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P A P E R

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Material Selection for Carbon

Dioxide Mineralization Plant

GEIR MOE
SENIOR MATERIAL ENGINEER
Hatch
Autoclave Technology Group
1075 North Service Road West, Unit 21
Oakville, Ontario L6M 2G2
Canada
T: 905-469-3403 x7355
F: 905-855-8270
E: gmoe@hatch.ca

Co-authors

HAROLD BOERRIGTER
Shell Global Solutions International BV

BEN C.M. IN T VEEN

Shell Global Solutions International BV

ALFRED P. MUTSAARS
Shell Global Solutions International BV

BIOGRAPHY
Geir Moe has a B.S. in Metallurgical
Engineering from Queens University,
Kingston, Ontario. His professional
experience includes 18 years as an
Application Metallurgist in stainless

C O R R O S I O N

KEYWORDS

steel and nickel alloy distribution

with Avesta Sheffield Canada and
Integris Metals. Geir is currently
Senior Material Engineer with Hatch
Autoclave Technology Group.

ABSTRACT
The potential impact of greenhouse
gas on world climate has created
much debate and concern. One of
the solutions to reduce the amount
of greenhouse gas released into the
atmosphere is to capture carbon
dioxide and sequester it as a solid
compound. Carbon dioxide and
suitable silicate minerals exposed
to elevated temperature and
pressure will result in the formation
of
carbonate,
effectively
sequestering the carbon dioxide via
mineralization. The object of this
investigation was to identify suitable
materials for construction of an
autoclave mineralization plant to
investigate
carbon
dioxide
mineralization with magnesium
silicate minerals at various
temperatures, pressures, and
electrolyte compositions.

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stainless steel
nickel alloy
titanium
autoclave
carbon dioxide sequestration
magnesium silicate
carbonate
mineralization
corrosion coupons
UNS S32750

INTRODUCTION
Carbon dioxide emissions from
mankinds fossil fuel based industrial
activities is one of the main reasons
for the climate change that is taking
place. Carbon Capture and
Sequestration (CCS) is one of the
main options for CO 2 mitigation.
Carbon
dioxide
carbonation
(mineralization) is another of the
CCS options. Others include
geological storage in aquifers and
empty oil and gas fields.
Mineralization is an industrial
mimic of the natural weathering
process, i.e., the exothermic
reaction of CO 2 with rocks to form

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carbonates via the reaction: mineral

+ CO 2 => carbonate + sand (SiO 2) +
heat. Due to the wide availability of
suitable
magnesium
silicate
minerals, mineralization is the only
CCS option without capacity
limitations. The products have
potential applications as filler or
aggregate in construction materials.
A key differentiator of mineralization
compared to the alternative storage
options, is that it is an inherent safe
and final CO 2 storage option
because the carbonates are
thermodynamically stable products.
The
Shell
Mineralization
Development started in 2001.
Initially, the use of calcium minerals
and residues was explored, aimed
at developing a cost-neutral CO 2
mineralization process (by using
waste streams as feed and
producing high-value specialties).
From mid 2006, the development
scope was changed to focus on
high-volume CO 2 mitigation based
on the abundant and widespread
magnesium
minerals.
Large
deposits are found in Canada, the
United States, Japan, and Australia.
Aspiration in the development is
making mineralization directly
applicable to dilute CO 2 streams
(i.e. 5 to 20 vol% of CO 2) and
specifically flue gases, thereby
making a separate (expensive)
capture
process
amine/CO 2
superfluous.
As
part
of
the
Shell
Mineralization Development, initial
design work was done on a
mineralization
pilot
plant.
Considering
the
specific
mineralization process conditions,
dedicated guidelines for the
materials of construction for
process equipment and piping
must
be
established.
In
cooperation with Hatch a controlled
program has been conducted to
test candidate materials and
provide a database to support a
decision
on
the
materials
specification for the autoclave and
the other process areas.
C O R R O S I O N

MATERIAL SELECTION
PHILOSOPHY

Philosophy for Rating Test

Results
Prior to conducting the test
program, pass / fail criteria were
established in order to interpret the
results of the program.
The following are grounds for
material rejection:

Material selection in process plants

typically focuses on corrosion issues
and the economic need to design
long lasting plants. In autoclave
applications, due to the nature of the
operating conditions, safety issues
are of critical importance to material
of construction discussions as the
failure of a pressure component (from
corrosion or metallurgy issues) can
lead to fatal consequences. In terms
of new processes, the risk is even
greater as typically the behavior of
the process is still not fully
understood, and it is likely the
system will be subjected to greater
variations in the operating conditions.

