Corrosion Resistance of Nickel and Nickel Containing Alloys in Caustic Soda and Other Alkalies

CORROSION RESISTANCE OF
NICI<EL AND NICI<EL-CONTAINING ALLOYS

IN CAUSTIC SODA
AND OTHER ALI<ALIES
Publication NQ 281 (CEB-2)
NiDI
Distributed by the
Nickel Development Institute,
courtesy of Inco Limited
Table of Contents
Page
PART I. INTRODUCTION 3
PART II. CORROSION BY CAUSTIC SODA........................... 4
A. Nickel .................................... _ . . . . . . . . . . . . . . . . . 4
1. Effect of Concentration, Temperature and Carbon Content ...... _ . . . . . . 4
2. Effect of Velocity ............... _ ... __ ..................... _ 6
3. Effect of Aeration .......................................... 6
4. Effect of System Thermal Gradients .............................. 7
5. Effect of Impurities .,. _ ................. _ ............ _ . . . . . . . 7
6. Effect of Stress ............................................. 8
7. Effect of Dissimilar Metal Contact .. _ ...... _ ...... _ ............. '. 8
8. Cathodic Protection. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
B. Nickel-Chromium Alloys (Alloy 600) .. _ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
C. NickelCopper Alloys (Alloy 400, Alloy K-500) ....................... _. 10
D. Copper-Nickel Alloys .... _ ...... _ ............. ___ ............ _ ., 11
Copper-Nickel Alloy CA 706 (90-10)
E. Iron-Nickel-Chromium Alloys (Alloy BOO) ......... _ .............. _ . .. 13
f. Austenitic Chromium-Nickel Stainless Steels (AISI 300 Series) . . . . . . . . . . .. 13
G. Iron-Base NickelChromium...copper-MoJybdenum AHoys and Nickel-Base Chro-
mium...copper-Molybdenum Alloys .......... _ ....... __ ............. , 15
{Alloy 825. CARPENTER 20Cb-3, HASTELlOY alloy G and cast ACt CN-7M alloys}
H. Nickel-Base Molybdenum or MolybdenumChromium-lron Alloys. . . . . . . . . . . 16
(HASTElLOY alloy C-276, Alloy 625. HASTEllOY alloy B)
I. Cast Irons and Ni-Resists .... _ . _ .... __ .. __ . __ . . . . . . . . . . . . . . . . . . . . 17
PART m. CORROSON BY OTHER ALKAliES.. ............... .... .... 19
A. Caustic Potash (KOH) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 19
B. Ammonia and Ammonium Hydroxide ............................... 20
C. Other Alkaline Solutions of Sodium and Potassium Salts ................ 22
PART IV. INDUSTRIAL APPLICATIONS. ... .... . ............... ...... 24
A. Caustic Soda Manufacture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 24
B. Caustic Potash Manufacture ..................................... 28
C. Caustic Soda Storage and Transportation .......................... ". 28
D. Soap Manufacture ....................... _ ......... _ . . . . . . . . . .. 30
E. Pulp and Paper Industry ...... __ ............... _ .. _ . . . . . . . . . . . ... 32
1_ Digesters _............................................ ... 32
2. liquor Heaters ............................................. 33
3. Black liquor Evaporators .................. _ . . . . . . . . . . . . . . . 34
4. Recausticizing ............................................. 34
f. Aluminum Industry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 35
G. Caustic fusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 35
H. Petroleum Refining ............ _ .............. _ . _ . . . . . . . . . . . . .. 36
I. Caustic DescaJing . _ . _ .................... _ . . . . . . . . . . . . . . . . 37
J_ Reclaiming Caustic for Economy and Pollution Control. . . . . . . . . . . . . . 37
PART V. WELDING ............. __ ..... _ . . . . . . . . . . . . . . . . . . . . . . 38
A. fabrication of NickelClad Equipment .. _ ..................... " 38.
B. Repair of Equipment in Caustic Service ......... _ ...... _ . . . . . . . . . . .. 39
References .......... _ ......................................... ' 40
Trademarks ..................................... . . ... Inside back cover
Table I
Nominal Compositions of Nickel Alloys in Use or Corrosion Tested in Caustic Solutions
Composition. %
M;aterial Hi Fe Cr Mo Cu C Si Mn
WROUGHT MATERIALS
Nickel
Hickel 200 99.5 0.15
-
-
0.05 0.06 0.05 0.25
Hickel20t 99.5 0.15 - -
0.05 0.01 0.05 0.20
DURAH.CKEL alloy 30t 94.0 0.15 - -
0.15 0.55 0.25 0.25
Nickel-Chromium Alloys
.HCOHEL alloy 600 16.0 7.2 15.8 - 0.10 0.04 0.20 0.20
H.MONtC alloy 75 71.4 0.5 20.5 - - 0.10 - -
Nickel-Copper Alloys
MONU alloy 400 66.0 1.35 - -
ll.5 0.12 0.15 0.90
MON!., al'lI1 K.SO!!:. 65.0 leO
-
- 29.5 0.15 0.15 0.60
Copper-NiCkel Alloys
Copper-Nkke:1 allo, CA 706 10.0 1.25 - - 88.0 - - 0.3
CopperNickel alloy CA 710 20.0 0.75 - -
78.0 - - 0.4
CoppefNlekel alloy cA 715 30.0 0.55
- -
61.0 - - 0.5
IronNickel-Chromium Alloys
'NCOLO"- alloy 800' 32.0 46.0 20.5 -
0.30 O.M 0.35 0.75
Stainless Steels
AISI Type :202 5.0 67.0 18.0
- - 0.15ma. 1.0 max 8.1
AISI Type 31)2 9.0 70.5 18.0
- -
0.15 max 0.5 1.5
AI5ITy, . 304 9.5 70.0 18.0 - -
0J)8 max 0.5 1.5
AISI TYlle 304l 10.0 69.0 18.0
- -
0.03 max 0.5 1.3
AISI tYPe 316 13.0 65.0 17.0 2.0mi ..
-
O.OS max 0.5 1.7
AISI tJllO 316l 13.0 65.0 17.0 2.0 min - 0.03 max 0.5 1.8
AISI Type 309 13.5 60.5 23.0 - - 0.20 malt 1.0 max 2.0m3X
AISI Type 310 20.0 52.0 25.0
-
- 0.25mn 1.0 max 2.0ma.
AISI Type 330 35.0 41.0 1.5.1) - - 0.25 rna. 1.0 rna. 2.0 mal
AISI Type 347 11.0 68.0 18.0 - - 0.08mu 1.0 max 2.0mu
AISI Type. 438
-
Bal 17.0 - - 0.12 max - -
Iron Base NicketChromium-Copper-MoIybxlenum Alloys
Stainless No. 20 <1' 29.0 43.0 20.0 2.0 min 3.0m;n 0.07 max 1.0 0.8
CARPEfC-rR' No. 2OCb-3 34.0 39.0 20.0 2.5 3.3 0.01 max 0.6 08
Nickel Ba';'e l'bn-ChromiumMoIybdenum Anoys
'HCOl.OY- a!Joy 825 41.8 30.0 21.5 3.0 1.8 0.03 0.35 0.65
HASTLLO .. " alloy G 45.0 19.5 22.2 6.5 2.0 0.03 0.35 1.3
:alloy C 5.0 15.5 16.0 - 0.08 max 1.0 rna. 1.0 max
HASTELLO .. - alloy C2l6 54.0 5.0 15.5 16.0 - 0.02 max 0.05max 1.0max
'HC_I:L - alloy 625 60.0 5.0ma. 21.5 9.0 - 0.10 max 0.5 max 0.5 max
Nickel Base Molybdenum Alioy
.. ASULLO'\'- alloy B 61.0 5.0 1.0 max 28.0 - 0.05 max
- -
CAST MATERIALS
Nickel
America .. Casti"e Institute
ACI CZl00 95.0 min 1.5 max
- - - 1.0 max 2 .. 0 1.5 max
NickelCh.romlumfron Alloy
ACI CY40 70.0 9.5 15.5 - - 0.3 3.0 max 1.5 max
Nickel-Copper Alloys
HickelCopper alloy 50S 64.0 2.0 - - 29.0 O.OS 4.0 0.80
ACI "'-35 64.0 3.5 max - -
29.5 (1.35 mall 2:.0 mat 1.5 max
Stainless Steels
ACI Cr-8 19.5 66.0 9.5
- -
0.08mllll: 2.0m,n 1.5 mall
ACI Cf8M 19.5 63.0 10.5 2.5
-
OJl8 max 1.5ma. 1.5 max
ACI CAtS 1.0 max 83.0 12.8 Q.5max
-
0.ISm3l 1.5mu 1.0ma.
ACt HA - 87.0 9.0 1.1
-
0,20mu' ).0 rna. O.S
Iron Base Nickel-ChromiUm-CjPper Alloys I
wo ...... tn: Stainless 24.0 48.0 20.0 3.0 1.75 0.1)7 max 3.3 0.6
ACI CN-7M "'0 29.0 44.0 20.0 2.0 mill 3.0 min 0.01 milx 1.0 UiJlnax
Nickel Base 'ron-ChromiumMolybdenum Alloys
CHLORIMT" 3 I 60.0 2.0 18.0 JUt - 0.01ma1l 1.0 1.0
ILLIUM' alloy to 56.0 6.5 22.5 U $.5 0.20 0.65 1.25
Nickel Base Molybdenum Alloy
.'
cHt.o,nMII!T 2 63.0 3.0ma. - 32.0
-
0.15 1.0 1 ..0
Nic,kel Base Sitleon Alloy
alloy D 82.0 2.0lllllx 1.0 rna.
-
3.0 O.l?max 90 0.51.25
Nickel Alloyed Cast Irons
NIRes)st Type 1 15.5 69.0 2.2
-
6.5 2.8 2.0 1.2
HIRu;st Type 2 20.0 70.0 2.2
-
05ma. 3.0 max 1.9 1.2
HI-Resist Type 3 30.0 62.0 3.0
-
O.Sma. 2.6ma. 1.5 0.6
NiResist Type 4 30.5 55.0 5.0
-
0.5 rna. 2.6 mal 5.5 06
NiResist Type D2 20.0 72.0 2.1 - -
3.0 max 2 . .f 0.9
HIResist Type D3 30.0 61.0 3.0
-
-
2.6 max 2.2 O.Sma.
(1) An improved version of this alloy. CARPENTER'" stainless',No. 20Cb3. has replaced CARPENJR'" No. 20
(2) An improved version of this alloy. HASTEllOY alloy C276. has replaced .. ASTUt:OY alloy C.
(3) Cast Alloy 20 alloys such as DUR,MUO alloy 20. ALOYCO" alloy 20. etc
See ins;de back cover for registered trademarks.
2
Otber
-
-
AI 4.5; Ii 0.5
-
Ii 0.l5; AI 0.15
-
AI 2.8: Ti 0.5
Pb 0.05 max; In 1.0 rna.
Pb 0.05 rna.; Zn 1.0 max
Pb 0.05 max; In 1.0 max
-
N 0.25 max
-
-
-
-
-
-
-
-
Cb;- Ta IOxC min
-
-
Cb+Ta 0.6
AI 0.15: Ii 0.9
W 0.5; Cn ,. Ta 2.12
Co 2.5ma<;
W 4.0: V 0.4 max
Co 2.5 rna.;
W 4.0: V OA max
Cb- Ta 3.65
Co 2.5 rna.: V 0.20A;
P 0.025 rna.;
S 0.030 max
-
-
-
-
-
-
-
-
-
-
-
-
-
Co 1.5 max
_.-
-
-
-
--
-
Corrosion Resistance of Nickel and Nickel-Containing
Alloys in Caustic Soda and Other Alkalies
PART I. INTRODUCTION
Caustic soda (sodium hydroxide) is the most
widely used and avaBablealkaline material. In the
United States almost all of the caustic soda is pro-
duced as a co-product in the production of chlorine
by the electrolysis of sodium chloride. The elec-
trolytic cells used can be divided into two general
types: mercury cells and diapllragm cells. With
mercury cells,high purity SOt;(. caustic is pro-
duced directly, whereas with diaphragm cells. the
caustic concentration produced is within the
range of 9 to 15 per cent, and has to be further
purified and concentrated before sale. A small
amount of caustic soda is produced by the lime-
soda proce$S which WaS formerly the prime source
for this chemical.
Caustic soda is generally marketed in concen-
trations of 50 percent, 73 per cent or anhydrous.
The chemical industry is the largest consumer of
caustie soda, followed by the rayon and film in-
dustries. the pulp and paper industry and the
aluminum industry.
A large number of alloys can be used for han-
dling caustic soda, and selection is based upon
such factors as concentration. temperature, im-
3
purities in the caustic, the necessity for product
purity. corrosion rate, susceptibility to stress-
corrosion cracking (caustic embrittlement) and
economics. Caustic soda can be handled in cast
iron or steel equipment at low temperatures. if
iron contamination is not detrimental to end use.
At elevated temperatures, however, iron and steel
are subject to caustic embrittlement and high cor-
rosionrates. Plant and laboratory tests and oper-
ating experience over many years have demon-
strated that nickel and nickel alloys are the
preferred materials for handling caustic solu-
tions in many applications. Nickel can be used for
practically an concentrations and temperatures.
In addition to caustic soda. several other im-
portant alkalies are discussed in this bulletin. but
no attempt has been made to be all-inclusive.
Nominal compositions of alloys referred to in
the text are shown in Table L Materials other
than nickel-eontaining alloys included in a num-
ber of tests are reported for reference purposes.
An corrosion rates are reported as mils pene-
tration per year (mpy). (1 mil = 0.001 inch.)
Fig. 1 - These caustic soda evaporator units are a
combination of both solid Nickel 200 and steel clad
with Nickel 200. Diaphragm cell liquor feeds into the
double-effect evaporator: overflow from a settler tank
feeds the single'effect evaporator for conc.entration to
50% caustic soda. The system produces 700 tons of
salt and delivers 434 tons of NaOH (100%1 per day.
Ph%qraDh by courtesy ot
the Swenson Division Of Whiting Corporation.
PART II. CORROSION BY CAUSTIC SODA
A. Nickel
1. Effect of Concentration, Temperature
and Carbon Content
Corrosion test results for nickel in commercial
caustic soda solutions were obtained by a number
of investigators at different times and locations.
Typical test data are shown in Table II and these
have been incorporated in the isocorrosion chart,
Figure 2. Only at high caustic concentration near
the boiling point does the corrosion rate exceed
one mil per year. This isocorrosion chart is in-
tended only as a guide; there are specific condi-
tions under which higher or possibly lower cor-
rosion rates can prevaiL These conditions are
discussed later.
700 r---..,.-----r---r----..,.---"r"> 371
600
500
u... 4oo
..
:;
"0
Q;
Q
100
f-
200
100
316
]60
'13
<OJ mpy
"- 0.1 mpy
38
o '--__ ....l.-_.L---l. __ --''--__ ...L-__ . 17.8
o 20 40 60 80 100
Fig. 2 -Isocorrosion chart for Nickel 200 and Nickel 201
in sodium
Some tests which have been carried out at
elevated temperature and pressure in autoclaves
indicate satisfactory performance for nickel in
caustic soda solutions even above the atmospheric
boiling point, as shown in Table IIU
4
Fig. 3 - View of caustic transfer piping from marine storage
tank area to terminal where rayon grade 50% caustic soeta
is loaded into a barge. Several hundred feet of lightweight.
welded Nickel 200 piping in 8-inch and 12-inch sizes are
used.
In caustic concentrations above 75 per cent and
including molten caustic soda. nickel is second
only to silver in resistance to corrosion. When
nickel is to be used at temperatures above 316 C
(600 F). a low-carbon grade, Nickel 201 (0.02% C
max). should be employed to preclude the possi-
bility of graphite precipitation in the grain boun-
daries and a resultant loss in ductility. Nickel 201
is often used for the construction of tubular evap-
orators for continuous vacuum concentration of
caustic soda from 50 and 73 per cent to anhy-
drous at temperatures up to 404 C (760 F). with
nickel pickup in the finished caustic of only one
to two ppm.
3
Molten caustic soda has been considered as a
heat transfer medium for nuclear energy appli-
cation. In static tests at Harwell in England,
Gregory. et concluded that Nickel 201 was a
satisfactory container material for molten caus-
tic soda at temperatures up to 580 C (l076 F)_
Some of their data are shown in Table IV.
Table II
Typical Corrosion Test Data for Nickel and High Nickel Alloys in Caustic Soda Solutions
HaOH
;oncen-
tration,
%
D-1
4
4
5-10
14
22
34
30"50
49-51
50
50
50
72-73
72
73
73
13
14
15
60 to
nearly
anbydrnus
Temperature
C F
3{l 86
30 86
3{l
86
21-32 70-90
88 190
50-60 12{)-140
65 150
81 178
55-75 131-167
31165 av 149
55-61 131-142
31158 a1l 136
60-70
av65 al/ 149
150 302
116 273
121 282
95-100 203-212
100-120 212-248
avll0 a1l230
104-116 244-251
av 110 av248
130 266
135 271
302-500
Less than 0.005 mils per year.
A.e1ation Agitation
Nooe Hone
Hone None
Air agitated Air agitated
Extensive due to
filling tank
None None
None due to
filling tank
Extensive Mild
None None
None due to
lining tank
None due to
filling tank
Moderate by lOOgpm
flow from
pump
None None
None due to
filling tank
Moderate due to
filling tank
None by rocking
of tank
None due to
filling tank
None due to
filling tank
Not specified by movement
of tank car
Not specified due 10
filling tank
None None
Test
Period,
days
27
1&2
1&2
124
90
133
37
16
30
135
393
14
183
119
111
52
126
II trips
of 7-9
days
35
2
5
Comments
Test coupons removed,
cleaned and dried each day
fOf lOdays
Average of tests run at
8 separate laboratories
Average of tests run at
8 separate laboratories
Storage lank
First effect of multiple-
effect evaporator
Storage tank coupons
immersed 95% of time
Storage tank in which air was
bubbled through from bottom
Single-effect evaporator_
Rates are average of 3 tests
fully immersed
Storage tank
T ransler piping. at pump
discharge
laboratory test on tubing;
average of 4 coupons
Storage tank
Storage tank
rest tank_ simulating action
of tank car
immersed 95% of time
lully immersed
Coupons in railroad
tank car
Storage tank between
evaporator and finishing pots.
Ammonia Soda Process
Concentration in caustic
evaporator
Corrosion Rate, mils per year
Hicke!
200
0.01
0.05
0.05
0.15
0_02
nil
0.03
0.09
0.02
0.02
0.07
-
0.3
OJ
0.13
0.05
0.02
0.3
1.6
3.9
Nickel-
Copper
Alloy
(MONEL
alloy
40ll)
0.01
0.16
0.21
O.ll
0.05
0_01
-
0.19
0.03
0.02
0.10
-
0.7
0.3
0.16
0.04
0.10
0.4
1.7
13.4
Nickel-
Chromium
Alloy
ltNCONEl
alloy
6nO\
nW
-
-
0.05
0.03
0_01
0.03
-
0.02
0.02
0.03
0.25
0.4
0_1
0.14
0.06
0.0\
-
1.3
-
Table llt
laboratory Corrosion Tests in Caustic Solutions at Elevated Temperatures
NaOH
Concen-
tration,
%
Temperature
C F
Test
Period,
hr
Nickel
206
20
110 262 15 nil
40
110 262 15 nil
60 llO 262 15 nil
80
110 262 15 nil
20 115 272 19 nil
40 115 272 19 nil
60 ll5 272 19 nil
80 US 272 19 nil
20 162 355 19 nil
40 162 355 19 nil
60 162 355 19 nil
80 162 355 19 nil
20 149 332 19
40 149 332 19
60 149 332 19
20
132 270 ]9
40 132 270 19
GO 132 270 19
80 132 270 19
20 111 340 19(2 tests}
40 111 340 19 (2 tests)
60
l7l 340
1912 testsl
80
17l 340 19 (2 tests)
20 156 345 20
40
156 345 20
GO 15G 345 20
86 156 345 20
20 127 293 15
40 127 293 15
GO 127 293 15
80 127 293 IS
20 150 334 18
46 150 334 18
GO 152 336 19
20 183 394 15
GO 183 394 15
80 183 394 15
2. Effect of Velocity
Velocity has little effect on the corrosion rate of
nickel in caustic at temperatures below 500 C
(932 F) but at 540 C (1004 F) and above, increas-
ing velocity may cause a several-fold increase in
the rate of attack. Figure 4 shows the results of
two-week laboratory experiments by Gregory,
et al., in high temperature molten caustic soda
under dynamic conditions.
6
MONEL
alloy
400
nil
3
1
WORTHITE sIs
(solution
quenched)
4
9
1
nil
25,69
36.28
2,38
nil. nil
14
17
33
1
3. Effect of Aeration
Hi-
Resist
Type 2
94
6
17
28
Cast ACI
CN7M
10
1
12
nil
151
2
Aeration has not been observed to accelerate
corrosion in lower concentration caustic soda
solutions. However, at high concentrations and
temperatures, such as occur when concentrating
to anhydrous, precautions should be taken to
minimize aeration.
M"lten Coust;c Sodo
720 C (1328 Fl
480
400
>-
680 C (1256 Fl
E
320

