Storage of Liquefied Anhydrous Ammonia

Advancements in storage tank concepts, materials, welding, and inspection provide owners with new
storage solutions that can improve safety and maintenance of new facilities. This paper explores
these advancements as well as relevant standards, both current and in development. A driver for ma-
terial selection, welding, fabrication, and inspection is ammonia stress corrosion cracking (ASCC).
This subject will also be explored including available solutions to reduce potential for ASCC.

John Blanchard
Principal Engineer Refrigerated Gas Storage
CB&I

Introduction Storage Concepts

S
torage of anhydrous ammonia at low pres- Selection of a storage tank configuration goes far
sure in fully refrigerated, liquefied form is beyond the single wall and double wall type tanks
an efficient, cost effective method of stor- built ten or more years ago. New concepts have
age. Over the past 30 plus years, various tank been developed and international design standards
configurations have been built, all with an excel- defining the concepts have been published.
lent performance record. However, in the mid to API Standard 620 including Appendix R has been
late 1980’s evidence of ammonia stress corrosion used for many years as the basis for design of fully
cracking, (ASCC) was found in fully refrigerated refrigerated liquefied anhydrous storage. This
storage tanks and testing confirmed that it could standard defines two types of tank configurations:
develop at low temperatures. Prior to this, the de- single wall with external insulation; and double
velopment of ASCC, was thought to only be an is- wall with insulation between the inner and outer
sue at ambient temperatures. tanks. The inner tank of the double wall tank can
This paper reviews the various storage concepts have a roof with the outer tank serving solely as an
typically used and the design standards that define insulation container, or can have an open top with
them. It addresses the drivers of ASCC and the suspended deck, making the outer tank the gas re-
methods of detection. It then covers what can be taining vapor boundary. Variations on these con-
done to the storage tank design to reduce the po- cepts have also been designed and built. One such
tential for ASCC and to increase the period be- variation is a double wall concept with the insula-
tween internal inspections. tion on the outside of the outer tank. This concept
requires both tanks to be made from low tempera-
ture materials.
In 1986 the European Equipment and Materials
Users Association (EEMUA), published “Recom-
mendations for the Design and Storage of Refrig-

2007 301 AMMONIA TECHNICAL MANUAL

 erated Liquefied Gas Storage Tanks”, publication
147, that included several new defined storage
concepts. That standard evolved into the BS7777
standard series and this year a new standard,
EN14620, has supplanted the BS standard. These
standards define storage in terms of containment,
primary and secondary. A new API standard, cur-
rently in development, will expand the current API
620 storage concept options to include those cov-
ered by EN14620. A simplified definition of the
three base concepts follows:
1 Primary Container (steel)
Single Containment: Primary liquid and gas con- 2 Secondary Container (steel or concrete bund wall)
tainment are provided by the tank. Secondary 3 Outer shell (only insulation container)
4 Secondary Containment Bottom
containment is provided by a dike or bund. API 5 Nozzles through Roof
620 R single and double wall tanks fall into this
category. Figure 2 –Double Containment Tank

Full containment: Primary and secondary liquid

containment are provided by a double walled tank.
In the event of leakage of liquid to the secondary
containment, vapor generated is contained and a
controlled release may occur through the tank
pressure safety relief vents (PSRV).

1 Primary Container (steel)

2 Secondary Container (bund wall)
3 Outer shell ( vapor & insulation container)
4 Shell/Bottom Nozzles

Figure 1 –Double Wall Single Containment

Tank

Double containment: Primary liquid and gas

containment are provided by a single containment 1 Primary Container (steel)
2 Secondary Container (steel or concrete wall)
tank built inside a secondary liquid containing 3 Secondary Containment Bottom
open top tank. 4 Nozzles through Roof

Figure 3 –Full Containment Tank

These three concepts and variations of them will

be referred to for the remainder of this paper.

