), No precaution for selection of

material

SSC Region 1: Material from A.2, A.3 or A.4 steels

SSC Region 2: Material from A.2 or A.3 steels

SSC Region 3: Material from A.2

Where A.2 is for SSC(sulfide stress cracking corrosion) resistant & low
alloy steel. A.2 is consistent with a previous established requirement of
NACE MR0175
A.3 is SSC resistant steels through out Region 2
A.4 is SSC resistant steels through out Region 1
A.2,A.3 &A.4 is in Annex A of Part B of NACE 2003

Important: Fig.1 of NACE 2003 is only for gas containing H2S

8

What is pH ?

pH
+
[H ]

0
1

Definition : pH = -Log[H+]

1
-1
10

2
-2
10

3
-3
10

pH < 3.5: Strong Acid

4
-4
10

5
-5
10

6
-6
10

Acid

7
-7
10

8
-8
10

9
-9
10

Alkali

Neutral : [H+] = [OH-]=10-7 gram ion/Liter

NACE-2003 ,Annex-D introduced pH of

condensed water under CO2 and H2S Pressure-1/2

100C
20C

Fig. D.1
Fig D.1 chart need to convert to Equation for
practical usage!
10

NACE-2003 ,Annex-D introduced pH of

condensed water under CO2 and H2S Pressure-2/2
pCO2+pH2S-kPa
pH
pH

Value below is read from Chart and converted into formula.

0.1
1
10
100
1000
10000
600
5.36
4.87
4.39
3.89
3.4
2.91
3.5
N/A
5.11
4.62
4.13
3.64
3.15
3.74

0.3
5.13
5.37

2023 Temp
3.25 At 20 C
N/A At 100 C

A. Proposed calculation formula based on approximation from D.1 Chart from NACE ( by AK on Feb
Y = - 0.49 Log 10 X + 4.87.( 1)
Y = - 0.49 Log 10 X + 5.11.( 2)

for T= 20C
for T= 100C

where Y: The pH of condensed water under CO2 & H2S

X: pCO2 + pH2S in kPA

Note: Fig. D-1 Chart is

redrawn by KL

0.1

10

100

1000

7
6
5
4
3
2
10000

pH

The pH at 20degC

pCO2+pH2S in kPA
11

To determine Wet or Dry at Inlet

PSIA
0.14
0.28
0.43
0.71
0.99
1.28
1.71
2.27
2.84
3.7
5.69
7.11

H2O Saturation Temp Vs Pressure

40
Partial Pressure-kPA

Temp-C kg/cm2A
6.7
0.01
17.202
0.02
23.771
0.03
32.55
0.05
38.66
0.07
43.41
0.09
49.05
0.12
54.93
0.16
59.66
0.2
65.43
0.26
75.41
0.4
80.86
0.5

Pressure
kPA
0.98
1.96
2.94
4.9
6.86
8.82
11.77
15.69
19.6
25.5
39.22
49.03

30

Wet
20

Dry

10
0
0

10

20

30

40

50

60

70

80

Temperature-degC

Note: H2S SSC and H2CO3 corrosion only occur at

presence of water
12

TableA.1:Guide to material selection

from Annex A of NACE 2003
Austenitic

Martensitic

Precipitation

S.Steel

S.Steel

Hardened
S.Steel

Any

Table A.2

Table A.18

Table A.26

Table A.6

Table A.22

Table A.30

Equipment or
Component
Compressor
Component

13

Martensitic Stainless Steel

Table A.18- Any equipment or component
Alloy UNS No
pH2S max-kPa
pH
S41000
J91540 (CA6NM) 10
3.5
S42400 (F6NM)

Table A.22-Compressor component

Alloy UNS No
pH2S max-kPa
S41000
J91540 (CA6NM) See remarks
S42400 (F6NM)

Sulfur resistant?
No data submitted

pH

Sulfur resistant?