0
oc
240
.----------
c
_Q
E
(;
u

600 C {I I 12 Fl
580 C {1076 Fl
540 C (l004 F)
635 C P 175 Fl

400 C ( 752 FI
500 C I 952 F)
100 200 300 400 500 600
Rotot;on $peed_ rpm
Fig. 4 - Corrosion rate of nickel as a function of rotational
speed.'
Table IV
Static Corrosion Rates of Nickel and Nickel Alloys
in Molten Caustic Soda
Temperature
460e 500e 58fl e 680e
Alloy (750 f) (932 f) (1076 f) (1256 f)
Hickel20t 0.9 1.3 2.5 37.8
HASTELLOY a!toy e 100.5
HASTELt.OY aUoy D 0.7 2.2 9.9
MONEl. alloy 400 1.8 5.1 17.6
INCONEL aUoy 600 U 2.4 5.1 66.4
OURANICKEI. alloy 30t 1.7 3.2 10.4 40.7
NIMONIC all01 75 1.1 14.3 20.8 47.6
(pitted)
Gained weight. Swollen outside surface largely oxide-heavily cor
roded.
4. Effect of System Thermal Gradients
In molten caustic soda at temperatures above
about 550 C (1022 F), nickel is subject to thermal
gradient mass transfer.:; 4;. 7 In this type of at-
tack, nickel is dissolved in caustic at a high tem-
perature surface and is precipitated at a low
temperature surface in a circulating system.
Gregory, et at, concluded that the corrosion rate
of nickel in molten caustic soda could be ten times
as great under dynamic conditions as it was
under static conditions because of the solubility-
temperature relationship.:;
The mass transfer effect can be inhibited but
not prevented by maintaining a hydrogen-con-
7
taining atmosphere in the vicinity where corro-
sion is occurring. Forestieri and Lad found that,
as a result of the presence of chromite ion
(CrO:I-
1
), mass transfer and cOITosion were
essentially eliminated for 50 hours by one per
cent addition of 325-mesh chromium powder in
a test loop operating at a fluid velocity of 15 fps
and 816 C (i500 F) with a temperature difference
of either 11 C (20 F) or 22 C (40 F) .>1.9 However,
a small mass transfer deposit was obtained after
250 hours, indicating that a single chromium ad-
dition would not protect a nickel system in-
definitely.
5. Effect of Impurities
Chlorates in caustic can increase corrosion rates
as indicated in the later section on caustic soda
manufacture (page 27). Small amounts of so-
dium chlorate are produced in electrolytic dia-
phragm cells. The effect of the chlorate on corro-
sion rate is not critical unless the chlorate is de-
composed. and thermal decomposition does not
occur below a temperature of 260 to 290 C (500 to
554 F). If it is intended to operate nickel equip-
ment at or above this temperature range. four
alternatives are available:
a. Use "rayon grade" caustic which has a speci-
fication of 5 ppm maximum chlorate content.
b. Use caustic produced by electrolytic mercury
cells or by the lime-soda process, or,
c. Use anhydrous caustic; there are no chlorates
in the anhydrous grade .
d. Add reducing agents as discussed in the sec-
tion on caustic soda manufacture (page 27) .
The presence of oxidizable sulfur compounds
in caustic soda tends to increase the corrosion
rate of nickel at elevated temperatures. This is
noted particularly with hydrogen sulfide, mer-
captans, or sodium sulfide, and to a much lesser
extent with partially oxidized compounds such as
thiosulfates and sulfites.
The effect of the addition of oxidizable sulfur
compounds to caustic soda on the corrosion rate
of nickel has been studied in the laboratory with
the results shown in Table V. Test 1 was made
during the evaporation of a commercial caustic
soda solution under 28 inches of vacuum. Sulfur
content of the original caustic. calculated as per
Table V
Effect of Oxidizable Sulfur Compounds on Corrosion
of Nickel 200 in Caustic Soda
Temperature: 130 C c::: 5 C (266 F c::: 9 Fl.
Corrosion
Test Rate,
No. Corrosive mils per year
Commercial Sodium Hydroxide being concentrated
from 50 to 75% NaOH (Sulfur content at start.
calculated as H,S. 0.009%} 1.7
2 75% C.P. Sodium Hydroxide 0.6
3 75% C.P. Sodium Hydroxide plus 0.75% Sodium
Sulfide 22.8

Sulfite 5.2
Su!!ate 0.6
Chemically pure.
cent H;!S in dry caustic, was 0.009 per cent. Test 2
was made in chemically pure caustic soda. Tests 3
through 6 were made in chemically pure caustic
to which the various sulfur compounds had been
added.
It has been found that the detrimental effect
of oxidizable sulfur compounds in caustic can be
counteracted by the addition of sufficient sodium
peroxide to form sulfates. An excess of peroxide
does not seem to be detrimental. as shown in
Table VI which compares the resistance of nickel,
iron, and copper to fused caustic soda with and
without an addition of 5c;. sodium peroxide.
lo
In each test, 5 grams of the substance were fused
for four hours in a laboratory crucible of the
given metal and analyzed for metal pickup.
6. Effect of Stress
Experience has indicated that Nickel 200 is not
subject to stress-corrosion cracking in pure
caustic solutions. However, it is subject to
stress-corrosion cracking by mercury, and there
have been a few cases of cracking of nickel when
"upsets" occur in producing plants that utilize
mercury cells.
In addition, cracking along precipitated grain
boundary jTraphite in Nickel 200 has occurred
after caustic soda exposure above 316 C (600 F).
As indicated previously. a low-carbon grade
8
(Nickel 201) will circumvent this problem.
Applied or residual stresses apparently do not
significantly affect the genera! corrosion rate of
nickeL 11
7. Effect of Dissimilar Metal Contact
Galvanic corrosion can occur in caustic soda solu-
tions if different materials of construction are
electrically connected. Whether this effect is aca-
demic or critical depends upon the specific condi-
tions that exist in a partiCUlar installation. For
instance, the data in Table VII illustrate that gray
cast iron corrodes from about one and one-half
Table VI
laboratory Tests in fused Caustic Soda with and
without Addition of 5% Sodium Peroxide
Temperature Metal Pickup. grams
COHosive
Caustic Soda
Caustic Soda
with 5% Sodium
Peroxide
SI rangly attacked
C
350
360
400
450
500
550
600
350
400
450
f Nickel Imn
662 .4
680 .01.02
752 Irace.02 .426
842 .01.02 .2.3
932 .005.015 .2.3
1022 .4.43
1112 .i3.3
662 .0024 .024
752 .0135 .025
842 .OBI .Il
Table VII
Galvanic Corrosion of Gray Cast Iron
Conditions: Corrodent: 5% sodium hydroxide.
Temperature: 43 C (ll 0 F).
Flow: 16 feet per minute.
Aeration: Saturated WIth air.
Cathode to anode area ratio 2: 1.
Copper
trace
.013
.03
Corrosion Rate of Corros ion Rate of
Gray Cast Iron. Cathodic Material,
mils per year mils per year
In In
Cathodic Galvanic Galvanic
Material Insulated Couple Insulated Couple
Nickel 200 l.l 1.5
Nickel 200 0.6 ]6 0 <0.1
MONEL alloy 400 0) 2.1 <01 <0.1
MONEL alloy 400 0.6 17 0 0
0.75 1.72
Average Average
Slight welgh1 gain
to three times its normal rate when connected to
Nickel 200 or MONEL alloy 400, under the given
set of conditions. However, the normal rate for
cast it-on in caustic is so low that these higher
corrosion rates are usually tolerable.
At higher caustic concentrations, tempera-
tures, and with large cathode to anode r;:ttios.
galvanic corrosion becomes more pronounced.
The galvanic current curves shown in Figure 5
are from tests made above and close to the upper
tube sheets of operating caustic evaporators. The
general conclusions to be drawn from these tests
are that in concentrated caustic soda solutions.
significant galvanic corrosion may occur on cast
iron or steel when in contact with nickel or cop-
per. In the construction of caustic evaporators.
it is desirable, if not actuaHy necessary, to use
nickel or nickel-clad steel tube sheets in conjunc-
tion with nickel tubes.

u.
q
b.O
5.0
t
Si 4.0
c

{; 3.0
" o
"
1.0
.(
GoJvonrc Current Flow Between
C05-t 1on end Copper
A"'?oe: !"on . C 3QS -;:: ;:.
Ccpoer 0.*9"4 ;-:: =.
JS
7.0,-----,..-----,----,..-----.--__ -,-____ ,--__ -,-__ --,