AMMONIA TECHNICAL MANUAL 302 2007

 Figures 2 and 3 show over the top inlets and out- aluminum or zinc near welds might be effective7.
lets. In-tank pumps are available for ammonia ser- However, the life of this method would be limited
vice. However, double and full containment tanks and the author is not aware that a practical appli-
can be built with side outlets if in-tank shut off cation of this has been found.
valves are provided and an external collection Research and experience has shown that the corro-
sump is provided for collection of liquid prior to
sion mechanism can be substantially reduced by
the in-tank valve closure. Double and full con- addition of a small percentage of water (> 0.2%)
tainment tanks do not require a dike because the to the stored product and the rate of the corrosion
secondary containment is provided as part of the can be slowed with reduction of temperature.
concept.
ASCC is a time dependant process and is depend-
ant on the oxygen level in solution. Therefore,
Ammonia Stress Corrosion Cracking steps should be taken to remove as much oxygen
As noted above, ASCC was found in fully refrig- as possible from the tank prior to introducing liq-
erated anhydrous ammonia storage tanks in the uid during tank cool-down. Purging of the tank
1980’s. The research performed afterwards con- can be done in two steps. First, a nitrogen purge
firmed the potential. Even though research has is performed to reduce the ammonia to oxygen ra-
shown that the potential is low, the consequences tio below flammable limits (10 to 12%). Next, a
of an ammonia tank failure are too severe to ig- warm ammonia purge is performed to reduce the
nore. remaining oxygen level to as low a level as practi-
cal. With an optimal purge set-up and procedure,
Since the 1980’s most ammonia tanks have been reaching 0.5% oxygen has been achieved. How-
internally inspected and most owners have a pro- ever, an optimal purge process may not be possible
gram of periodic inspection of their tanks. How- on some tanks. Initial introduction of liquid am-
ever, internal inspection requires the tank to be monia with a higher than normal water content, or
taken out of service, the liquid removed, the tank even placing a small amount of water in the tank
warmed up, the ammonia gas purged out and the prior to introducing ammonia, has been sug-
ammonia concentration reduced to near zero. gested7. This is intended to tie up free oxygen en-
Once the inspection is completed, the process is trained in the liquid during the cool-down process.
reversed to put the tank back into service. This Most of the remaining gaseous free oxygen will
process is very expensive, but the largest deterrent remain in gas form and can be reduced through the
to performing an in-tank inspection is that the boil-off gas recovery process. For processes that
process can increase the potential for the very cannot tolerate water, the reduction of oxygen in
thing that the inspection is intended to detect by the tank prior to introducing liquid ammonia is
introducing oxygen into the tank. even more important.
The ASCC mechanism is complex and not fully The last of the three drivers, stress, cannot be
understood, but some aspects of the process are eliminated in a storage tank, but the magnitude of
known. Stress corrosion cracking must have three stress can. This area will be explored further in
things present to occur. There must be a corro- the topics below.
sion driver, there must be oxygen present, and
there must be tensile stress in the material.
Storage Solutions to Reduce the Potential for
The ASCC process has been determined to be an- ASCC
odic. Thus cathodic protection would be expected
to be beneficial. However, the conductivity of There are several things that can be done with the
ammonia is so poor that suspended anodes are in- storage tank design that can reduce the potential
effective. It has been suggested that flame sprayed