Pitting corrosion
Crevice corrosion
Stress-corrosion cracking
Any etching of the surface categorized
as superficial where the measured
corrosion rate is less than 0.1
mm/year (4 mils/year) is acceptable.
Pitting corrosion is a localized
corrosive attack that occurs on an
open surface that may eventually
perforate the metal. In an oxidizing
environment where stainless steel is
able to develop a protective passive
layer, pitting corrosion is dependent
on many factors and thus is difficult
to predict. Chloride ions can disrupt
the passive layer at weak points.
This produces very small anodes of
active metal surrounded by a large
cathodic area consisting of passive
surface. This provides the conditions
necessary for the rapid dissolution
of the metal in a small localized area
that will eventually result in full
penetration of the metal, provided
the chloride ions are able to remain
in the pit and the electrolyte contains
a sufficient quantity of oxidizing
agent to maintain passivity of the
cathodic surface.
Crevice corrosion is a localized
corrosive attack that occurs within
crevices. A common example is the
space between a gasket and flange
face. It may also occur in other
shielded areas on the metal surface,
such as surface deposits. In an
oxidizing environment the corrosion
mechanism is similar to pitting
corrosion, but initiates more easily
than pitting corrosion because the
crevice allows for the concentration
of chloride ions and the weakening
of the passive surface in the crevice
due to restricted movement of

Philosophy for Plant Design

Plant areas within the scope of a
mineralization plant can be broken
into four principal areas:
Feed preparation (low
temperature, atmospheric
pressure)
Autoclave and pressure
systems (high temperature
and pressure)
Discharge system (elevated
temperature, atmospheric
pressure)
Utilities
The key purpose of the corrosion
test program was to further
understand the behavior of materials
under
autoclave
conditions.
Autoclave conditions present the
highest risk should a failure occur.
As such, any corrosion testing results
should consider a margin above
direct result for safety purposes. In
areas at lower temperatures and
atmospheric pressure (feed and
discharge systems), there is less risk
in terms of operator safety (a leak as
opposed to a depressurization) and
selection can follow closely with the
minimum material that meets the
corrosion criteria. Utility systems
follow industry standard practice for
system material design selection.

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Titanium Grade 2 (UNS

R50400)

Figure 1. U-bend coupon.

The testing utilized U-bend coupons

so the susceptibility to chloride
stress-corrosion cracking could be
assessed along with general
corrosion resistance because of the
strong probability that stresscorrosion cracking is a degradation
mechanism that may be active
under these test conditions.

oxidizing agent into the crevice.

Crevice corrosion, like pitting
corrosion, is dependent on many
factors and thus is difficult to predict.
Stress-corrosion cracking is
cracking
caused
by
the
simultaneous presence of a tensile
stress and a specific corrosive
medium. With respect to stainless
steels, the most common form is
chloride stress-corrosion cracking.
Stress-corrosion cracking, like
pitting corrosion, is dependent on
many factors and thus is difficult to
predict.

Equipment Set-up
The initial coupons, Figure 1, were
all prepared in the laboratory to
ensure that the coupons were all
similar so performance comparisons
are valid. The internal temperature
and pressure of the autoclaves was
monitored during testing. The vapor
space and solution were purged
with carbon dioxide before the
autoclaves were heated and
pressurized. The pressure and overpressure of the carbon dioxide was
maintained during testing in an effort
to imitate the expected field
conditions as closely as possible in
the laboratory. The autoclaves were
limited to six coupons at a time;
three in the vapor space and three
in the liquid phase. Tests were run
for a total of 120 days, with
shutdown and inspection at 30, 60,
and 90 days. Liquid replenishment
was performed at the same time.
These coupons are not standard
design but preparation procedures
for the tests and corrosion coupons
reference ASTM and NACE
standards.
U-bend
coupon
preparation follows ASTM G30
(Standard Practice for Making and
Using U-Bend Stress Corrosion Test
Specimens), and test procedures
follow ASTM G111 (Guide for
Corrosion Tests in High Temperature
or High-Pressure Environment, or
Both) and NACE TM0171 (Autoclave
Corrosion Testing of Metals in High
Temperature Water). Standard
practice is to use TFE fluorocarbon
crevice formers with a torque of 0.28
Nm applied.