See remarks

No data submitted

14

Precipitation Hardened S.Steel

Table A.27-Wellhead,Christmas tree component, valves& other subsurface equipment
Alloy UNS No
pH2S max-kPa
pH
Sulfur resistant?
S 17400
3.4
No data submitted
4.5
Note: Table 26 is for material of UNS S 66286 which is not applicable to DR.
Table A.30-Compressor component
Alloy UNS No
pH2S max-kPa
S 17400
See remarks

pH
See remarks

Sulfur resistant?
No data submitted

() Our interpretation of NACE 2003 for Martensitic and hardened precipitation S. Steel
S17400 (17-4PH) is good for pH max of 4.5 by NASE.
S41000( AISI410 ) is good for pH max of 3.5 by NACE. DR has same criteria
J91450 (CA6NM) is good for pH max of 3.5 per NACE, but is operated at lower pH for
Shell job
S42400(F6NM) is good for pH max of 3.5 per NACE, but is OK for max pH of 3.29 by
DR, Further it is under NACE testing in Olean. June 2006 will know result
N07718 ( 718 Inconel) is good for pH lower up to 2.5 by DR

15

D-R metallurgist view for 410 SS

410 Stainless Steel NACE Testing
1E-3
6.0

0.01

0.1

100
6.0

Fail, 0 PPM Chloride

Fail, 100 PPM Chloride

5.5

Nace MR0175
Approved

5.0

Solution pH

10

5.5
5.0

4.5

4.5

4.0

4.0

3.5

3.5

3.0

3.0

2.5
1E-3

0.01

0.1

10

2.5
100

H2S Partial Pressure (bar)

410 is good for max. pH 3.5 with max H2S

partial pressure of 0.1Bar(10kPA) based on
NACE test
F6NM NACE test is good for max. pH 3.29
16

High CO2 Gas+H2S Vs NACE

Check of past successful 100% CO2 gas with Equation 1

derived from Fig.1

pH calculation and comment for On-going project with

high CO2+H2S

17

pH Check for past CO2 compressors-1/2

Contract/ Ship
DML-6073E,
1977

CT21124,
1981

DML-6130E,
1982

MDR-1016,
1993

MDR-1020C,
1994

pH = -0.49Log10 X + 4.87 which is equal to Fig. D.1 of NACE 2003.

1st Stg Ps
pH
Actual
Ts-deg F
calculated Impeller
Comp
Section
psia
kPa
4M9-5
1
15.5
106
131
3.87 AISI410
3M10-7
2
63.6
438
109.4
3.57 AISI410
3
248
1709
109.4
3.28 AISI410
272B6/4
4
1041
7177
129
2.98 AISI410
3M4-3
1
16.8
116
109.4
3.85 AISI410
553B10-8
2
59.3
409
115
3.59 AISI410
3
203
1399
115
3.32 AISI410
161B5/5
4
687.4
4739
115
3.06 AISI410
1
20.4
140
113
3.81 AISI410
3M9-7
2
66.1
456
113
3.56 AISI410
3
240.9
1661
113
3.29 AISI410
272B5/4
4
896.5
6181
113
3.01 AISI410
1
20.8
143
107.6
3.81 AISI410
3M8-7
2
104.95
724
107.6
3.46 AISI410
3
406
2799
107.6
3.18 AISI410
26.08B5/4
4
1250.3
8621
131
2.94 AISI410
1
23.3
161
103
3.78 AISI410
3M8-7
2
103.5
713
104
3.47 AISI410
3
347.7
2397
104
3.21 AISI410
26.08B5/4
4
1047
7219
122
2.98 AISI410
18

pH Check for past CO2 compressors-2/2

pH for 100% wet CO2 application fallen into pH lower than

3.5 , but all units are operating well with S41000( AISI 410)
impeller material. Note Table 18 for 410 says pH 3.5

As stated in para 8.2 of NACE 2003 ( Qualification based

upon field experience) and wet CO2 gas is only contribute to
corrosion in lieu of stress cracking corrosion, we can

conclude that pH judgment for wet CO2 gas is not

correct method

19

Thank You.

20

 Copyright 2004

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