2007 303 AMMONIA TECHNICAL MANUAL

 for ASCC. Magnitudes for drivers found in the tanks with 38ksi (260 MPa) and 50ksi (345MPa)
list below are discussed later in this paper. minimum yield materials with good results from
• The material selected for direct exposure to both materials.
ammonia liquid should have a low yield stress.
Increased material toughness improves crack ini-
• The material selected should have a refined
tiation and propagation resistance. Since a way to
grain structure and low impurities.
totally eliminate the potential for ASCC has not
• The weld material strength used should be
been found thus far, the potential for cracks to
matched to the plate material strength.
form must be expected. Increased toughness in-
• The weld material and process should have
creases the size of flaw, or crack, that the material
low hardness.
can tolerate safely. Thus, increased toughness
• Initial tank inspection should leave the tank
provides a higher margin of safety against brittle
free of crack initiation locations.
fracture and, as discussed below, increased tough-
• The material chosen should have increased
ness can also facilitate increased inspection inter-
toughness.
vals through Risk Based Inspection methods.
Plate Material Selection Increasing plate material toughness to a level that
can allow through thickness cracks without unsta-
Research and experience has shown that the po- ble crack propagation, leak-before-break theory, is
tential for ASCC is reduced with low yield stress possible. However, weld metals and weld proce-
and low hardness materials. Low material yield dures do not provide the same level of toughness
stress reduces the residual weld stresses which are as in plates, and residual stress patterns are such
one of the key drivers to ASCC. Low hardness that 100% assurance of a leak-before-break design
also increases local residual stress levels and crack may not be able to be assured. For example, if
initiation locations. Common practice is to set the ASCC formed parallel to the longitudinal weld, it
minimum specified yield stress of the plate material could follow the surface residual stresses forming
at less than 52 ksi (360 MPa). However, when in- a long shallow crack. If that occurred when the
creasing the toughness of this material is specified tank remained at a low liquid level, subsequent
to a mill, the strength of the material is sometimes raising of the liquid level could cause the crack to
increased by the mill to levels significantly above propagate through thickness and reach a critical
normal levels. Since the residual stress levels are size before leaking. Development of weld proce-
connected to the actual yield stress, it is clear that dures that assure limited longitudinal crack propa-
a maximum yield stress must also be specified. A gation combined with increased material and weld
value of 65 ksi (450 MPa) is suggested but will be toughness might lead to a leak-before-break solu-
dependant on the material selected and the mill tion.
producing the steel.
Increasing material toughness to the level of crack
Reducing the material minimum specified yield arrest would also provide a leak-before-break de-
stress lower than the 52 ksi (360 MPa) level noted sign. Published Document PD 7777 was written
above has been specified by some owners in an at- as an extension of BS7777 to allow tanks to be
tempt to reduce the residual stress level and thus hydrotested at a level below the design liquid level.
the ASCC potential further. The ASCC threshold The premise behind the document is to require
stress level is not known but is likely to also be crack arrest materials. The approach requires the
connected to material purity and grain refinement nil-ductility temperature, NDTT, to be 40oC colder
as well as material toughness and hardness. than the required design metal temperature. For
Therefore, reducing the minimum specified yield ammonia that would require an NDTT of -100oF
stress may do little more than increase the initial (-73oC). Satisfying that requirement would exceed
thickness and cost of the tank. CB&I have built the limits of C-Mn steels and would require plate

AMMONIA TECHNICAL MANUAL 304 2007

 and weld materials such as C-Ni steels not previ- in-service inspections should be made by plant per-
ously used in ammonia service. These materials sonnel on a regular basis. Periodic external in-
usually have much higher yield strengths and weld spections by an engineer experienced in the design
hardness. Thus, through thickness cracks could be and operation of ammonia tanks should be made
tolerated, but the potential for ASCC would be in- every 2 to 5 years. An internal tank inspection by
creased considerably. an engineer experienced in the design and con-
Stress relief, both thermal and mechanical, can re- struction of refrigerated ammonia tanks should be
duce the residual stresses and thus reduce the po- made 5 to 10 years after the tank is initially placed
tential for ASCC. Large shell nozzles in thick ma- in service. The next internal inspection is set
terial, which have higher local membrane stress based on the findings from the first inspection.
levels in addition to residual weld stresses, are re- Detecting ASCC in its early stages normally re-
quired by API 620 to be thermally stress relieved. quires a very sensitive inspection process. Wet
However, stress relief of smaller nozzles and noz- florescent magnetic particle inspection (WFMT),
zles in thin shells is not required by API 620. Re- has been considered the best method available.
quiring all shell nozzles to be stress relieved would Tank inspections in the last 20 years indicate that
improve their resistance to ASCC. Although it is all internal surface welds exposed to liquid ammo-
impractical to thermally stress relieve a large tank, nia should be investigated and that typical cracking
hydrostatically testing the tank at the design liquid is transverse to the weld with the initiation point in
level provides a partial mechanical stress relief of the weld or heat affected zone (HAZ). Areas
the vertical welds due to the difference in specific where temporary erection attachments were re-
gravities of ammonia and water, (0.682 to 1.0). moved may also produce findings. Since WFMT
is more sensitive than the inspection required by
Weld Material and Weld Procedures the design standard API 620 R, the initial internal
inspection should require the same level of inspec-
Selection of weld metal and weld procedures is a tion as will be used for later internal tank inspec-
balancing act. Weld materials that match the tions.
strength of the base plate materials generally will ASCC initiates at locations of high stress and ma-
produce lower residual stresses and lower hard- terial flaws. The potential for ASCC initiation can
ness. However, available weld materials with low be reduced by reducing the size of flaws remaining
strength properties generally produce lower tough- after tank erection. This can be done by increasing
ness at -30oF (-34.5oC). Weld materials with vari- the weld inspection sensitivity.
ous amounts of nickel produce higher toughness
welds. However, higher residual stresses and Almost all ASCC cracks found during inspections
hardness can accompany use of these materials and are shallow and can be ground out, though some
thus can potentially increase the rate of ASCC. cracks are deep enough to require a weld repair.
Weld repairs can introduce new locations for
The best solution is to match the weld material ASCC to start. Thus weld materials and proce-
strength as close as possible with the base plate dures need to be selected to minimize high residual
material and to apply weld procedures and plate stresses and hardness. Another approach, which
selection that will produce higher toughness and would allow grinding out of almost all ASCC find-
low hardness. ings, would be to add a corrosion allowance to the
shell plates.
Inspection