CO 2, 450 mg/L NaCl, 1 M

NaHCO 3, 20 mg/l
magnesium silicate
Test Solution 2
200C (392F), 40 bar(a)
CO 2, 450 mg/L NaCl, 0 M
NaHCO 3, 20 mg/l
magnesium silicate
Test Solution 3
150C (302F), 20 bar(a)
CO 2, 110 mg/L NaCl, 0.1 M
NaHCO 3, 20 mg/l
magnesium silicate
Test Solution 4
30C (86F), 2 bar(a) CO 2,
0.6 M NaCl, 0 M NaHCO 3,
20 mg/l magnesium silicate

TEST PROGRAM
Test Conditions
Four testing conditions were
determined for identification of
material for the autoclave. The test
program included the design
condition (Test Solution 3) and
variations to design maxima with
respect to the buffering bicarbonate
in the electrolyte and at maximum
pressure (Test Solutions 1 and 2).
Furthermore, a test was included to
simulate conditions of mineralization
at low CO 2 pressure in seawater
electrolyte.
The four testing conditions
determined were:
Test Solution 1
200C (392F), 40 bar(a)
C O R R O S I O N

Test Material Coupon Selection

A range of materials were selected
based on expected corrosion
resistance, general availability (non
proprietary alloys), and past
application experience.
The six materials selected to be
tested in the four test conditions were:
316L (UNS S31603) Austenitic
stainless steel
904L (UNS N08904)
Austenitic stainless steel
2205 (UNS S32205) Duplex
stainless steel
2507 (UNS S32750) Duplex
stainless steel (commonly
called Super Duplex)
Alloy C-276 (UNS N10276)
Nickel Alloy

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EVALUATION OF CORROSION
RESULTS
The results of the four test solutions
are presented in order of increasing
temperature
and
anticipated
increasing corrosivity to facilitate the
evaluation of the corrosion results.
Results of visual examination of
corrosion coupons after each 30 day
period are presented in Table1.
Corrosion rate after 120 days is
presented in Table 1. Condition of
coupons after cleaning, for Test
Solution 2, are presented in Figure 4.
Test Solution 4: 30C, 2 bar (a)
CO2 , 0.6 M NaCl, 0 M NaHCO3 ,
20 mg/l mineral
This chloride concentration is similar
to seawater. If this solution was
normally aerated by exposure to air,
at ambient temperature, pitting and
crevice corrosion of the 316L, 2205,
and 904L would be expected.
The titanium coupon exhibited
surface cracks (Figure 2) after 60
days and after re-examination of the
30-day photo there appears to be
evidence of this cracking. The
second coupon did not crack after
60 days. Currently it is suspected
that the cracking was due to alpha
case possibly due to oxygen
contamination when applying the
weld bead to the corrosion coupon
and inadequate coupon preparation
failed to remove the embrittled
surface. The titanium coupon was
replaced and after 60 days the
second coupon did not exhibit any

surface cracks.
Otherwise, there is no pitting or
crevice corrosion on any material.
The most likely explanation for this
lack of attack is the absence of
oxygen, due to the carbon dioxide
purge. Thus all metals tested would
be considered corrosion-resistant
under these conditions.

than the vapor phase where the pH

should be lower. The measured
weight loss is at least a couple of
orders of magnitude below 0.1
mm/yr, which is the commonly used
definition of corrosion resistance.
Thus all metals tested would be
considered corrosion-resistant
under these conditions.