0
"
?
U
" "D
"
.(
3.0
2.0
1.0
0
Q
S
Golvonic Cv ... enf flow Between
Cad Iron ond Niclel
Af"-e:2 =-.C J c.
C,+ode: ...:. il.24; 5.;)::.
Fig. 5 -- Current measurements between cast <ron, copper
and nickel specimens set up above and near the upper tube
sheet of an evaporator concentrating caustic soda from 47
to 60 per cent. NaOH under 26 in. vacuum using steam at
a pressure of 75 Ib per sq in.
9
8. Cathodic Protection
In the continuous production of anhydrous caus-
tic, experience has shown that cathodic protection
can be applied successfully to nickel evaporating
equipment. In one such case, a cathode current
density of about 1 ampere per square foot of ex-
posed nickel surface provided satisfactory pro-
tection. In other less corrosive applications, as in
storage of caustic, current densities as low
as 0.01 ampere per square foot have been reported
effective. Nickel 200 anodes are used in these ap-
plications_ Laboratory tests in 75% caustic soda
at 120 C (250 F) and also in fused anhydrous
caustic soda at 480 C (900 F) have shown that
\",ith equal areas of nickel for anode and c.athode,
and with an applied anode current density of
10 amps per square foot, the corrosion rate of
the nickel anode does not exceed that of uncoupled
nickel. A pure technical grade of sodium hydrox-
ide was in these tests, which contained less
than 0.04 per cent of heavy metal impurities. The
result.c; are shown in Table VIn.
Table Viti
laboratory Tests of Nickel 200 Anodes and Cathodes
in 75 Per Cent and Fused Caustic Soda
Temperature: 120C (250F) for 75% caustic.
480 C (900 F) for fused caustic.
Duration of Tests: 1821 hr.
Volume of Solution Used: 1 liter.
Anode Current Density: 10 amp per sq ft.
Area of Specimens: 0.066-0.087 sq ft.
Average Corrosion Rate.
mils lIer year
Nickel 200 Anode
Nickel 200 Cathode
NickeI200-Uncollpletl
75% Caustic
0.8
0.2
1.0
fused Caustic
11.3
0.9
11.2
Note that the cathodic nickel surface benefited
from cathodic protection, while the corrosion rate
of the nickel anode was not increased.
B. Nickel-Chromium Alloys
Nickel-chromium alloys, such as INCONEL alloy
600, are approximately equi\'alent to nickel in
corrosion resistance in caustic soda, as shown in
Tables II, IV and XL.
Alloy 600 is commonly used in equipment for
the production of anhydrous caustic when sulfur-
bearing fuels are used for heating because it is
more resistant to sulfidation than nickel.
There have been a few instances of stress-
corrosion cracking of Alloy 600 in some strongly
alkaline environments. A review of these serviee
failures has indicated that they usually occurred
in concentrated caustic solutions at high tempera-
tures, 190 to 450 C (374 to 842 F). In seven-day
laboratory tests, caustic concentration, tempera-
ture, and the presence of air were shown to be
important variables, as shown in Tables IX and
XIV. No stress-corrosion cracki ng occurred if the
Alloy 600 U-bend specimens were stress-relieved
at 900 C (1650 F) for one hour or 769 C (1400 F)
for four hours after bending.
Table IX
StressCorrosion Cracking of INCONEl Alloy 600
U-Bend Specimens in Caustic Solutions-
Seven-Day Tests
Temperature Over-
pressure.
Caustic CORcentratiolt, weight %
C f 150 psi Caustic 10 50 90
200 390 Air NaOH OK OK
250 480 Air NaOH stress-cracked
300 570 Air NaO" OK stresscracked stresscracked
200 390 Argon NaO" OK OK
250 480 Argon NaOH OK
300 570 Argon NaOH OK OK OK
200 390 Air KOH OK slight inter
granular
penetration
250 480 Air KOH stresscracked
300 570 Air KOH OK OK stress-cracked
Note: Testing performed in autoclaves under static conditions without
replenishment of air or argon.
C. Nickel-Copper Alloys
Nickel-copper anoys, such as MONEL alloy 400,
are practically as resistant to caustic soda as
nickel, as shown in Table II.
The corrosion rate of Alloy 400 is higher than
nickel at caustic soda concentrations above 75 per
cent when concentrating to anhydrous. It is also
10
Fig. 6 - This barge has eight tanks with a capacity of
34,000 barrels .. The are used to carry fuel oil or as
and a specli;ll 54.00barret tank fabricated of INCONEl
alloy 600-clad steel is used to carry 73
0
10 caustic soda, am
moniabasefertilizers, or jet fuels.
higher than nickel at temperatures above the
atmospheric boiling point, as shown in Table III.
However, it should be noted that even in those
cases where AHoy 400 is inferior to nickel, the
corrosion rates are still quite low.
There have been a few reports of stress-corro-
sion cracking of cold-worked and stressed Alloy
400 in caustic soda. However, the eXact conditions
under which most of these failures occurred are
not known. It is known that some of the reported
failures associated with mercury cell caustic were
caused by intergranular attaek by mercury and
subsequent loss of ductility.
Laboratory tests have shown that Alloys 400
and K-500 can be susceptible to stress-corrosion
cracking unde.r extreme exposure conditions. that
is, high stresses in combination with high tem-
peratures and concentrated caustic soda can cause
cracking. Table X shows the results observed
with tensile loaded specimens tested at 300 C
(570 F) in condensing steam after being coated
with either potassium or sodium hydroxide.
Under these exposure conditions, Alloy 400,
which had been cold-worked or cold-worked and
stress-relieved prior to testing, was susceptible
to stress-corrosion cold-worked mate-
rial that had been annealed at 850 C (1560 F) or
950 C (1740 F) prior to testing was resistant. As
with Alloy 400. Alloy K-500 cracked when cold-
Table X
Stress-Corrosion Tests on MONEL Alloy 400 and MONEl Alloy K-500
Alloy Heat Treatment
MONEL alloy 4(1(1 None-as cold-drawn
850 C (1562 fltIti hr/W.O.
MONEL alloy 40(1 Stress relieved
540 C 11004 fl/ z hr
MONEL alloy 40(1 Works anneal
950 C U742 fll Y2 hr
MONEL alloy KS(I(I None-as COld-drawn
870 C U598 f)f5 min/W.O.
580 C (1076 fl/S hf/fC
810 C US98 A/S min/W.O.
+ 580 C {1016 fl/16 hr/FC
MONEL alloy K500 None-as colddrawn
870 C (1598 fl/5 min/W.O.
580 C n076 AIS hrl FC
870 C (1598 fl/5 min/W.Q.
+ saocno76 flfl6 hr/fe
Fumace-coaled at about 10 C (18 Fl/nr to 480 C
(896 Fl then "if.-coa!ed to room lef'lperature.
NO = Not Determined
o == Specimen fractured
1 == Coarse 'cracks visible to naked eye
2 == Fine cracks visible to naked eye
3 == Deep cracks visible under microscope
worked and was resistant in the annealed condi-
tion. However. the thermal-hardening treatment
at 580 C (1076 F) rendered the alloy very suscep-
tible to cracking.
The practical interpretation of these data is
difficult because threshold values of stress, caustic
soda concentration, and temperature at which
stress-corrosion cracking will occur have not been
established. With these limitations in mind, it
would appear prudent to stress-relieve AHoy 400
in the range of 538 to 566 C (1000 to 1050 F) or
anneal it ill the range of 760 to 816 C (1400 to
1500 F) for one to three hours when it is to be
used in higher strength caustic at elevated tem-
peratures.
D. Copper-Nickel Alloys
The corrosion resistance of copper-nickel alloys
in can.stic soda solutions is dependent upon the
nickel content of the alloy, as illustrated in Fig-
ure 7. There are a limited amount of additional
data which are shown in Table XI.
11
Yield Applie II
Strength, Stress,
ton/ S1l in. tonI sq in.
43.8 33.1
12.8 16.3
24.0 20.1
11.4 8.3
52.5 33.1
21.2 10.3
65.5 37.2
44.9 37.2
53.2 33.1
NO 10.3
NO 37.2
NO 37.2
Type and Degree of
Cracking
NaO\( KO\(
IIG 41'11
5 5
OIG OIG
5 5
3IG+TG 5
5 5
4TG 5
OrG OIG
4NI
5
OIG
DIG
4 = Shallow cracks visible under microscope
5 = No cracks
TG = Transgranular cracks
IG == Intergranula. cracks
I'll = Type of cracking nQt jdentified-cracks very
short.
>-
0-
E
'" 12
o
a::
5 8
.;;;
l?
4
20 40 60
Per Cent Nidel in Copper.Nickel Alloys
100
Fig. 7 - Results of corrosion tests of copper-nickel alloys
in 50% caustic soda evaporator.
Copper-nickel alloy CA 715 (70% Cu-30% Ni)
possesses excellent resistance to dilute concen-
trations of caustic soda at low temperatures and
appears to have useful resistance to caustic soda
solutions of up to 73 per cent at the boiling point.
However, this resistance does not extend to fused
caustic. Alloy CA 715 has been used successfully
as evaporator tubes for concentrating to 50 per
cent where copper pickup by the caustic could be
tolerated.
Copper-nickel alloys CA 706 Ni)
Table XI
Corrosion of Copper-Nickel Alloys by Caustic Soda Solutions
Nominal
HaOM
Alloy
Composition
Concen- Copper-
Temperature
tration, Hickel Wt% Wt%
% Alloy Cu Hi C F
5 - 60 40 15-20 I 59-68
11 60 40 Hot-Exact temperature
unknown
5 70 30 1520 .1. 59-68
11 70 30 Hot-Exact temperature
unknown
50 70 30 95 203
50 CA 715 70 30 65 149
73 70 30 105 221
60-75 70 30 150-175 302347
60-1Im 70 30 150260 302500
100 70 30 400410 752770
5 80 20 1520 5968
6075 80 20 150-175 302347
CA 710
60100 80 20 150260 302500
100 80 20 400410 752770
50 90 10 95 203
CA 706
73 90 10 105 221
,. Less than 0.1 mit per year.
and CA 710 (80% Cu-20% Ni) have useful resist-
ance to caustic soda solutions but their applica-
tion is limited to lower concentrations and tem-
peratures than AHoy CA 715. Because of the
limited data available it is difficult to define limits
for these two alloys.
While corrosion of the copper-nickel alloys by
caustic solutions may be aggravated by the pres-
ence of sulfur compounds, Alloy CA 715 is able
to resist attack under some conditions, as shown
in Table XII. No data appear to be available on
the susceptibility of these alloys to stress-corro-
sion cracking in caustic soda solutions.
Test Corrosion
Dura- Rate,
tion, mils per
days year Comments
21 Nil laboratory test in glass bottle.
25 0.5 Diaphragm cell liquor
coupons in distributor box to settlers.
25 4.3 Diaphragm cell liquor
coupons in distributor box to settlers.
67 0.8 Velocity 1.8 ftl sec. Salt saturated.
30 Nil In storage tank.
118 1.2
l/Z 4.4 In evaporator concentrating from 60-75%.
2 21 In evaporator concentrating
from 60% to anhydrous.
1 70 In anhydrous melt.
liz 8.1 In evaporator concentrating
from 6075%.
2 28 In evaporator concentrating
from 60% to anhydrous.
1 90 In anhydrous melt.
67 1.8 Velocity 1.8 ft/sec. Salt
saturated.
118 2.0
Table XII
Corrosion Rate of Copper-Nickel Alloy CA 715
in Alkaline Solutions Containing Sulfur Compounds
Corrosion
Duration, Rate,
Conditions of Exposure days mils per year
1. In open tank used to boil 1822 per cent
NaGH to release mercaptans at 80 C (175 fl 30
2. In reboiler of caustic stripper, 12 per cent
NaDH.3 per cent Na,S. 10 per cent sodium
phenolate + 0.7 mg per liter as sodium
25
mercaptides at 124 C (255 Fl 131
3. In 10 per cent sodium sulfide in storage
tank at atmospheric temperature 81
4. In 60 per cent sodium sulfide in flaker
14 feed tank at 171 C (340 f) 28
5. In regenerator reboiler for steam stripping
of mercaptans from solutizer solution
25.2 per cent potassium hydroxide
37.8 per cent potassium isobutyrate
5.5 per cent potassium sulfide
1.9 per cent potassium mercaptides
2.1 per cent potassium carbonate
at 141 C (286 f) 140 15
6. In vapors from solution in item 5 140 12
Pitting up to 3 mils depth.
12
(.
E. IronNickelChromium Alloys
Based upon data obtained in several test expo-
sures and shown in Tables Xln and XL, it appears
that INCOLOY alloy 800 approaches INCONEL alloy
600 in resistance to caustic soda. However, Alloy
800 is more susceptible to stress-corrosion crack-
ing than Alloy 600, as shown in Table XIV.
There has not been sufficient experimental
work on the stre.ss-corrosion cracking of Alloy
800 to determine if stress-relieving in a tempera-
ture range which will cause sensitization (pre-
cipitation of chromium carbides in a continuous
network) renders the alloy more susceptible to
this form of attack. Therefore, it would appear
prudent to anneal the alloy in the range of 1120 to
1150 C (2050 to 2100 F) or stress-relieve and sta-
bilize at 870 C (1600 F) for one to two hours when
it is to be used in higher strength caustic soda
at elevated temperatures.
Table XIV
Laboratory Tests-Results of U-Bend
Specimens in 90% Caustic Soda at 300 C (572 F)
Maximum Depth of Cracks, mils
Argon 15 psig 50 psig 150 psig
atm. air air air
Material 1 week 1 week 8 weeks 1 week
INeOLOY alloy 800 10 7 120lal 1151bl
INCONEL alloy 600 0 0 75 115
Type 304
Stainless Steel 100 110 11 10
(a) Removed at four weeks.
(b) Twoweek test.
Note: Testing performed in autoclaves under static conditions without
replenishment of air or argon.
Table XIII
Plant Tests-Corrosion Rates in Caustic Production Equipment Using Electrolytic Diaphragm Cell Caustic
Exposure times vary from 24 to 29 days
Conditions
NaOH NaGI
Temperature
Concen- Concen
Av Max Min
tration, tration,
% %
G F G F C
10 12 88 190 91 195 82
23 J.8 93 200 104 220 82
35-40 67 116 240 127 102
50 1015 93 200 104 220 71
72 ? 121 250 124 255 119
F. Austenitic Chromium-Nickel
Stainless Steels
F
180
180
215
160
245
Austenitic chromium-nickel stainless steels offer
good corrosion resistance to boiling caustic soda
solutions up to about 10 per cent concentration,
but from 10 to 50 per cent, the temperature for
satisfactory service probably would not exceed
93 to 100 C (200 to 212 F). Generally more severe
but inconsistent corrosion rates occur in more
'"
'"

'"
'"
'"

=
=

M

'"

:'a;
:Sa:;
.,.

"

"
.e.e

'"
'"
" '"
<n<n <n<n <n<n
,.
'"
'"
.,. .,. .,.
] c
0
N

W
'" '" '"

1':
0; w
Z M M M
.;;;
t;
0
z
0

'"
"
"

0
"

Z

"'

z
<0.1 <0.1 <0.1 <0.1 0.2 <0.1 0.2 0.2 5 4
0.2 0.1 0.3 0.1 0.4 2 0.4 1 9 2
0.6 0.4 1 0.5 1 2 0.9 3 46 49
<0.1 <0.1 0.2 <0.1 0.2 0.2 0.4 0.4 5 6
13
0.1 <0.1 OJ <0.1 4 3 0.3 5 4 16
concentrated solutions and at higher tempera-
tures. An isocorrosion chart (Figure 8) sum-
marizes the corrosion behavior of austenitic
stainless steels in caustic soda.
Typical corrosion rates for several stainless
steels are shown in Tables XV and XL. Type 316
stainless steel does not appear to offer any ap-
preciable improvement in corrosion resistance
over Type 304 stainless steel in caustic soda solu-
tions.
700 .-----r-------,-----r----r------.-. 3 It
600
500
'-'-. 400

"
Q.
E

200
100
.
\ .1\ I
C'OC';"1 Bou"cio,y
\ Bo;';n9 P;i",
\ 0' 30moy
\.
,
f to ' .......
50 mpy
.-: 1 ::npv
AU Grades
lib
2&0
Q)
19
17 S
OL-____
o 20 &0 ,,-' 100
fig. 8 - Isocorrosion chart for austenitic chromium nickel
'stainless steels in sodium hydroxide,
J. M. Stone observed that Type 304 stainless
steel sensitized for one hour at 677 C (1250 F)
was not susceptible to intergranular corrosion
during 40-week exposures in: 1:!0
1. 10% NaOH at room temperature
2. 10% NaOH boiling at about 102 C (216 F)
3. 50% NaOH at room temperature. and
4. 50% NaOH at 60 C (140 F).
Therefore. post-weld heat treatment of regular
(0.08 max) carbon grades or the selection of a
low-carbon or stabilized grade of stainless steel
does not appeal' to be required for these exposure
conditions. However, intergranular corrosion of
sensitized Type 304 stainless steel was observed
by Agrawal and Staehle in boiling solutions of
20 to 80('; NaOH.I:t
Chromium-nickel stainless steels are subject
to stress-corrosion cracking in caustic soda solu-
tions at elevated temperatures. Nathorst
H
re-
ported several cases of stress-corrosion cracking
of austenitic stainless i3teels caused by alkalies.
A comparison of the cracking behavior of Type
304 and Alloys 600 and 800 is given in Table XIV.
A stress-corrosion cracking zone based upon these
and other known failures reported in the litera-
ture is shown in Figure 8. A dashed line was used
to indicate the temperature-concentration bound-
ary because this zone is probably not completely
defined. Agrawal and Staehle have shown that
sensitized Type 304 stainless steel is more prone
than annealed material to stress-corrosion crack-
ing in boiling caustic sodaP A portion of their
data is shown in Figure 9. The cracking obtained
was predominantly intergranular in the sensi-
tized material and predominantly transgranular
in the annealed material.
Commercial standard grade 50r;. caustic soda
from diaphragm cells can have up to 11.000 ppm
chlorides. and commercial 50
c
; caustic soda from
mercury cells and reagent grade anhydrous caus-
tic can have up to 50 ppm chlorides. It has been
Table XV
Corrosion of Stainless Steels by Caustic Soda Solutions
HaOH
Concel!-
Temperature
Test Corrosion
AISI tration. Duration. Rate.
Type % C F days mils per year Comments
302 20 5060 122140 134 <0.1 storage tank
309 20 50-60 122140 134 <0.1 storage tank
310 20 50-60 122140 134 <0.1 storage tank
304 22 50..60 122140 133 <0.1 storage tank
309 34 65 149 37 <0.1 storage tank
310 34 65 149 37 <0.1 ;Iorage tank
309 50 21 70 134 <001 storage tank
3to 50 21 70 134 <0.1 storage tank
202 50 5065 122149 167 0.5 storage tank
304 50 50..65 122149 167 <01 storage tank
14
10'
L