Test Solution 3: 150C, 20 bar

(a) CO2 , 110 mg/L NaCl, 0.1 M
NaHCO3 , 20 mg/l mineral
This concentration of chloride in a
normally aerated neutral aqueous
solution exposed to air should be
relatively benign, even up to the
boiling point, to any of the stainless
steels used in this corrosion study.
The vapor phase would be more
corrosive because it would allow the
chloride to concentrate on the
corrosion coupon, particularly under
a crevice washer. Chloride stresscorrosion cracking may also be likely.
To the naked eye there is no
visible evidence of pitting or crevice
corrosion on the coupons in either
phase. This is most likely due to the
absence of oxygen. Some
superficial surface etching on the
316L, 2205, and 2507 coupons in
the vapor phase was noted when
examined under magnification. This
etching is most likely due to attack
by carbonic acid. The carbonic acid
in the liquid phase would be
neutralized to some degree by the
bicarbonate and serpentine addition
and thus would be less corrosive

Test Solution 1: 200C, 40 bar

(a) CO2 , 450 mg/L NaCl, 1 M
NaHCO3 , 20 mg/l mineral
As in Test Solution 3, this
concentration of chloride in a
normally aerated neutral aqueous
solution exposed to air should be
relatively benign, even up to the
boiling point, to any of the stainless
steels used in this corrosion study.
The vapor phase would be more
corrosive because it would allow
the chloride to concentrate on the
corrosion coupon, particularly
under a crevice washer. Chloride
stress corrosion cracking may also
be likely.
The Alloy C-276 coupons
exhibited surface cracks after 120
days, Figure 3, the shallow cracks
in the Alloy C-276 are unexpected,
but after discussion with another
metallurgist such cracks are not
unusual in highly stressed coupons
of higher strength material such as
Alloy C-276. This Alloy C-276
coupon was produced from sheet
with actual yield strength of 51,000
psi. The measured mechanical
properties of this material are well

Figure 2. Surface cracks in titanium coupon after 60 days.

C O R R O S I O N

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Figure 3. Surface cracks in Alloy C-276 coupon after 120 days.

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Legend:

Table 1a. Corrosion test results (visual). Athena Project: Hatch Reference H-329175.

NOTE: This table is continued as Table 1b on the following page.

2E MATERIAL SELECTION FOR CARBON DIOXIDE MINERALIZATION PLANT

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Legend:

Table 1b. Corrosion test results (visual). Athena Project: Hatch Reference H-329175.

NOTE: This table is continued from Table 1a on the previous page.

2E MATERIAL SELECTION FOR CARBON DIOXIDE MINERALIZATION PLANT

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within the requirements of ASTM

Specification B-575. Apparently, the
pickling operation for nickel alloys
can preferentially attack the grain
boundaries creating small stress
raisers, and then during a severe
forming operation such as preparing
a U-bend specimen these stress
raisers can open up. The
photomicrograph in Figure 3 shows
that the cracks are intergranular.
Thus these cracks were most likely
the result of the preparation of the
U-bend coupon and not due to the
test environment.
Otherwise, to the naked eye
there is no visible evidence of pitting
or crevice corrosion on the coupons
in either phase. This is most likely
due to the absence of oxygen.
Some superficial surface etching on
the 316L, 2205, and 2507 coupons
in both the liquid and vapor phase
was noted when examined under
magnification. This etching is most
likely due to general corrosion by
carbonic acid as in Test Solution 3.
The measured weight loss is at least
a couple of orders of magnitude
below 0.1 mm/yr, which is the
commonly used definition of
corrosion resistance. Thus all metals
tested would be considered
corrosion-resistant under these
conditions.
Test Solution 2: 200C, 40 bar
(a) CO2 , 450 mg/L NaCl, 0 M
NaHCO3 , 20 mg/l mineral
As in Test Solution 1, this
concentration of chloride in a
normally aerated neutral aqueous
solution exposed to air should be
relatively benign, even up to the
boiling point, to any of the stainless
steels used in this corrosion study.
The vapor phase would be more
corrosive because it would allow the
chloride to concentrate on the
corrosion coupon, particularly under
a crevice washer. Chloride stresscorrosion cracking may also be likely.
However, all the stainless steels
in this test solution are suffering
localized corrosion (pitting and
C O R R O S I O N

Figure 4. Test solution 2 (vapor).

stress-corrosion cracking). The

degree of pitting corrosion on
coupons in the vapor space is much
greater than observed in the liquid
phase. In fact the 904L coupon in
the vapor phase was replaced after
30 days. Surprisingly, there is no
evidence of crevice corrosion in
either phase. In a solution containing
dissolved oxygen and chlorides,
where a stainless steel suffers pitting
corrosion there should be crevice
corrosion, because the corrosion
mechanisms are similar, and crevice

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corrosion occurs more easily since

the crevice restricts oxygen access
making maintenance of the passive
layer more difficult.
Thus none of the stainless
steels are acceptable under these
conditions.