'"
.}
j
10
So;\;"9
lcood JOO
e
"_ Y e':i >'tres,"
,O','="O----::l:?O=----=li:-O--.. -'=0---SOL----/,L.O---L70---180
Fig. 9 - Stresscorrosion cracking of annealed and sensi
tized Type 304 stainless steel in caustic soda solutions.
l3
suggested that unreported chloride impurities
are responsible for some of the stress-corrosion
cracking. I;; Whether the reported cracking was
caused by caustic solutions or the chlorides these
solutions contain is an academic point. In any
case. consideration should be given to the tem-
perature and stress limitations of austenitic
stainless steel in caustic soda solutions.
Autoclave tests have been run on some of the
cast stainless steels at temperatures both above
and below the boiling point. II; Data for ACI alloy
CF-8 from these tests are shown in Table XVI.
Table XVI
Corrosion of Cast ACI AUoy CF8
in Caustic Soda at High Temperature
HaOH
Concentration,
%
20
40
60
80
Temperature
C f
119 245
138 280
185 365
119 245
138 280
185 365
219 425
119 245
138 280
185 365
219 425
119 245
138 280
185 365
Corrosion Rate Range,
mils per year
05
2050
20-50
05
20-50
50-200
>200
5-20
50-200
50-200
>200
0-5
5-20
2050
15
Fig. 10 - Piping and certain internal parts of these two
KAMYR digesters used in the pulp and paper industry are
Type 316L stainless steel to resist caustic soda and sodium
sulfide. Insulation sheathing is Type 304 stainless steel to
resist alkaline spills.
See inside back cove<for registered trademarks_
The authors reported that the results for ACI
CF -8M were similar. Alloys CF -8 (cast equivalent
of wrought Type 304) and CF-8M (cast equiva-
lent of wrought Type 316) both exhibited increas-
ing corrosion rates with increasing temperature.
G. Iron-Base Nickel-Chromium-
Copper-Molybdenum Alloys
and
Nickel-Base Chromium-Copper-
Molybdenum Alloys
The limited corrosion test data for wrought alloys
such as CARPENTER 20Cb-3. INCOLOY alloy 825.
HASTELLOY alloy G, and cast ACI CN-7M composi-
tions in caustic soda solutions. shown in Tables
III, XVII and XL, indicate appreciable corrosion
resistance. These alloys fall between the austenitic
chromium-nickel stainless steels su!:h as Type 304
or cast ACI CF-8 and the nickel-chromium alloys
such as Alloy 600 in resistance to caustic soda
solutions. They are markedly superior to Type
304 stainless steel and ACf CF-8 in concentrated
solutions above 95 C (205 F)_
At least one plant has used WORTHITE stainless
steel pumps for handling 73('; caustic soda at
140 C (284 F).I' However, the same reference
also cites high corrosion rates for alloys of less
than 70'; nickel, which would include WORTHITE
stainless steel, in a storage tank handling 73'";
caustic soda at temperatures ranging from 120 to
171 C (248 to 340 F). Thus, the 140 C (284 F) ap-
plication may be at the upper limit of usefulness
for this aHoy.
if these alloys are to be used in conjunction
with nickel and high nickel alloy equipment in
strong caustic soda solutions at elevated tempera-
tures, consideration should be given to electrical
insulation between the dissimilar alloys so as to
prevent harmful galvanic effects.
H. Nickel-Base Molybdenum or
Molybdenum-Chromium-Iron Alloys
Materials such as HASTELLOY alloys Band C-276.
INCONEL alloy 625 and cast CHLORIMET alloys 2
and 3 have not been used to any great extent in
caustic soda solutions. Ag a result. corrosion data
for them are rather Tables IV and XVIII
show the results of some iabonltory corrOfiion
tests. From these data. it is evident that HASTEL-
LOY alloy B can be in concentrations up to 50
per cent at the boiling point and that the tempera-
ture limit for HASTELLOY alloy C-276 would be
somewhat less than with Alloy B. Temperature
limitations in caustic soda concentrations
Table XVIII
Corrosion of HASTEllOY Alloys Band C
in Caustic Soda Solutions 18
NaOH
Temperature Corrosion Rate. mils per year
Concen-
tration. HASTEllOY HASTELlOY
% C F alloy B aUoyC
5 Room Room Nil Nil
5 66 150 Nil Nil
5 102 215 Nil Nil
to Room Room Nil Nil
10 103 217 <2 220
10 121 250 220
20 107 225 <2 220
25 Room Room Nil Nil
25 66 150 Nil Nil
30 166 240 <2 220
40 128 261 <2 2-20
50 66 150 Nil Nil
50 144 291 <2 220
50 400 750 152
60 165 328 220 220
70 191 375 220 2-20
Note: I) N.t means no measurable corrosion was observed in five
24hour test periods.
2) 2-20 means corrosion (ate was within this range.
than 50 per cent C.lllnot be determined with the
exi::;ting data. HASTELLOY alloy C and INCONEL
alloy 625 were both found to be subject to stre::;s-
corrosion cracking in seven-day tests in aerated
90'; NaOH at 300 C (572 F). but did not crack if
was Sub5tituted for the air in tests at the
Paul D. Merica Laboratory of The Inter-
national Xickel Company. Inc.
Table XVII
HaOH
toncel}-
tration.
%
10
10
13
74
Iron Base Nickel-Chromium-Copper-Molybdenum Alloys
and
Nickel Base ChromiumCopper-Molybdenum Alloys
in Caustic Soda Solutions
Temperature
C F
24 75
66 150
95100 203212
130 265
Test
Period.
days
111
II trips
of 79 days
16
Comments
laboratory test.
INCOLOY alloy 825
laboratory test.
INCOlOY alloy 825
Test tank simulating
action of lank car.
WORTHITE stainless steet
rest iOl tank car.
CARP[NHR alloy 20
Corrosion
Rate.
mils per year
<0.1
<0.1
0.2
0.30.9
I. Cast Irons and Ni-Resists
The beneficial etred of nickel additions 011 the
corro:,ioll t'esistance of cast irons in moderately
concentrated caustic alkali is shown by data in
Tables XIX, XX Hnd XX I. It is evident that nickel
contents of 20 to 30 per cent pro\'ide vet'y marked
improvement in resistance to corrosion as com-
pared 'with unalloyed cast iron. It is also apparent
that as lo'w as 3 to 5
c
; nickel may improve the
corrosion resistance of cast iron in some con-
centration ranges,
Table XIX
Effect of Nickel Additions on Corrosion Rates
of Cast Irons in 50 to 65% Caustic Soda
Temperature: Boiling under 26 in. (mercury) vacuum.
Duration: 81 days.
Nickel, %
o
o
o
3.5
5
15
20
20 (plus 2% Chromiuml
30
Corrosion Rate,
mils per year
73
91
86
47
49
30
3.3
S.O
0.4
In practice. the nickel cast irons most widely
used with caustic solutions, where minimum con-
tamination of the caustic is desired. are the Ni-
Resist alloys and their spheroidHl graphite coun-
terparts. the ductile Ni-Resist alloys, The corro-
sion rates of these alloys fora number of different
exposures are shown in Table XXII.
Table XX
Corrosion of Nickel Cast Irons in the
Evaporation of Caustic Soda from 37 to 50 Per Cent
Average Temperature: 120 C (248 F).
Duration: 51 days.
Corrosion
Nickel, Chromium, Copper, Silicon. Carbon. Rate.
% % % % % mils per year
28.60 1.71 1.30 2.87 17
28.37 1.50 2.72 18
14.26 2.39 6.08 1.62 3.15 22
19.40 1.42 3.15 24
19.02 2.90 1.22 3.18 28
20.53 1.25 2.91 31
17
Fig. 11 - Moiten sodium hydroxide at an initial tempera
ture of 370 C (700 F) is converted to flake caustic by this
flaker and breaker. All surfaces exposed to caustic are nickel
except for l'li'Resist Type 3 cooling drum.
Table XXI
Plant Corrosion Test in 74%
Caustic Soda in Storage Tank
Specimens exposed for total of 32 days (20 days in liquid
and 12 days in vapor).
Corrosion rates based on 20 days exposure to liquid.
Temperature:. 125 C (260 n.
Material
MONEl. alloy 400
H.i-Resist Type 3
HiResist Ductile rron Type 02
Hi-Resist TYlIe 2
Type 304 Stainless Steel
Mild Steel
Cast Iron
Corrosion Rate,
mils per year
0.9
2.5
5
6
15
75
76
Copper-free Ni-Resist Type 2 may be used in
preference to Xi-Resist Type 1 (6.50:-; copper)
where it is desired to keep copper content of the
solution at a minimum, The 30
r
;. nickel cast iron
(Ni-Resist Type 3), in addition to having some-
what g-rcater resistance to corrosion by hot caus-
tic solutions than Ni-Resist TypeS 1 and 2, has a
low coefticient of expansion, an advantage for
expOSUI"C conditions invo!\'ing sudden changes in
temperature.
Of the fi\'e basic types of Type 3 ap-
pear:' to be the best suited to meet the require-
ments for caustic sen"ice. !'\i-l1e::;ist Type 3 or
Type D3 can be con::;idered as alternate materials
to nickel and the high nickel alloys for caustic
soda concentrations up to 73 per cent, but nickel
is preferred for higher concentrations.
There have been occasional stress-corrosion
cracking failures with the Ni-Resists in high-
chloride aqueous environments. Although these
environments did not include caustic soda, it
\\"ollld appear a reasonable precaution to stress-
reliew these alloys at 677 C (1250 F) for one
hour before use in hot caustic soda solutions.
Table XXII
Corrosion Rates of the Ni-Resists in Caustic Soda
Corrosion Rate. mils per year
NaOH
'" '" '" '"
c