DISCUSSION & CONCLUSIONS

Comparing the results of Test
Solution 1 to Test Solution 2,
bicarbonate appears necessary to
inhibit pitting corrosion and stress

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corrosion cracking in a de-aerated

carbonic acid environment at
elevated
temperatures
and
pressures.
The primary corrosive in all test
solutions is carbonic acid, plus the
possible effect of the chloride
addition. The vapor space is more
corrosive than the liquid space and
this is most likely due to less
buffering of the carbonic acid that
forms in the vapor space.
Since there is no crevice
corrosion observed in Test Solution
2, the pitting corrosion mechanism
must be different than what a
stainless steel would normally
experience in a solution containing
dissolved oxygen. The corrosion
observed may be typical of the
pitting corrosion observed on
carbon steel, since there is no
oxygen to maintain a passive layer.
This may explain why the visible
corrosion on 2507 is quite
substantial when compared to
316L. In solutions containing
dissolved oxygen, 2507 possesses

substantially greater corrosion

resistance than 316L.
Testing was performed in sealed
autoclaves where each test solution
was purged with carbon dioxide and
then a carbon dioxide over pressure
was applied and maintained for the
duration of the test. The absence of
oxygen will prevent a stainless steel
from developing passivity, thus the
absence of corrosion in Test
Solutions 1 and 3 is mostly due to
the absence of oxygen. In a plant
operation there will most likely be
dissolved oxygen present because
it should enter with the feed
materials. How much oxygen may
be present and whether it will be
sufficient to develop passivity on a
stainless steel is unknown. If
passivity is developed, all of the
stainless steels in this study may be
susceptible to pitting corrosion by
chloride ions.
With respect of carbon steels,
the corrosivity of carbonic acid
solutions is increased by the
presence of dissolved oxygen.

Dissolved oxygen accelerates the

corrosion
rate
by
cathode
depolarization by oxygen reduction
(acid solutions):
O 2 + 4H + + 4e - 2H 2O
In the case of stainless steel,
sufficient dissolved oxygen will allow
formation of the passive layer, and
with a fully developed passive layer
stainless steels such as 316L are
immune to attack by carbonic acid
under atmospheric conditions at all
temperatures. However, in the
presence of chlorides there is always
the possibility of localized attack
(pitting corrosion, crevice corrosion,
and stress-corrosion cracking).
In the presence of dissolved
oxygen, the possibility of chloride
stress corrosion cracking in a
neutral media should eliminate
316L, despite its corrosion
resistance demonstrated in Test
Solutions 1 and 3. At minimum,
duplex stainless steel should be
considered for its greater resistance
to stress-corrosion cracking.
When selecting a material of
construction for the autoclave, the
discussion on the effect of dissolved
oxygen, the evaluation of the
corrosion coupons and the Material
Selection philosophy must all be
considered. Since it is not possible
to determine the potential for
localized corrosion in Test Solutions
1 and 3 with the presence of
dissolved oxygen, 2507 should be
preferred for its substantially higher
resistance to localized corrosion, in
particular chloride stress-corrosion
cracking, Figure 5.
Further material testing is
suggested to further validate
materials selected and potentially
identify more economical materials
such as 316 or 2205 for the
commercial application of the
process. The pilot plant autoclave
has been designed to include
coupon racks in the liquid zone in
the first and last compartment. a

Figure 5. Stress corrosion in the drop evaporation test with sodium chloride solution at
120C (248F) showing the stress at which cracking will initiate.

Extracted from High-Performance Stainless Steels, published by Nickel Development Institute,

Reference Book Series No. 11 021, June 2000.

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