C>
Concen-
Temperature
Test

";:;fN "Vi v
tration, Period,
"'", "'", "'", "'", .- '"
'70.. '70.. '70.. '70..
'" % C F Aeration Agitation days - >-
.- >. .- >. .- >. =:Ii ..!. >..
'"
x>- X..- 201- XI- c2O>- c..>
8.5-9 82 180 None due to 32 plus 1515.5% 2.5 0.8 1.5 15
filling tank NaCI in storage
tank
10 88 190 Moderate due to 279 plus 12');' NaCl
0.2 4
filling tank in storage tank
I
!
14 88 190 None due loevap. 90 lirst eHect of
i
8
multiple effect !
evaporator
I
23 93 200 Moderate Medium 48 plus 7-8% NaCI 1.2 21
in salt settler
30 85 185 Moderate Moderate 82 plus heavy con- 0.8 0.4 0.1 0.5 6
centratlOn of
suspended NaG!
in sail settler
35-45 116 240 Moderate Small 24 plus 6-7% NaGI 3.3 49
in salt settler.
Intermittent ex-
I
posure to vapor
49-51 55 149 None due to 30 storage tank
I
II
filling tank
50 55 131 Moderate 1.8 Ips 173 plus heavy con- 0.5 0.2 I <0.1 0.2 1.2
cen,ration of
,
I
I
suspended NaC!
I
in transfer line
I I
50 71-104 160-220 Moderate 1 Ips llS plus 1015% NaG! OA 6
in cooling tank
50 95 203 Moderate 1.8 Ips 67 plus heavy con- 1.0 0.6 0.4 11
cent ration of
suspended NaGl
in transfer line
50 21-127 70-260 None None 10 days
@250F
laboratory test 4.7 5.0
& 4 days
@70r
50-65 Boiling None due to evap. 81 30 3.3 OA 86
50-70 121 250 None due to evap. 10 in evaporator
90 290
72 121 250 Moderate very small 1]9 star age lank 4.7 15
74 127 260 Above & Slight 20 specImens
6 2.5 5.5
Below
exposed in storage
liquid
lank for 32 days
level
(20 days in liquid
and 12 days in vaporl.
Corrosion
rales based on 20 days
I None
exposure in liquid
!60
100 510 950
Moderate 14 concentratIOn in 70 87 534 60 141
open pot
18
PART III. CORROSION BY OTHER ALKALIES
A. Caustic Potash (KOH)
Caustic potash is produced by the electrolysis
of muriate (potassium chloride) brine. Several
types and concentrations of KOH are available,
but 45 and 50 per cent liquid and 85 and 90 per
cent solid are most commonly marketed. Above
about 50 per cent concentration, caustic potash
has a higher boiling point than caustic soda of
the same concentration. This differential is espe-
cially pronounced at high concentrations. For
this reason. the commercial product is usually not
concentrated above 90 per cent because of the
high temperatures involved.
In general. those materials which are useful in
caustic soda are also suitable for caustic potash.
Nickel 200 and INCONEL aHoy 600 are both suit-
able for service in hot caustic potash. as indicated
by the data presented in Table XXIII. Negligible
data exist for other nickel alloys in caustic potash.
Gegner has suggested that because caustic potash
is so similar to caustic soda. the corrosion data in
caustic soda of similar concentration and tem-
perature can be used to approximate corrosion
resistance in caustic potash. Iff
Under extreme conditions, some nickel alloys
are subject to stress-corrosion cracking in caustic
potash solutions. However, the information pre-
sented in Tables IX and X suggests that stress
corrosion cracking of Alloy 600, Alloy 400 and
Alloy K-500 is not quite as severe with caustic
potash as with caustic soda.
The beneficial effect of nickel in cast iron ex-
posed to caustic potash is shown in Table XXIV.
The reductions in corrosion rates are similar to
those obtained in caustic soda solutions.
Table XXV shows the results of laboratory cor-
rosion tests of several Ni-Resist alloys in hot. con-
centrated caustic potash. Lower corrosion rates
would be expected with a decrease in either tem-
perature or caustic potash concentration. Ni-
Resist Type 3 appears to have equivalent, and
sometimes superior. corrosion resistance in com-
parigon to Types 1 and 2.
Table XXIII
KO"
COllcen-
tration.
%
13
30
47
50
50
50
10
10
Temperature
C F
30 85
113 236
139 281
28 82
150 300
.
150 300
150 300
150 300
Aeration
None
None
None
None
None
None
None
None
Corrosion Tests in Caustic Potash Solutions
Agitation
due to
filling tank
Boiling
Boiling
due to
lilting lank
2\.61pm
3481pm'
21.6fpm
3481pm"
Test
Period.
days
207
26
26
207
7
35
7
35
Comments
storage tank impurities-
K Jeo J 3 gpl. KCf 170 gpl.
KClO .. 0.1%
laboratory test-saturated
with KCf. 0.05% KClO,
laboratory test-saturated
with KG\. 0.18% KClO,
storage tank impurilies-
K,CO. 0.3%. KGI 0.75%.
KGto, 0.10%
laboratory test-UBend
specimen showed
no cracking
laboratory test
laboratory test
laboratory test
nil-less than 0.05 mils pel'" year. l-liQuid V-Vapor
." Specimens m ~ v e at th!s veloc11y fof'" 8 hr each working day and at zero ft per mtn overn1ght and duong
weekends. Th,s was equlvatent to ten 24 hour days at the high velocity rate.
19
Nickel
200
nil'
l. 0.2
V.0.3
l. 0.1
V.O.3
nil
nil
nil
0.4
1.6
INCONEl.
alloy
600
nil
l. 0.1
V.O.1
l. 0.4
V.O.1
nil
0.5
0.5
0.7
5.7
MONEl.
aUoy
400
nil
nil
Table XX'V
Effect of Nickel in Cast Iron
on Corrosion by Caustic Potash
Concentration: 950 g KOH per liter.
Temperature: 400 C (750 F).
Nickel Content of Alloy Iron,
%
o
3
6.5
12.4
Table XXV
Corrosion Rate,
mils per year
21-30
3.0
2.0
0.4
Corrosion of Ni-Resists in Caustic Potash
Hi-Resist ClIrrosjon Rate,
Type Exposure mils per year
1 68-hour test in 81 % KOlt at 225 C (437 f) 30
2 68-hour test in 81% KOH at 225 C (437 f) 20
3 68-hour test in 81 % KOH at 225 C (437 f) 10
2 36-hour test in 92% KOlt at 268 C 1516 f) 10
3 3S-hour test in 92% KOlt at 268 C (516 f) 10
B. Ammonia and
Ammonium Hydroxide
Most of the nickel-base alloys, with the exception
of the nickel-copper alloys and nickel itself, resist
all concentrations of ammonium hydroxide up to
the boiling point.
Among the nickel-containing alloys, the aus-
tenitic stainless steels are most frequently em-
ployed in ammonia and ammonium hydroxide
solutions. Austenitic stainless steels exhibit good
resistance to all concentrations of ammonia and
ammonium hydroxide up to the boiling point.
Tables XXVI through XXIX show the results of
plant corrosion tests in ammonia- and ammonium
hydroxide-containing process streams.
Stone .determined that Type 304 stainless steel,
which had been sensitized at 677 C (1250 F) for
one hour, was not subject to intergranular corro-
sion during a 40-week exposure in 28% NH4 0H
at room temperature.
12
However, this resistance
does not extend to elevated temperatures in com-
mercial solutions, as shown in Table XXVI.
20
Considerable amounts of Types 316 and 316L
stainless steels are used in the ammonia-soda
process for the production of soda ash (Na2C03 ).
The main reaction involves the carbonation of an
ammoniated brine to form sodium bicarbonate
and ammonium chloride. The ammonia is recov-
Table XXVI
Plant Corrosion Test in Ammonia
Surge Vessel of Urea Manufacturing Plant
Solution: 22% NH, 71 % H,O, 7% CO, and trace of
NH.NO, .
Temperature: 66C (150 F).
Test Period: 300 days.
Aeration: None.
Agitation: Moderate.
Location: Uquid phase at bottom of aqua ammonia surge
vessel.
Material
INCOlOY alloy 825
Type 304 Stainless Steet
Type 316 Stainless Steel <Sensitized)
CARPENTER alloy 20
INCONEL alloy 600
Type 304 Stainless SteellSensitized)
Mild Steel
Table XXVII
Corrosion Rate,
mUs per year
<0.1
<0.1
<0.1
0.3
0.3
0.4
3.4
7.6
Missing-presumed
corroded away
Missing-presumed
corroded away
Plant Corrosion Test in Mixed Ammonia-Carbon
Dioxide Gas Stream in a Chemical Plant
Gas: Mixture of NHJ and CO2 with probably some moisture
present.
Temperature: 20 to SOC (68 to 176 F).
Aeration: None.
Agitation: Gas flow.
Location: Suspended in gas stream.
Material
MONEL alloy 400
tNCONEL alloy 600
Mild Steel
Nickel 200
Silicon Bronze
Nil == Less than 0.01 mill><" year.
Corrosion Rate,
mils per year
Nil
Nil
2.2
3.0
5.1
5.3
72
Table XXVIII
Plant Corrosion Test in Ammonia-Carbon
Dioxide Gas Stream in a Metal Refining Plant
Gas: 26% NHJ 14% CO,. balance water vapor.
Temperatur-e: 66 ro 93 C (150 to 200 F); Average 82 C
(l80 F).
Aeration: Moderate.
Agitation; 25 to 40 fps gas flow.
Location: H C O ~ stripping still overhead line.
Material
INCOlOY alloy 825
INCOLOY alloy 800
INCONEl alloy 600
Mild Steet
Table XXIX
Corrosion Rate.
mils per year
<0.1
<0.1
<0.1
<0.1
1.5
4.1
0.1
20
22
Plant Corrosion Test in Contaminated
Ammonia Vapors in a Coke By-Products Plant
Gas: Ammonia vapors plus H,S. CO,. HCN. phenols and
steam.
Temperature: 100 to 110 C (212 to 230 F); Average 105 C
(221 F).
Aeration: None.
Agitation: High velocity gas flow.
location: Ammonia liquor still vapor outlet.
Material
I NCONEl alloy 600
Mild Steel
MONEL alloy 400
Nickel 200
Nil "" 1.ess tban 0.04 mils per year.
Corrosion Rate,
mils per year
KiI-
Nil'
0.1
S.O
>40
(corroded away)
>40
(corroded away)
ered in this process for reuse. Table XXX shows
corrosion rates for metals and alloys in an am-
monia recovery still in a soda ash plant. The pos-
sibility of pitting must be taken into account in
the design of equipment where there are such
high chloride levels, so as to avoid crevices where
chlorides can concentrate to even higher levels
and promote crevice corrosion.
21
Table XXX
Plant Corrosion Test in Ammonia Recovery Still,
Ammonia-Soda Process for Production
of Sodium Carbonate
Middle Section
Temperature: 60 to 71 C (140 to 160 F).
Liquor Composition: 2% NHl , 9% NH.CI,
14% NaCl, 2% CO2
Top Section
Liquor Composition: 5% NHl 9% NH.CI,
14% NaCl, 3.4% CO2
Middle lop
Material Section Section
Type 316 Stainless Steel OJ 0.1
Zirconium 0.1 0.1
Titanium 0.1 0.2
HASTEllOY alloy C 0.1 14'
Nickel 200 >33" >32"
Mild Steet >73" >71"
Specimen pitted in crevice beneath insulating wasber.
Specimens cQrroded away ..
Nickel is not attacked by anhydrous ammonia,
but is resistant to ammonium hydroxide solutions
in concentrations only up to about one per cent.
Aeration may induce passivity in concentrations
under 10 per cent, but even in the presence of air,
more concentrated solutions are highly corrosive
to nickel. The corrosion data shown in Table XXXI
were obtained in room-temperature laboratory
tests ()f 48-hour duration in one normal ammo-
nium hydroxide, following a previous 48-hour ex-
Table XXXI
Corrosionof Nickel 200 in One Normal
Ammonium Hydroxide (1.7% NHa)
Test Condition
Total Immersion
Quiet
Air"'Agitated
Alternate Immersion
Conti!luous
lntermittent
Spray {4 to 30 Daysl
Corrosion Rate,
milspllryear
0.8
<0.1
2.7
0.4
<0.1
Specimens exposed at room temperature tor 2 days after a previous
2-day exposure except for spray expo'Sure.
posure. The of 20-hour tests in highly
agitated ammonium hydroxide solutions at room
tempelature are shown in Table XXXII. Typical
corrosion rates for Nickel 200 in several indus-
trial exposures are also given in Table3 XXVII,
XXIX and XXX.
Table XXXU
Corrosion of Nickel 200 in
Ammonium Hydroxide Solutions
NH.OH Cancentration,
%
1.1
12.9
20.2
27.1
CCIfI"lISion Rate,
mils per year
o
560
370
180
Tests run to agitated solution at room temperature for 20 hours.
Nickel-copper alloys. such as Alloy 400, are re-
sistant to anhydrous ammonia and are slightly
more resistant than commercially pure nickel in
ammonium hydroxide solutions. as shown in Table
XXXIII. However, their usefulness is restricted
to dilute solutions up to about 3<1 ammonium
hydroxide. In solutions of higher concentration.
corrosion rates are increased considerably by
aeration and agitation.
TableXXXm
laboratory Corrosion Tests of
MONEL alloy 400 in Ammonium Hydroxide
Temperature: Room. Test Period: 20 hours.
Agitation: 371 feet per minute.
HH3 Cancentration,
%
2.7
3.6
5.5
8.2
11.1
18.3
25.8
Carrosian Rate,
mils per year
o
70
298
317
327
231
36
C. Other Alkaline Solutions of
Sodium and Potassium Salts
Salts as sodium sulfide. sodium carbonate,
sodium silicates, trisodium phosphate and others
form alkaline water solutions. These alkaline
22
Fig. 12 - Sodium carbonate filters use Type 304 stainless
steel or MONEL alloy 400 for the perforated backing sheet or
winding wire. The same materials are also used for back
ing wire cloth and facing cloth .
salt solutions can be handled in the same materials
suitable for caustic soda. As with caustic soda,
dilute solutions at low temperature are not very
corrosive to carbon steel and may even act as cor-
rosion inhibitors, but concentrated solutions at
high temperatures often require nickel or high
nickel alloys.
The results of tests within an evaporator han-
dling sodium metasilicate are shown in Table
XXXIV.
Another plant test in a kettle during the dis-
solving of silicates in strong caustic soda gave the
corrosion rates shown in Table XXXV.
The superiority of Alloy 400 and austenitic
stainless steels for a phosphate hydration was
demonstrated in a short-duration test shown in
Table XXXVI.
Nickel and high nickel alloys offer good resist-
ance to corrosion by sodium sulfide solutions. In
Table XXXIV
Corrosion Tests in Sodium Metasilicate
Composition: 50% sodium silicate. 50% sodium hydroxide.
Temperature: HOC (230 F). Test Period: 6 weeks.
Material
Nickel 200
MONEL alloy 400
INCONEL alloy 600
Hi-Resist Type 1
Mild Steel
Cast Iron
Corrosion Rate.
mils per year
<0.1
<0.1
<0.1
0.4
13
18
Table XXXV
Corrosion T e.sts During Dissolving of
Silicates in Caustic Soda
Location: Test specimens suspended near bottom of kettle.
Temperature: 77 C (170 f). Test Period; 32 days.
Material
Nickel 200
Ni:Resist Type 3
Ni:Resist Type 2
Nickel Cast Iron (3% Ni)
Cast Iron
Mild Steel
Table XXXVI
COffoswn Rate,
mils per year
0.1
0.2
0.5
8
33
41
Conosion Tests in Phosphate Hydrator
Composition: 50% solution of sodit.t1l1 tripolyphosphate and
sodit.tm tetrapotyphosphate.
Average Temperature: 74 C (165 F}. Test Period: 60 hours.
Aeration: Extensive. Agitation: Considerable.
Material
MONEt. alloy 400
Mild Steel
Corroswn Rate,
mils pet year
0.1
0:4
0.7
133
10:t sodium sulfide. the corrosion rates are quite
Jow. as shown in Table XXXVII. The most severe
service conditions are encountered in hot. concen-
trated solutions. The results of two plant corro-
sion tests in direct-fired evaporators which con-
Table XXXVII
Plant Corrosion Test in a
Sodium Sulfide Storage Tank
Solution: 10% Na2S. Aeration: Open tank.
Temperature: Atmospheric. Agitation: Only due to filling tank.
Matl!rial
. Nickel lO!l
MQNEL alloy 400
tNCONEL alloy 600
KASrELLOY all.oy B
HAsrULOY atloy C
ILLlUM G
DURIMEr 20
Copper-Nickel alloy CA 715
Corrosiolt Rate.
mils per year
<OJ
<OJ
<OJ
<0.1
<OJ
<0.1
<0.1
<fU
<0.1
1.3
centrate sodium sulfide from 25 to 60 per cent
are given in Tables XXXVIU and XXXIX. Oper-
ating experience over a number of years with
evaporator tubes in sodium sulfide evaporation
has shown that Nickel 200 and Alloy 400 are
satisfactory for this application.
23
Experience has also demonstrated that Alloy
600 is useful .for direct-tired pans in which sodium
sulfide is eoncentrated from 25 per eent to 60 per
cent. Operating temperatures on the order of 150
to 177 C (300 to 350 F) prevaiL Under sueh condi-
tions. Alloy 600 has given a service life of up to
eight years.
Table XXXVIlI
Plant Corrosion Test in DirectFired Open Pot Used
for Concentrating Sodium Sulfide to 60 Per Cent
Temperature: 100 to 180C (212 to 356 f).
Material
MONEL altoy 400
fMCOJltEl.. alloy 600
Nickel 200
Copper-Nickel alloy CA 715
HASTELLOY alloy B
ILLiUM G
KASrELLOY alloy C
DURIMEr alloy 20
Specimens corroded away.
Table XXXIX
Corrosion Rate.
mils per year
8
10
16
20
22
48
>72*
>73*
>85*
110
Plant Corrosion Test in Gas-fired
Open Tray Used for Concentrating
Sodium Sulfide from 25 to 60 Per Cent
Temperature: 125to 175C (257 to 347 f).
Material
MONEL alloy 400
Nickel 200
INcoNELa1loy 600
Type 3D2 Stainless Steel
Mild Steel
Spedmens corroded away.
Corroswn Rate.
mils per year
3
7
8
11
22
84
230
>290*
>300'
>600*
PART IV. INDUSTRIAL APPLICATIONS
A. Caustic Soda Manufacture
Service records, often dating back for 20 to 30
years, have demonstrated the satisfactory service
of nickel and nickel alloys in caustic soda manu-
facture. In one plant, nickel centrifugal pumps
handling 50% caustic soda from mercury cells are
27 years old and are still in operation. In another
plant, nickel evaporators continue to give good
service after 30 years' use. Nickel 200, low-car-
bon Nickel 201, Alloy 600, Alloy 400 and their
cast counterparts are "standard" materials of
construction, either solid or as a cladding for
equipment such as evaporators, heat exchanger
tubing, pumps, crystallizers, valves, fittings, etc.,
used in the concentration and handling of caustic
soda. Corrosion test data cited earlier in this bul-
letin were obtained largely in caustic soda manu-
facturing processes.
A comparison of the corrosiveness of caustic
soda produced from mercury cells with that pro-
duced by diaphragm cells was made by Committee
T5A-3D of the National Association of Corrosion
Engineers. Data obtained in this survey are
shown in Table XL. It appears that there is not a
Fig. 13 - Triple-effect evaporators for the concentration of diaphragm cell liquor to 50% caustic soda_ All threeevapora-
tors are constructed entirely of Nickel 200 and Nickel 200-clad steel.
Photograph courtesy of Blaw-Knox Company_
24
Table Xl
"Round Robin" Test Program by Four Caustic Soda Producers-Comparison of
Corrosiveness of Diaphragm Cell vs. Mercury Cell Caustic-
Conducted by NACE Committee TSA-3D
Average Temperature
Company
1 2 3
Material Corredent C f C f C F
Nickel 200 50% NaOH-Oiaphragm Cell 35 95 29 85 88 190
Hickel 200 50% NaaHt>iaphragm Cell 40 104 - - -
-
Hickel 200 50% NaOHMercury Ceil 38 100 105 221 82 180
Nickel 200 50% NaOHMercury Cell 37 98 45 113
- -
Nickel 20:0 50% NaOHMercury Cell - - Ambient - -
Nickel 20:0 73% NaOMHapluagm Cell 119 246 - - 99 210
Nickel 200 73% NaOH-Oiaphragm Cell 125 257 - - - -
Nickel 200 NaOHMercury Cell 114236 - - - -
INCONEL alloy tioo: 50% NaOK-Diaphragm Cell 35 95 29 85 88 190
INCONEL alloy 601} 50% HaOMDiaphragm Cel! 40 104 - - - -
INCONEL alloy 600 50% NaOHMercury Cell 38 100 105 221 82 180
INCONEL alloy 600 NaOHMercury Cell 37 98 45 113
-
-
INCONEl alley 600 NaOH-Mercury Cell
- - Ambient
- -
INCONEL alley 600 73% NaOH-Diaphragm Cell 119 246 - - 99210
INCONEl alloy 6{}0 73% NaOHDiaphragm Cell 125 257 - - - -
INCONEL alley 600: 73% NaOHMercury Cell 114 236 - -
- -
MONEL alloy 400: 50% NaOHOiaphraglll Cen 35 95 29 85 88190
MONR alloy 400 50% Cell 40 104 - - - -
MONEL aliDY 41111 50% NaOH;Mercury Cell 38 100 105 221 82180
MONEL aUoy 400 50% NaOHMercury Cell 37 98 45 113
-
-
MONEL alloy 400 50% NaOH-Mercury Cell
- -
Ambient - -
MONEL alloy 400 73kNaoHOlaphraglll Cell 119246
- -
99 210
MONEL alley 400 73% NaOH-Diaphraglll Cell 125.257. -
,...,...
-
,....
MONEL aUoy 400 13% HIlOaMercury Cell 114236 - - - -
INCOLOY alloy 800 50% NIlOHOiaphragm Cell 35 95 29 85 88 190.
INCOLOY alloy 800 50%: HIlOHtliaphragm Cell 40 104
-
-
- -
INCOLOY alloy 800 50% NaOHMercury Celt 38100 105 221 82180
INCOLOY alloy 800 5{)%NaOH.Mercury Cell 37 98 45 113 -
INCOLOY alloy 800 NaOH.Mercury Cell
- -
Ambient
-
-
IHCOLOY alloy 800 73% NaOIH)iaphragm Cell 119246 -
-
99.210
IHCOLOY alloy 800 73% NaOH-Diaphragm Cell 125251
- - - -
INCOLOY alloy 800 73% NaoNMercury Cell U4.236
- -
-

CARPENfER alloy 20 Cb3 50'!';' NaOHDiaphragm Cell 35 95 29 85 88 190
CARPEtffER alloy 20 Cb-3 50'!" NaOHOiaphragm Cell 40 104
- -
- -
CARPENfER alloy 20 Cb3 50% NaOK-Mercury Cell 38100 105 221 82 1811
CAftPEtffER alloy 20 50% NaOH,Mercury Cell 37 98. 45.113
-

CARPENTER alloy 20 Ch3 50% NaON-Mercury Cell
-
-
Ambient - -
CARPENTER allDY 20 (:b3 73% NaOHOiapllragm Cell U9246
- -
210
CARPENTER alley 20 tb3 73% NaOHOiilplnagm Cell 125 257
- - - -
CARPENTER alllly20 (:b3 73% NaOHMercury Cell H4236
-
- - -
ACI tN-7M 50% NaOHOiaphragm Cell 35 95 29" 85 8'8 190
ACt CN7M 50% NaOHDiaphragm Cell 40 104 - - - -
ACI CtOM 50?{. NaOHMer(;ury Cell 38 100 105 221 82 180
ACl eN7M - 504 NaOHMen:ury Cell 37 98 45 il3 - -
ACt CN-1M 50% NaOHMeJ.eury Cell
- - Ambient - -
ACI CN-1M Cell 119 246 - - 99210
ACI CN-7M NlIOH,OillPhraCm Cell 125 257
-
- - -
ACI CN"7M 13% NaOH.MetClifY Cell 114 236
- - - -
NiRe.sist Type 3 50% NaOHDiapbragm Cell 35 95 29 85 88 190
Ni-Resist Type 3 50% NaOHDiaphragm Cell 40 104 - - -
-
Hi-Resist Type 3 50% NaOHMercury Cell 38 100 105 221 82 180
4
C F
54 130
Ambient
60 140
Ambient
Ambient
-
-
- -
- -
54 130
Ambient
60 140
Ambient
Ambient
-
-
-
-
-
-
54 130
Ambient
60140
Ambient
Ambient
- -
- -
- -
54130
Ambient
60 140
Ambient
Ambienl
- -
- -
-
54 130
Ambient
60 140
Ambient
Ambient
- -
-
-
- -
54130
Ambient
60 140
Ambient
Ambient
- -
- -
-
-'
54 130
Ambient
60 140
1
<0_1
<0.1
<0'\
<0.1
<0.1
0.2
0.3
<0.1 (l)
<0.1
<0J
<O.!
<0.1
0.3
0.2
<0.1
<OJ
<OJ
<O.}
<0.1
0.4
0.5
<OJ
<IU
<0.1
<0.1
OJ
0.5
O.3IU
<0.1
<0.1
<(j.l
<0.1
0.4
0.5
0.4
<0.1
<0.\
<0.1
<0.1
lU
Corrosion Rate.
mils per year
C.Dmpany
2 3
<0.1 <0.1
<0'\ 1.0
<0.1
<0J
0.2
--
<0.1 <0.1
<0.1 <0.1
<0.\
<0.1
0.2
<0.1 <0.1
0.1 0.2
<0J
<0.1
0.8
<0.1 <0.1
l.l <OJ
<0.1
<0.1
4..l (2)
<0.1 <0.1
<OJ <0.1
<OJ
<OJ
1.5(3)
<0.1 <0.1
<0.1 <0.1
<OJ
<0.1
9.3
1.2 (J)
G.4
0.2 <0.1
0.4 (4)
0.6
<0.1 <0.1 <0.1
4
<OJ
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<OJ
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<OJ
<0.1
<OJ
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<OJ
<0.1
<0.1
<0.1
<0.1
0.2
<01
Table XL (Cont'd.)
"Round Robin" Test Program by Four Caustic Soda Producers-Comparison of
Corrosiveness of Diaphragm Cell vs. Mercury Cell Caustic-
Conducted by NACE Committee T5A-3D
Average Tempe,ature
Company
2 3 4
Material Corrodent C f C f C f C f
HiResist Type 3 50% NaOM.Mercury Cell 37 98 45 113 - - Ambient
Ni:Resist Type 3 50% NaOJ1,Mercury Cell
- -
Ambient
- -
Ambient
Ni:Resist Type 3 73% NaOH-Oiaphragm Cell 119 241> - - 99 2W - -
Hi:Resist Type 3 73% NaOM-Diaphragm Cell 125 257
-
- - - - -
Hi:Resist Type 3 73% NaOHMercury Cell 114 236
- - - - - -
Type 3.16 Stainless Steel 50% Cell 35 95 29 85 88 190 54 130
Type 3Ui Stainless Steel 50% Cell 40 104
- - - -
Ambient
Type 316 Stainless Steel 50% NaOHMercury Cell 38 100 105 221 82 180 60 140
Type 316 Stainless Steel 50% NaOHMercuI}' Celt 31 98 45 113
-
- Ambient
Type 316 Stainless .Steet NaOHMercury Cell -
-
Ambient - -
Ambient
Type 316 Stainless Steel 73% Cell 119 246
-
- 99 210 - -
Type 3l6.stainless Steet 13% NaOH-Oiapbragm Cell 125 257 -
- - - - -
Type :116 Stainless Steel 13% NaOH'Mercury Cell 114236 - - - -
-. -
Type 304 Stainless Steel 50% NaOHDiapllragm Cell 35 95 29 85 88190 54 130
Type 304Stainle$$.Sieei 50% NaOlH)iallhragm Cell 40 104 - - - - Ambient
Type Steel 50% NaOn-Mercury Cell 38 100 105 221 82 180 .60 140
Type 304 Stainless Steel 50% NaOHMercury Cell 37 98 45 113
- -
Ambient
1ype304 StaiRtessSteel 50% NaGH.Mercury Cell - -
Ambient
- -
Ambient
Type 304 Stainles$.steel NaOH-Oiapbragm Cell 119246 -
-
99 210 - -
Type 304 Stainless Steel 73% NaOH-Oiaphragm Cell 125 257 - - - - - -
Type 304 Stainless Steel 73% NaOHMercury Cell 114 236
- - - - - -
Ductile Cast Iren 50% NaOllDiaphragm Celt 35 95 29 85 88 190 54130
Ductile Cast Iron 50% NaOli-Diaphragm Cell 40 104
- - - -
Ambient
Ductile Cast Iron 50% NaOHMercury Cell 38 100 105 221 82 180 60 140
Iron 50% NaOliMercury Ce:t 37 98 45113
- -
Ambient
Ductile Cast IllIn 50% NaOJt..Men:l.lry tet!
- -
Ambient
- -
Ambient
D1Ictile Cast Iren 73% Cell 119246
- -
99 210 - -
Ductile Cast illln 73% Celt 125 251
- - - - -
-
Ductile cast Iron 13% NaOH.MercuI)' Celt 114236
- - - -
- -
Gray Cast Iron 50% NaOH-Oiaphragm Cell 35 95 29 85 88 190 54 130
Gray Cast Iroll 50% Na(lli-Diaphragm Cell 40 104
-
-
-
-
Ambi'lnt
Gray Cast Iron 50% NaQli-Mercury Cell 38 100 105 221 82 100 60140
Gray Cast Iron 50% NaOHMercury Cell 31 98 45 113
- -
Ambient
Gray Cast Iron 50% NaOli-Mercury Cell
-
-
Ambient
- -
Ambient
Gray Cast Iron 73% NaOli-Dia.phragm CeU H9246
-
-
99 2It}
- -
Gray Cast Iron 73% NaOn-Diaphragm Cell 125 257
-
- - -
- -
Gray Cast Iron 73% NaOK-MereuI}' Cell 114 236
-
- - -
- -
MildSteeJ 50% HaOH-Oiapbragm Cell 35 95 29 85 88 190 54130
Mild Steel 50% 4D 104 - -
-
- Iynbient
Mild Steel 50% NaOHMercury Cell 38 100 105 221 82 180 60 140
Mild Steel 50% NaOHMercury Cell 37 98 45 113 - - Ambient
Mild Steel
-
50% NaOM-Mercury Cell - - Ambient
-
Ambient
-
Mild Steel 13% NaOHl)iapilragm Cell 119 246 - - 99210 - -
Mild Steel 73% NaOfl..Diapbragm Cell 125 251 - - - - -
-
Mild Steel 73% NaOMMercury Cell 114 236 - - - - - -
(1) Pitted to a maximum dept" Qt 1 mHo
(2) Pitted to a maximum depth of 4 mils.
(3) Pitted t<> a maximum depth of 5 mils.
(4) Stress-corrosion crack through
(5) Pitted to a ma.ximlJm depth Qt 3 mils.
(6) Mercury droplets in tao". 2 rates shown
are for the duplicate speCimens
one of the identifying punch marks.
(not averaged): specimen with high rate
showed stress-acce1erated local attack.
26
1
0.2
0.3
2.3
1.2
<0.1
0.2
<0.1
<0.1
6
(4)
13.1(5)
10
{4}
<0.1
<0.1
<0.1
<0.1
15
(4)
19.4 t5}
15
(4)
1.4
l.5!S)
0.4
1.8
73
106
103
2.1
1.9
0.4
2.1
54
44
82
UJ5}
1.5 (5)
O.SISI
1.4
59
dissolved
>38
71
Corrosion Rate.
mils per year
Company
2 3
0.1
<0.1
8.4
<0.1 3.3
<0.1 0.2
0.1
<0.1
8.7
<0.1 1.1
0.1 n. 61 0.3
11.0
<0.1
<OJ
13 m
3.1 12
0.3 0.6
2 (81
3.7
18
1.9 13
2 t9) 2.6
3
4.5
21
1.4 nO} 20
3 {6.1ID 1.8m
21
2
5.1
5.7
4
0.1
0.2
<0.1
<0.1
<0.1
0.3
<0.1
<0.1
<0.1
<0.1
0.4
<0.1
2.6
52
1.0
6.2(2
2.6
2.9
7.9
1.7
5.1
3.5
2.1
3.2
1.2
2.9(5
1.9
(8) Pitted to a maximum depth of 2 milS.
(10) Pitted to " maximum depth of 11 mils.
great deal of difference in the corrosiveness of the
caustic produced by these two types of cells, al,'ld
that other variables such as temperature and con-
centration are more important in influencing cor-
rosion rates.
Prior to about 1946, the concentration of 50%
or 73 % caustic soda to anhydrous was carried out
entirely in direct-tired caustic pots in a batch
operation. These pots Were usually constructed of
gray cast iron. Nicl<:el could not be used because
of the practice of "sulfur shading" (sulfur addi-
tion for the removal of iron and other contamin-
ants to achieve higher purity and better product
color), which caused severe sulfur embritllement
of the nickel at the high temperatures involved.
Subsequent to 1946, these pots have been
repla<:ed to a very great extent by nicl<:el and
nickel anoy equipment for continuous vacuum
evaporation, which has proven to yield a higher
quality product more economically.3.20 The pro-
duction of anhydrous caustic soda in corrosion-
resistant Nickel 201 and AHoy 600 equipment has
eliminated the necessity of sulfur shading.
fig. 14 --Evaporator bodies and vapor piping at a large
chlorine-caustic soda plant for concentraticn t.o 730/0 NaOH.
All evaporatcrs are constructed entirely .of Nickel 200 and
Nickel 200clad steel.
Chlorates are removed from diaphragm cell
caustic soda when concentrating to anhydrous in
nickel or high nickel alloys to minimize corrosion
rates. Some corrosion test data showing the ef-
fects of chlor;;ltes upon the corrosion of Nickel 200
and INCONEL alloy 600 in high temperature caus-
tic soda are shown in Tables XLI and XLII. There
are several means by which chlorates can be re-
27
Table XU
Plant Corrosion Test During Concentration of
Diaphragm Cell Caustic Soda from
50 Per Cent to Anhydrous
Feed liquor c.ontained 0.24% scdium chl.orate and 1.0%
scdium chloride .on S.olid caustic basis. Rapid circulation
of liqu.or.
Temperature: 400 C (750 fl.
Test Period: 243 hcurs .operaticn.
Material
Hickel 2DD
tHCONEt. anoy 6IJD
liquid Vapor
51.0
87.0
TableXUl
0.5
5.0
laboratory Corrosion Test in Evaporation
of Caustic Soda from 73 tQ 96 Per Cent
with and without Chlorate
Temperature: 180 C (360 F) t.o 450 C (840 F).
lest Pericd: 24 h.ours.
Material
Nickel 2IltJ
IHCOHEt. alloy 6flO
Corrosion Rate, mils pef year
Without Witll fl.3% Clllorate
Chlorate (Solid C;tIIStic Basis)
1.5
2.2
260
380
moved; the addition of sucrose (U. S. Patent
2,610,105) or dextrin (British Patent 778.226)
appear to be the most common. While these ad-
ditions minimize corrosion and attendant metal
contamination of the product,- they do increase
the carbonate concentration. Bradbury and
Cooper have shown that the addition of sorbitol
and subsequent heating will also remove chlo-
rates but with the formation of less carbonate.
21
Liquid-liquid extraction with ammonia is also
widely used to remove chlorates and chlorides.
22
In the continuous vacuum concentration and
production of anhydrous caustic soda, low-carbon
Nickel 201 and Nickel 201-clad steel equipment
have given excellent service as evaporator tubes.
tube sheets and shells, and as receiving tanks and
piping.
Alloy 600 has also been used extensively for
producing anhydrous caustic soda and is the
preferred material of construction where the
heating is accomplished with any media in which
there is a po:.;sibility of sulfur compounds being
present. Alloy 600 for this service should be
stress-relieved or annealed as indicated in the dis-
cussion of nickel-chromium alloys in Part II of
this bulletin.
Fig. 15 - Tubes fabricated from Nickel 200 afe used in the
inclined heat exchanger in front of the Nickel 200-dad
evaporator which prodl.l<.:es 50% caustic soda.
separator atop the system. which separates
sodium chloride and other salts from the caustic solution.
is also Nickel 200.
B.Caustic Potash Manufacture
The production of caustic potash is carried out
in nickel and nickel alloy equipment in a similar
manner t9 the production of caustic soda. One
important difference. however, is the higher
boiling point encountered in caustic potash above
50 per cent concentration. Because of the higher
temperahx ~ involved. cathodic protection is
often used for low-carbon Nickel 201 or high
nickel alloy equipment u:=;ed for the production of
caustic potash at concentratiolls of 90 per cent
and above.
28
C. Caustic Soda Storage and
Transportation
After extreme care has been taken to assure
high purity in the production of caustic. it is
important that storage and transportation facili-
ties provide for continuing product purity. NickeI-
clad steel tank cars have been used for transport-
ing iron-free caustic since 1930. Nickel and nickel-
clad steel barrels are also in use for the transpor-
tation of smaller quantities. More recently. nickel-
plated steel tank cars and piping have been
employed.
The first tank-trailer constructed of INCOLOY
alloy 825 was put in service in 1963 to haul 50%
caustic soda. This alloy was selected because of its
versatility in its ability to transport other corro-
sive materials induding sulfuric. nitric and phos-
phoric acids. INCONEL aHoy 600 was selected for
barge tanks to carry 73 (-; caustic one way and
return with ammonia-base fertilizers or jet fueL
Fig. 16 - Marine terminal where caustic soda is unloaded
from barge. Nickel 200 lined caustic transfer pipe is at right
foreground.
Tt'an;;fer of materia! to and from storage tanks
usually requires pumps. Table XLIII shovv's the
results of a plant test in which Xickel 200, MONEL
alloy 400 and INCONEL alloy 600 corrosion coupons
wet'e subject to turbulent flow just downstream of
a pump handling caustic soda. Similar cor-
rosion resistance would be expected fl'O!1l the cast
counterparts of these wrought materials (ACI
CZ-IOO, M-35 and CY-40). Pumps cast from ACI
CZ-IOOhave given over 25 years service as previ-
ollsly noted.
Table XLIII
field Test in 50% Caustic Soda
Just Downstream of a Pump
Temperature: 60 to 70 C (140 to 158 f);
AI/erage 65 C (149 f).
Aeration: Moderate.
flow; 100 gpm in 3inch pipe.
Material
Nidle1200
alloy 600
MONEL aUoy 400
_ ..
Corrosion Rate.
mils per year
a.OJ
0.03
0.10
fig. 17 This barge carries 50%. caustic soda from a
mercury cell plant to storage facilities'along the Tennessee.
Ohio and Mi Rivers. Four cylindrical tanks have a
total capacit liquid tons. To insure a long sef\lice
life for the ge and to protect product purity. all cargo
piping is either solid Nickel 200 or Nickel 2oo-clad steel with
Nickel 200 fittings: The cargo fromal! four tanks empties
into a Ni,ckeI2oo-clad steel well from which ,it ispl.lmped to
on-shore facilities_' .' . '
The use of nickel;..cla<i steel .tanks offers par-
ticularj\dvantage.<; in the storage and shipment
of caustic soda. To a\'Qid solidification;caus-
tic of. this must be loaded hot and main-
fig. J,8 -:- INCOLOY aUoy 8,25 ,is used for the inner tank and all internal parts that come into contact with corrosil/e cargoes
in these two trailers-inner shell and heads. manhole ring and cover. dip tubes. spill dam and discharge pipe. Although
presently used for hauling 50% caustic soda. the corrosion resistance of this material will allow the hauling of a variety of
corrosives.
tained above the freezing point. Tables XLIV and
XLV give the results of tests in transportation
and storage facilities.
It is common practice to load and unload cars
of 73% caustic through Nickel 200 heat exhang-
ers, pumps and piping.
Table XLIV
Field Test in Tank Car Transporting
74% Caustic Soda
Test Period: 11 trips of 79 days.
Aeration: None. Agitation: By movement of tank cars.
Material
Nit;lle1200
INCOlOY alloy 825
MONEL alloy 400
CARPENTER alloy 20
Corrosion Rate,
mils per year
0.3
0.3
0.4
0.9
8.4
Fig. 19 - 1300 feet of transfer pipe with a rolled and
welded internal lining of Nicke1 200 carries 50% caustic
soda from a marine terminal to a Nickel 2ooc1ad storage
tank. Nickel 200-clad tank cars are in the background.
Table XLV
Field Test in Storage Tank for 73% Caustic Soda
Aeration: None. Agitation: None except for filling of tank.
-Material
Nickel 200
I NCONEl alloy 600
MONEL alloy 400
Zirconium
Titanium
Mild Steel
Corrosion Rate,
mils per year
0.3
0.4
0.7
L4
4.7
Destroyed during test
30
D. Soap Manufacture
Soaps are made by the reaction, called "saponi-
fication,"between alkali and fatty oils (gly_
cerides) and fatty acids of animal or vegetable
origin, or a mixture of both. The largest produc-
tion, and the most familiar, is "hard" soap made
with caustic soda as the saponifier. Caustic potash
produces a "soft" or liquid soap.
In certain high grade soaps, it is necessary to
avoid contamination by such metals as iron and
copper in order to obtain a high quality product.
Therefore, pure caustic must be used in combina-
tion with corrosion-resistant equipment. The
matter of iron contamination is particularly sig-
nificant in soap-boiling kettles because the soap
spends so much time there. particularly in the fuH-
boiled process. This is especially significant in the
upper parts of the kettles where corrosion rates
are highest. Table XLVI shows the results of one
plant corrosion test in a soap-boiling kettle. Some
of the earliest applications of
materials were in the construction of soap kettles.
Table XLVI
Plant Corrosion Test in SoapBoiling Kettle
Specimens immersed near the top of the settling cone duro
ing saponification and graining.
Material
Hit;ke1200
MONEL alloy 400
.NCOffEl. alley 600
HiResist Type 1
Mild Steel
Cast Iron
Corrosion Rate.
mils per year
<0.1
<0.1
<0.1
0.1
3.2
11.0
The first step. in most cases, was to line the upper
portions of existing steel kettles with Nickel 200.
AHoy 400 or either Type 304 or Type 316 stain-
less steel. Because of occasional difficulties win
these lined vessels (usually weld cracks in thE
liner because of differential thermal expansior
between the steel kettle and the liner) , new vessel:
were sometimes constructed completely from cla(
plate. The same materials are also used for heat
ing coils. swing pipe, kettle covers and othe
accessory equipment.
Much of the corrosion test work in soap plants
has been concerned with the treatment of spent
soap lye and recovery of glycerine. since these
processes represent particularly corrosive condi-
tions. The pH of the solution during acid treat-
ment is usually 4 to 4.5 and sometimes as low as
3, due to the presence of hydrochloric or sulfuric
acids. Agitation of the mixture with air, a com-
mon practice, tends to increase the corrosion rate
of steel. The results of six tests during acid treat-
ment in four different soap plants are shown in
Table XLVII.
Alloy 400 and Nickel 200 or steel clad with
these materials are used for both acid-treating
and caustic-treating tanks because of their resist-
ance in both environments. Austenitic chromium-
nickel stainless steel and Alloy 600 are also used
but pitting is possible with these alloys under
certain conditions as shown in Table XLVII. Ni-
Resist Type 3 is used instead of Types 1 or 2 for
Table XLVII
Plant Corrosion Tests in Acid Treatment of Spent Soap lye
Test 1: Immersed in acid treating tank in mixture of 13% NaCI and 4.5% glycerine to which
is added 150 Ib of 28% HCI and 75 Ib of 17% aluminum sulfate per 30,000 Ib soap
lye. Temperature: 1 to 82 C (30 to 180 F). Test Period: 167 days. Plant L
Test 2: Immersed halfway down in acid treating tank in mixture of 18% NaCI plus glyce.rine
to which is added 0.5% solution of aluminum chloride. Aerated. Average tempera
ture: 74 C (160 F). Test Period: 65 days. Plant 2.
Test 3: Immersed in trough of filter in acid treated filtrate from Test 2. Aerated. Average
temperature: 71 C (160 F}. Test Period: 65 days. Plant 2.
Test 4: Immersed halfway down in acidtreating tank in mixture of 8 to 10% NaCI and 4.5%
glycerine made acid to pH 4.5 with HCI and ferric chloride. Air agitation. Temperature:
21 to 71 C (70 to 160 F). Test period: 28 days. Plant 3.
Test 5: In acid treating tank in spent soap lye made acid to pH 4.5 with HCI and ferric chlo
ride, and aluminum sulfate. Agitated wiUl1iIir. Temperature: 54 to 79 C (130 to 114 F).
Test Period: 45 days. Plant 3.
a. Immersed in bottom of tank near air inlet.
b. In vapor in top of tank. .
Test 6: Immersed halfway down in solution containing 13 to .16% NaCI plus Na2S0. and
10 to 12% glycerine made acid to pH 4.5 with sulfuric acid and ferric chloride.
Aerated. Temperature: 32 to 100 C (90 to 212 fl. Average 85 C (180 Fl. Test Period:
105 days. P\ant4.
C.onosion llate.lIllJs per year
Test 1 Test 2 Test 3 . TesH Test Sa Test Sh TestS
Material Plant 1 Plant 2 Plant! Plant 3 Plal1t3 Plant 3 fitaltt4
MOHEL alloy 400 .9 0.3 4.8 2.9 5.6 4.4 16.0
Hickel 200 1.1 0.9 3.7 L8 5.1 4.7 10.0
IHCOHEL aUoy SOO .6 <.1 .7 0.8 .7
Type 302 stainless steel <.1
.7 (a) O.5!d
Type 304 stainless steel .5!d LOlh)
Type 316 stainless steel
<.1
A (b) LO(i)
CopperNickel alloy CA 715 27.0
Aluminum. Type 1100 4.4 (d)
HiResist Type 3 3.0
Hi Resist Type 2 2.7 1.0 4.0
HiResist Type 1 2.5 0.9 3.4 5.0
Mild Steel 5.3 3.0 17.0 16.0 29.0 (e) 34.0(gl 14.0
Wrought Iron 18.0 24.0 (f) 44.01gl 14.0
Cast Iron 11.0 6.0 16.0 14.0
(a) Perlorated by pitting. original thickness 31 mils. (f) Pitted to maximum depth of 9 milS.
(bl Pitted to maximum depth of 11 mils. (gl Pitted to maximum depth of 8 mils.
(e) Pitted to maximum depth of 5 mils. (h) Pitted to maximum depth of 6 mils.
(d) Pitted to maximum depth of 3 milS. (i) Pitted to maximum depth of 14 mils.
(e) Pitted to maximum depth of 20 mils.
31
the construction of soap lye filters and filter plates
to withstand possible therma' shock when the hot
solutions enter a cold filter process. Pumps of
iron-base nickel-chromium-copper-molybdenum
alloys such as WORTHITE or DURIMET 20 have given
good performance handling both acid- and
alkali-treated soap lye. Austenitic chromium-
nickel stainless steels, usually Type 304, have been
used to advantage for "finishing and packaging"
equipment.
Although a considerable amount of the world's
soap is still produced batch-wise, efforts to reduce
the 4 to 11 days required with the fun-boiled kettle
method have resulted in a number of continuous
processes for soap manufacture. In one such
process, blended fats with zinc oxide catalyst are
reacted countercurrently with water in a 65-foot-
high. Type 316 stainless steel hydrolyzing tower
maintained at 282 to 260 C (450 to 5(,)0 F) and
600-700 psi. Fatty acids are continuously drawn
off the top and crude glycerol off the bottom of the
column. The fatty acids arevacuum-distiUed and
then neutraiized in a high-speed mixer with a
caustic soda solution containing salt. thus produc-
ing soap in about four hours.
24
In other continuous processes which usually
utilize centrifuges. the corrosives encountered
are much the same and considerable quantities of
austenitic chromium-nickel stainless steel. Alloy
400 and Nickel 200 are utilized. Tables XLVIII
and XLIX indicate the corrosion rates eneoun-
Table XLVIII
Plant Corrosion TestinfourthStage lye Tank
Immersed in tank containing soap lye with 2% MaOH and
11% MaC!..
Temperature: 88 to 96C (190 to 205 F).
Corrosion Rate,
Material mils per year
Nickel zno Nil
o
MONEL alloy 400 Nil
INcolfEl aUoy 600 Nit
Type 316 Stainless Steel Nil
Type 341 Stainless Steel Nil
Type 304 Stainless Steel 0.1
HiResist Type 1 0.1
Mild Steel 1.0
Cast Iron 3.0
Less than 0.05 mils pel' year.
Maximum Depth
of Pitting, mils
None
None
None
None
None
None
None
7
22
tered in a lye tank and a centrifuge in one of these
processes.
Table XLIX
Plant Corrosion Test in Third-Stage Centrifuge
Specimens located at soap discharge. Mixture contained
15% NaOH and 11 % NaC!. Low aeration, flow 350 gallons
per hour through 4inch pipe. .
32
C orrusion Rate, Maximum Depth
Material mils pef year of Pitting, mils
Nickel ZOO Nil
o
None
MONEL alloy 400 Nil None
I/'ICONE.L alloy 600 Nil None
Type 304 Stainless Steel 0.1 None
Hi-Resist Type 1 0.4 None
Mild Steel 10 Perforated
Cast Iron 12 55
Less than 0.05 mils per year.
E. Pulp and Paper Industry
Over a million tons of caustic soda are used
annually in the pulp and paper industry, prin-
cipally for the extraction of alkali-soluble impuri-
ties in multistage bleaching and for pH control.
Small amounts are used for preimpregnation of
wood chips and for the production of soda pulp.
More than two-thirds of aU paper is pX'Qduced
by the Kraft process. Digestion of certain soluble
portions of wood chips is accomplished by a hot
alkaline liquor consisting of a mixture of dilute
caustic soda and sodium sulfide with a total alka-
linity of about 3 per cent. The following are prin-
cipal areas where carbon steel may corrode at
an excessive rate and nickel-containing alloys
(usually austenitic chromium-nickel stainless
steels) can be used to advantage.
1. Digesters
Batch-type Kraft digesters are commonly built
of carbon steel with a corrosion allowance in
excess of one inch. Until recent years this resulted
in a service life of about 15 years, but with the
increasingly severe conditions imposed. by modern
pulping methods, service life was reduced to about
7 to 9 years. Weld overlays employing A WS E310,
or A WS E310-Mo. have been employed to extend
the service life of corroded steel batch digesters.
Table L indicates the excellent corrosion resist-
ance of stainless steel and several other nickel
alloys in one Kraft digester.
Table l
Plant Corrosion Test in a Sulfate Process,
Alkaline, Wood Pulp Digester
Temperature: 177 C (350 f).
Aeration: None.
Agitation: Violent boiling during cook.
Top--Vapors in the top of the digester. Occa
sional splashing of chips, pulp and cooking
liquors.
Bottom-Liquid and slurry on bottom screen of
digester.
Specime(ls: Combination of stress and general COrrosion.
Strips were stressed beyond the yield point by
bolting down over a fulcrum. Some specimens
were welded or contained weld overlays as
noted. No stress corrosion cracking occurred.
Material Condition
INCONEL alloy 600 Plate. asreceived
CARPENTR alloy 20 Welded
INCoNEL alloy 600 Welded
INCOlOY alloy 825 Plat.e. asreceived
INCOlOY alloy 825 Welded
Type 316 Stainless Steel Plate, asreceived
Type 316t. StainJess steel Plate. asreceived
Type 31Sl Stainless Steef Welded
Type 316 Stainless Steel Welded
AViS Eltflllveriay on Steel Weld Overlay
Note: A dash indicates no coupon was exposed.
Corrosion Rate,
mils per year
Top Bottom
0.02 0.21
0.03 0.09
0.03 0.23
0.03 0.09
0.03
0.04 0.15
0.05
0.06 0.17
0.06 0.15
0.05 0.17
There are a few Kraft digesters that utilize a
duplex process in which the charge is initially acid
(pH 4) and later alkaline. Table LI shows corro-
sion rates in this process.
There are several hundred continuous digesters
operating on wood chips in the United States.
These are constructed primarily from carbon
steel with high corrosion rate areas lined or clad
with Type 316L stainless steeL These high corro-
sion rate areas include the upper section. where
fresh, hot alkaline liquor is injected, and the
bottom section in the area of the blow valve.
Internal accessories such as scrapers and chip
screens are usually fabricated from Type 316L
stainless steeL Construction of digesters with clad
Type 316L stainless steel would allow for con-
Table LI
Plant Corrosion Test in a Digester Utilizing
a Duplex Sulfate Process
Temperature: 100 to 171 C (212 to 340 f).
Cycle: Chips steamed for one hour, temperature rises from
100 C to 118 C (212 to 244 f). Acid liquor removed.
Alkaline liquor containing 82 gpl NaOH and 25 gpl
Na,S added. Charge brought to 171 C (340 f). cooked
for total of 5 hours.
location: In vapor. Test Period: 731 days.
33
Material
Type. 316 Stainless Steel
CARPENTER alloy 20
INCj)NELalloy Spo
MONEL alloy 400
Titanium
Mild Steel
Corrosion Rate,
mils per year
0.1
0.1
0.1
OJ
23
55
107
Fig. 20 This top separator on a KAMYR continuous di
gester separates the chips from the flushing liquor. With the
exception of the drive mechanism. this separator is can
structed of Type 304 stainless steel.
siderably reduced wall thickness and much lower
maintenance costs.
2. liquor Heaters
Shell and tube heat exchangers are used to heat
the digester liquor prior to its introduction into
both batch and continuous digesters., Results of a
corrosion test in such a heater are shown in Table
LII. These data may indicate a lower than actual
corrosion rate for carbon steel, since the heat
exchanger tube walls are at a temperature higher
than the liquor in which the test specimens were
exposed. The liquor contains a large proportion of
fresh caustic and sulfide in addition to some black
liquor recovered from a previous digester cook.
Experience over many years has proven the ade-
quacy of annealed Type 304 stainless steel for this
service. The use of "as-welded" tubes has some-
times resulted in failure by intergranular cor-
rosion immediately adjacent to the weld. This type
of corrosion has not been observed when tubes
are used that have been made in compliance with
ASTM A 249. This specification caUs for welded,
drawn, quench-annealed tubing. Tubes of this
type have been known to last in excess of.10 years,
but service life is dependent on specific operating
conditions. In a few instances, the Type 304 stain-
less steel tubes have been subject to failure by
chloride stress-corrosion crackng. Alloy 600 and
Alloy 20 have been successfully employed to resist
this type of attack.
3. Black liquor Evaporators
To permit recovery of chemical values in the
digester liquor when chip cooking is complete, it
is necessary to concentrate the liquor, together
with the chip wash water. This is required to raise
the solids content to more than 50 per cent. which
will permit burning in the recovery furnace.
Kraft liquor vacuum evaporators are multiple
units usually consisting of one or more sets of six
long tube vertical effects connected in series.
Corrosive conditions on the tubes are somewhat
less severe than in digester liquor heaters since
the vacuum operation results in lower boiling
temperatures. The first effect operates at the
highest temperature of about 135 C (275 F). Tem-
peratures decrease in each succeeding effect. It
has been customary to use Type 304 stainless
steel for tubes in the first effect and often in the
second effect. A number of installations have used
Type 304 stainless steel tubes in all effects, re-
sulting in less frequent downtime fer cleaning,
long service Hfe, and maintenance of high heat
transfer rates.
34
Table lit
Corrosion Test in Kraft Pulping
Exposed 68 Days in Head of liquor Heater
Flow rate of 2400 gpm at temperature of 173 C (344 F).
Material
INCONEL alloy 600
MONEL alloy 400
Nickel 200
Mild Steel
Cast Iron
Corrosion Rate,
mils per year
0.5
0.8
0.9
38
57
95
342
Vapor domes in the hottest effects are often clad
with Type 804Lor Type 316L stainless steel, since
carbon steel in this area may corrode at a rate
exceeding 100 mils per year. There are also instal-
lations where sta.inless-elad steel has been used for
the entire evaporator body. Advantages of such
construction.inelude less carry..over of corrosion
products and less fouling of the evaporator tubes
by these products.
Defiectorpla.tes and auxiliary piping are usu-
any made of solid Type 804L stainless steeL For
valves and pumps, Ni-Resist Type 2, CF-8 and
CF -8M castings are used.
4. Recausticizing
As part of the operation to regenerate chemi-
cals reclaimed from the recovery furnace, sodium
carbonate is treated calcium hydroxide
(milk of lime) to produce sodium hydroxide.
Table lin
Corrosion Test in Kraft Pulping
Exposed 68 days in green Uquor. 175 to gpl as Na2 CO,
in flow bQx.from recovery furnace to claSSIfiers.
Temperature: 66 to 99 C.(150to 210 F).
Some aeration and agitation.
Material
tN(:ONEL alloy 600
Type 302 Stain1ess Steel
Nickel 200
MONEL alloy 400
Mild Steel
Cast Iron
Corrosion Rate,
mils per year
<0.1
0.1
0.1
0.1
0.2
0.3
0.5
115
176
Carbon steel, with a corrosion allowance. has
been used for most of the equipment. As shown
in Table LIII, fairly high rates can occur on car-
bon steeL Light gauge Type 304 stainless steel
is an economic selection for troublesome areas.
F. Aluminum
Despite extensive use of caustic soda by the
aluminum illdustry for the extractioRofhydrated
alumina from bauxite in the Bayer process, rela-
Fig. 21 - This llfoot long. 16inch diameter pipe has been
electmplated with nickel to yield a 30-mil thick deposit on
the inner diameter and about 2 mils on the outer diameter.
Sections like this are welded toget:he( to form piping used
in bauxite refining in the aluminum industry. Lengths of
greater than 11 feet can also be plated.
Photo by courtesy of Plating Engineering Company. Milwaukee. Wise.
35
tively smallam{llwts of nickel and nickel altoys
have been utiJized in these plants.
Alloy 400 tubes have been successfully em-
ployed for digester preheaters. and Alloy 400
insert ferrules have been used to overcome the
inlet end corrosion in other steel preheater tubes.
Relatively thick (30 mils minimum) electroplated
nickel {lll steel has been used to advantage for
piping and digester preheater channels. Nickel
weld-overlays haVe proven \Iseful on pump cas-
ings, and cast nickel (ACI CZ-IOO) has given good
service as pump impellers. valve bodies and for
other instrumentation.
However. the present practice with bauxite
digesters is to use thick-walled carbon steel at
low stress levels. Some cases of stress-corrosion
cracking (If steel have occurred in plants handling
caustic soda solutions in the Bayer extraction
process.
z
::>
The recent trend awaYI;r;om ores high in gibbs-
ite C{lntent toward the use of Ores relatively high
in boehmite c()ntent has necessitated digester
operation at higher pressures and temperatures.
This increases the pos!;;ibHity of caustic embrittle-
ment of steeL Thus. nickel or nickel-clad steel
should be given consideration for the processing
of these higher boehmite bauxites.
G. Caustic FuSions
Nickel 200 and Nickel 201 are useful as mate-
rials of construction for vessels for the caustic
fusi{ln of organic comp{lunds. Where tempera-
tures exceed 316 C (600 F). the low.-carb{ln
Nickel 201 is preferred to preclude grain bound-
ary precipitation of carbon which greatly reduces
duetility. For those reactions where sulfur com-
pounds are present at temperatures over 250 to
300 C (482 to 572 F). either in the process or the
heating medium, nickel may be attacked inter-
granularly and Alloy 600 is preferred.
One process for the production of resorcinol
has involved the caustic fusion of benzene meta
disulfonic acid at 325 C (617 F). Equipment for
this production has been made of wrought Alloy
600 and ACI CY -40 castings. Both alloys should
be stress-relieved as indicated in the section on
nickel-chromium alloys (Part II B).
H. Petroleum Refining
soda or, occasionally, caustic potash or
sodium carbonate is used in petroleum refining
for acid neutralization and the removal of unde-
sirables such as mercaptans and hydrogen sulfide.
Aqueous solutions may range from 2 to 50
per cent.
For many of the applications where temper-
ature and concentration are low, the corrosive
conditions are mild enough that steel can be used.
Where the corrosive conditions are more aggres-
sive, Nickel 200, AHoy 400 or Alloy 600 are used.
Very often Alloy 400 is used because it appears to
have a greater tolerance for the impurities
present in the process.
Fig. 22 - Nickelcopper alloy 400 was used for the walls of
the caustic stripper towers. reboiler tube bundles and hot
caustic lines in this refinery. After 10 years of service. the
Alloy 400 components continue to withstand the corrosive
mineral acids. sulfur compounds and hot caustic soda in
the fluid hydroformer and caustic regenerating equipment.
In the t'egeneration of caustic solutions, it is
common practice to use Alloy 400 in critical por-
tions of the system where steel is unsuitable.
These locations include the regenerator reboiler,
preheaters and piping for handling hot caustic
solutions and sometimes for the bottom sections
of the regenerator towers. These components may
be either solid or clad. ACI CZ-IOO, ACI M-35
ductile Ni-Resists and WORTHITE stainless steei
have been used for valves and pumps. The results
of plant corrosion tests in the reboilers of caustic
regenerator units are shown in Table LIV.
36
Table ltV
Plant Corrosion Tests in
Caustic Regeneration Units
Test A-In open tank used to boil 18 to 22% caustic soda
plus merca pta ns and cresolates for regeneration of
caustic solution. Test specimens were immersed in
solution above heating coils.
Temperature 38 to 104 C (100 to 220 F).
Average 80 C (175 F).
Test a-Just reboiler inlet below bottom tray of reo
generating tower. Solution 18% caustic soda for
tified with naphthenic acid. cresols and phenols to
22 to 28 Be. Solution also contained 0.040/0 mer
captan sulfur.
Temperature: 21 to 116 C (70 to 240 f).
Average 107 C (225 F).
Test C-At bottom of stripping tower 18 inches above reo
boiler tubes. Solution 7 % caustic soda with trace
of mercaptans.
Average 135 C (275 Fl.
Test o-In vapor of caustic soda regeneration unit.
Solution entenng contained' 13.2% caustic soda.
0.37% sulfide sulfur and 0.80% mercaptide sulfur.
Material TestA TestS Test C Test D
INCONEl alloy 600
<0.1 <0.1 <0.1 0.3
Type 304 Stainless Steel" 0.1 0.1 0.1
Nickel 200 0.1 0.2 1.1 2.0
MONEL alloy 400 0.3 0.1 0.9 2.0
Type 316 Stainless Steel" 0.4 0.2
CopperNickel alloy CA 715 1.1 4.5
HiResist Type 1 3.8 4.0 13.0
Cast Iron 13.0 10.0
Carbon Steel 29 12.0 33.0
.., Subject to pitting.
"') May be 'Subject to stress-corrosion cracking_
In view of its good resistance to caustic alkalies
containing hydrogen sulfide and mercaptans, Al-
loy 600 is also a useful material for evaporator
tubes or other parts of regenerator systems. Alloy
600, rather than Nickel 200 or AHoy 400, should be
used in this service where metal temperatures in
excess of about 250 to 300 C (482 to 572 F) are
encountered, since Nickel 200 and Alloy 400 are
subject to sulfidation at higher temperatures.
A caustic stripper, at a major Louisiana refin-
ery, constructed of MONEL alloy 400, exhibited no
detectable metal loss after more than 4 l'2 years'
service handling up to 45<; caustic soda at tem-
peratures up to 143 to 149 C (290 to 300 F). It is
still giving repair-free service after 15 years.
In one Texas refinery, mercaptains are removed
by the Dualayer Process * which utilizes two
layers of immiscible solvents. The first solvent
layer, a water solution of caustic potash and
potassium cresylate, removes the mercaptans.
The second and lower layer is a water solution
of caustic potash that maintains the composition
of the upper layer. Water and potassium hydrox-
ide migrate between lower and upper levels, sus-
taining the equilibrium. MONEL alloy 400 was used
for the stripper preheater, reboiler. and stripping
tower trays and. in a cast form (ACI M-35), for
the bottom pump. The tower itself was lined with
MONEL aHoy 400 and stress-relieved. This equip-
ment continues in operation after 20 years.
Nickel-copper alloy 505 has excellent non-
galling properties and can be combined with cast
nickel-copper alloy ACI M-35 in pump assemblies
to avoid seizing. particularly in mixtures contain-
ing gasoline or similar solvent materials where
lubrication is practically impossible.
L Caustic Oescaling
Several processes involving molten caustic soda
are in commercial use for the descaling of various
metals and-alloys, particularly the stainless steels.
Some of these processes involve addition to the
caustic of reducing agents to reduce the metallic
oxides to metal or lower metal oxides, most of
which flake off in the subsequent water quench.
Patented Process. Mohil Oil Corp.
37
I n one process, the parts to be descaled are immer-
sed in a 370 C (700 F) bath of molten caustic soda
containing 1.5-2% sodium hydride. Other proc-
esses operate with molten caustic at 480 C (900
F) or higher.
Carbon steels are often used for the equipment
handling these fused caustic baths up to about
480 C (900 F). In cases where carbon steel has
not proven satisfactory. Nickel 201 and Alloy
600 have been demonstrated to give good per-
formance. Nickel 201 is used for sodium hydride
generators in one process. Both Nickel 201 and
Alloy 600 are used for sheathing on electric heat-
ing elements in caustic baths. AHoy 600 is used
for gas-fired heater tubes in some cases. In cases
where the caustic baths are operated at higher
temperatures than usual, such as 566 to 621 C
(1050 to 1150 F), Nickel 201 is used instead of
carbon steel for pickling tanks and associated
equipment. A plant corrosion test in a commercial
molten caustic pickling bath operating at 482 C
(900 F) showed a corrosion rate of one mil per
year for nickel in a 60-day test.
J. Reclaiming Caustic for Economy
and Pollution Control
In the diverse industries which make use of
caustic solutions, numerous companies have
found that it is economically attractive to reclaim
and concentrate the caustic values of their effiu-
ents. Even the return on investment for
caustic recovery units is not high enough for justi-
fication on this basis alone. pollution control is
desirable and may become mandatory as local
anti-pollution laws become more stringent.
Recovery and concentration plants are commer-
cially available for some industries. Of the total
caustic soda purchased yeariy by a textile mill
for mercerizing cotton. often as much as 65 per
cent can be recovered from the mercerizingframes
and up to 95 per cent at the mercerizer. The con-
centration of caustic soda is from about 5 per cent
in contaminated liquor to the d e ~ j r e d concentra-
tion for the particular mercerizing operation.
These plants utilize nickel or high nickel alloys for
evaporators and associated equipment .
PART V. WELDING
A. Fabrication of
Nickel-Clad Equipment
In the welding of nickel-clad equipment, a cer-
tain amount of iron dilution of the nickel weld
deposit occurs. Special precautions are usually
taken in order to minimize this dilution. With
special precautions, the n i k ~ l welds in a nickel-
clad tank for a chemical tanker were limited to
an iron content of 0.35-3.29%.26 Gegner has sug-
gested that considerably more iron than this can
be tolerated.
27
Although iron-contaminated nickel weld metal
and nickel-iron alloys are not severely attacked in
73% caustic soda at 121 C (250 F). as shown by
data in Tables LV and LVI, nickel-iron alloys can
be the anode in an electrolytic cell with nickel,
as shown in Table LVII. Note that the 20% iron
alloy corroded at three to five times the rate it did
when it was not coupled to nickel. Even greater .
increases in rate would be expected in large pieces
of equipment where the relative ratio of cathodic
area (cladding) to anodic areas (weld) is greater
than the 10:1 ratio of the test.
Table LVII
Table LV
Corrosion of IronContaminated Nickel Welds
in 73% Caustic Soda at 121 C (250 F) 27
Iron
in Weld,
%
0.51
5.56
11.43
13.15
17.62
22.85
First
Exposure,
30 days
8
8
7
7
7
6
Second
Exposure,
60 days
5
5
5
4
5
4
Table lVI
Total
Exposure,
90 days
6
6
5
5
5
5
Corrosion of Nickel and NickellronAlloys
in 73% Caustic Soda at 121 C {250 f)27
Corrosion Rate,
Iron. % mils per year
0 7
0 7
5 8
5 8
10 6
to 8
20 8
20 8
Galvanic Corrosion Tests in Caustic Soda
of Nickel to Nickel-Iron Alloy Couples
Area: Nickel
Nickellron Alloy
Motion: None.
0.5 sq dm
O.05sq dm
Aeration: None.
Couple
No.
2
3
Notes:
Couple
Materials
5% FeNi
Nickel
10% feNi
Nickel
20% FeNi
Nickel
23% NaOH at 105 C (221 Fl
Coupled Uncoupled
1.6 1.4
0.6 0.4
2.6 L2
0.4 0.4
3.6 0]
0.6 0.4
1. The ironnicket alloys were in the form of castings.
2. No tests were made, uncoupled. in the 500/0 NaOH solution.
38
50% HaOH at
15C (161 Fl 15% NaOH at 126 C (259 Fl
Coupled Coupled Uncoupled
2.4 1.0 1.0
0.8 1.6 1.5
2.0 1.5 1.4
0.6 LO 1.5
1.6 1.8 0.6
0.4 1.1 1.5
B. Repair of Equipment in
Caustic Service
Before doing any repair or maintenance weld-
ing of nickel or nickel-containing alloys or dad-
steel plate that has been in caustic service, it is
necessary to remove products of corrosion, and
any other foreign material, from the vicinity of
the area to be welded. (The caustic soda and other
impurities present can cause loss of ductility and
cracking if present during welding.) Therefore,
great care should be taken to obtain a clean, bright
metal surface over an area extending 2 to 3 inches
from the site of welding on both sides of the piece.
Cleaning mechanicalIy, by grinding with either a
fine wheel or a disc grinder, or chemically, by
pickling, is recommended. After cleaning, the
welding procedures outlined for new metal should
be followed in every detaiL
Flash pickling solutions are effective for clean-
ing nickel and high nickel alloy surfaces. These
may be applied with long-handled swabs or
brushes where equipment is large, or may be held
in glass or ceramic crocks for pieces that are
easily handled. such as the ends of nickel caustic
evaporator tubes that have been removed from
evaporator service and are to be used for pipe-
lines. The tubes can be dipped vertically and
cleaned for a minimum distance of 3 inches from
the end.
AVAILABLE LITERATURE
The following Corrosion Engineering Bulletins are available for your use:
"Resistance of Nickel and High Nickel Alloys to Corrosion by Sulfuric
Acid"
"Corrosion Resistance of Nickel and Nickel-Containing Alloys in Caustic
Soda and Other Alkalies"
"Resistance of Nickel and High Nickel Alloys to Corrosion by Hydro-
chloric Acid, Hydrogen Chloride and Chlorine"
"Corrosion Resistance of Nickel-Containing Alloys In Phosphoric Acid"
"Corrosion Resistance of Nickel-Containing Alloys in Hydrofluoric Acid,
Hydrogen Fluoride and Fluorine"
39
REFERENCES
1. Swandby, R. K., "Corrosion Charts: Guides to Ma-
terials Selection", Chen!. Eng., Vol. 69, No. 11, Nov.
12, 1962, p. 197.
2. Fontana, M. G., "Corrosion at Elevated Temperatures
and Pressures", The Ohio State University Research
Foundation, Report No. 10, Project 350, May 1, 1951,
p.F2.
3. Badger, W. L. and Standiford, F. C., "Anhydrous
NaOH: Today's Technology", Chern. Eng., 61, Feb.
1954, pp. 183-187.
4. Gregory, J. N., Hodge, N. and Iredale, J. V. G., "The
Static Corrosion of Nickel and Other Materials in
Molten Caustic Soda", AERE CIM 272, March, 1958.
5. Gregory, J. N., Hodge, Nand Iredale, J. V. G., "The
Corrosion and Erosion of Nickel by Molten Caustic
Soda and Sodium Uranate Suspensions Under Dy-
namic Conditions", AERE CIM 273, March, 1956.
6. Lad, R. A. and Simon, S. L., "A Study of Corrosion
and Mass Transfer of Nickel by Molten Sodium
Hydroxide", Corrosion, 10, December. 1954, pp. 435-
439.
7. Smith; G. P., Sieidlitz, M' E. and Hoffman, E. E.,
"Corrosion and Metal Transport in Fused Sodium
Hydroxide", Co)Tosion. 13, September, October, 1957.
pp. 561t-564tand 627t-630t.
8. Forestieri, A. F. and Lad, R. A., "The Use of Metallic
Inhibitors for Eliminating Mass Transfer and Corro-
sion in Nickel and Nickel Alloys by Molten Sodium
Hydroxide", Lewis Flight Propulsion Laboratory,
Cleveland, Ohio, February, 1955, NACA RM E54L13.
9. May, C. E_, "Correlation Between Pressure
and Protective Action of Additives in the Molten
Sodium Hydroxide-Nickel System", Lewis Flight
Propulsion Laboratory, Cleveland, Ohio, February,
1966. NACA RM E55LOl.
10. Wallace, T. and Fleck, A., "Some Properties of Fused
Sodium Hydroxide", Jourl/al Chelll. Suc., 119, 1921,
p. 1839.
11. Uhlig, H. H., Ed., Corrosion Handbook. N. Y., John
Wiley, and Sons, Inc., 1948, pp. 576-577.
12. Stone, J. M., "Solutions Intergranular Cor-
rosion of Stainless Steels", Information from Internal
Document by courtesy of E. L du Pont de Nemours and
Co., October, 1955.
13. Agrawal, A. K. and Staehle, R. W., "Stress-Corro-
sion Cracking of Fe-Cr-Ni Alloys in Caustic Environ-
40
ments", Report No. COO-2018-21 (Q6) for period
April 15, 1970-July 14, 1970, Ohio State University,
Columbus, Ohio.
14. Nathorst, H., "Stress Corrosion Cracking of Stainless
Steels-Part I Practical Experiences", Welding Re-
search Council Bulletin, No.6, October, 1950, pp. 6-7
and 10.
15. ASM Committee on Stainless Steel in Chemical Corro-
sion Service,lHetals Handbook, Am. Soc. Metals, 1961,
p.566.
16. Beck, F. H. and Fontana, M. G., "Corrosion by
Aqueous Solutions at Elevated Temperatures and
Pressures", Corrosiun, Vol. 9, No.8, August, 1953. pp.
287-293.
17. Pratt. W. E., "Corrosion Resistance of Worthite in
Caustic Soda", Chemical EnginC(!ring, Vol. 56, No. 12,
1949, pp. 213-214 and VoL 57, No.1, 1950, pp. 213-214.
18. "Hastelloy Corrosion-Resistant Alloys", Union Car-
bide Corporation, 10th Edition, May, 1957 and private
communication from Haynes Stellite Co.
19. P. J., "Corrosion in Alkaline Environments",
ProcecdiJlgs of Shmt Course 0)/ Pl"(lCeSS Industry
Corrosio)t, National Association of Corrosion Engi-
l!eers, September 12-16. 1960, p. 1 L
20. McCallion, J., et at, "Switch to Continuous Evapora-
tion Boosts Capacity But Not Manpower", Chemical
P"ocessing, August, 1968. pp. 20-21.
21. U. S. Patent 3,380,806, April 30, 1968.
22. Twiehaus, H. C. and Ehlers, N. J., "Caustic Purifica-
tion by Liquid-Liquid Extraction", Chemical Indus-
tries, August, 1948, pp. 230-233.
23. Friend, '.V. Z. and Mason, J. F., "Corrosion Tests in
the Processing of Soap and Fatty Acids", Corrosion,
Vol. 5, No. 11, 1949, p. 358.
24. Kirk-Othmer, Ellcyclopl'tiia <If Chcmical Technology,
Second Edition, 1969, Vol. 18, p. -123.
2;). Champion, F. A., "Some Aspects of the Stress-Corro-
sion of Steel in Caustic Soda Solutions", Chemistr1l
{fllel Il/dustl'1f, July 13, 1957, pp. 967-975.
26. Phelps, H. C .. "NickelLined Ship for Liquid Chemi-
cals", The Weldil/g Engil/eer, Vol. 39, No.4, 1954,
pp. 41-44.
27. Gegner, P. J., "Corrosion in Caustic of Nickel-Iron
Welds Obtained in Fabrication of Nickel-Clad Ves-
sels", CUI'rosiol/, Vol. 12, No.6, 1!:5C, pp. 26lt-262t.
TRADEMARKS
Following is a list of the registered trademarks referred to in this publication
together with the names of the trademark owners .

ALOYCO Registered trademark of Aloyco Inc.
CARPENTER Registered trademark of Carpenter Technology Corporation.
CHLORIMET Registered trademark of The Duriron Company. Inc.
DURANICKEL Registered trademark of The International Nickel Company. Inc.
DURIMET Registered trademark of The Duriron Company. Inc.
HASTELLOY Registered trademark of Cabot Corporation.
ILLIUM Registered trademark of Stainless Foundry & Engineering, Inc.
I NCOLOY Registered trademark of The International Nickel Company. Inc.
INCONEL Registered trademark of The International Nickel Company. Inc.
KAMYR Registered trademark of Kamyr Inc.
MONEL Registered trademark of The International Nickel Company. Inc.
NIMONIC Registered trademark of The International Nickel Company. Inc.
WORTHITE Registered trademark of Worthington Corp.

Corrosion Resistance of Nickel and Nickel Containing Alloys in Caustic Soda and Other Alkalies

Transféré par

Informations du document

Copyright

Formats disponibles

Partager ce document

Partager ou intégrer le document

Options de partage

Avez-vous trouvé ce document utile ?

Ce contenu est-il inapproprié ?

Droits d'auteur :

Formats disponibles

Corrosion Resistance of Nickel and Nickel Containing Alloys in Caustic Soda and Other Alkalies

Transféré par

Droits d'auteur :

Formats disponibles

CORROSION RESISTANCE OF

NICI<EL AND NICI<EL-CONTAINING ALLOYS

Vous aimerez peut-être aussi