After placement into service, ammonia tank in-

spections should consist of three levels. Routine

2007 305 AMMONIA TECHNICAL MANUAL

 Risk Based Inspection In-service Inspection
API 653 provides guidance for extending the pe- Acoustic emission (AE) testing has advanced in
riod between internal inspections. Application of recent years and has been applied to detect ASCC.
Risk Based Inspection (RBI) is considered a viable However, crack size cannot be accurately deter-
method of evaluating the inspection interval for in- mined with this method and in several cases pre-
ternal inspections. The method leads to evaluation dictions of cracking have turned up false upon sur-
of crack growth rate and how large a flaw that can face inspection. It is the author’s opinion that this
be tolerated. That evaluation process normally in- method cannot detect ASCC until cracks grow to
volves application of fitness for service methods a significant size. Thus, AE testing could be part
defined by API 579. of a RBI based inspection program by increasing
Most tanks in service today have been built to base the material toughness level to match the minimum
design standard notch toughness requirements. flaw size that can be reliably detected with the AE
Specifically, the toughness level of the materials process.
and welds combined with the inspection methods AE testing has been employed on single wall tanks
and acceptance criteria applied, cannot be deter- by placing probes through the external insulation.
mined to meet levels higher than the minimum Placing probes on the inner tank of a double wall
needed for the structure unless the criteria applied suspended deck tank has not been done, due to the
during tank erection was set higher than required unavailability of probes that can be placed perma-
by the standard. Therefore, RBI applied to a stan- nently in an ammonia environment.
dard API 620 tank will not likely provide any new
information that would allow the inspection inter-
Additional Considerations
val to be increased on most existing tanks.
Application of the RBI process thus requires the Most of the previous discussion has centered on
application of materials, and welding processes ASCC, its detection and what can be done to re-
that have a higher than minimum level of tough- duce the potential for it. However, there are many
ness. The RBI process will also be aided by re- other conditions that should be considered in the
ducing the maximum acceptable flaw size as dis- selection of the storage tank configuration.
cussed under Inspection above. EN 14620 includes the following for evaluation of
For new tanks, incorporating RBI into an inspec- tank type:
tion program requires a higher material toughness • Natural external hazards such as wind,
margin and a smaller initial flaw size. Initial sur- and seismic
face defects can be reduced to a very low level by
applying the same method that would be applied • Infrastructure external hazards such as fire,
during the first internal service inspection, WFMT projectiles, and blast overpressure waves
examination. 100% of shell and bottom welds from adjacent facilities
should be inspected. In addition, vertical welds • Internal considerations such as overfilling
should be examined by the ultrasonic inspection
method, UT, found in API 620 Appendix U. Ra- • Operational component failures such as
diographic inspection has poor sensitivity to de- frost heave,
tecting planar flaws; UT examination provides a • Consequences of failure such as vapor ex-
basis for establishing an initial flaw size necessary posure, and fire.
for the procedure.
External hazards can be addressed by selection of
the secondary containment type, material and de-
sign. For example, redundancy can be provided

AMMONIA TECHNICAL MANUAL 306 2007

 against a seismic failure by selecting a double or 3. Materials selected for the primary liquid
full containment type tank. A blast or vapor cloud container should have a minimum specified
ignition pressure wave, or projectile can be with- yield stress of less than 52 ksi (360 MPa)
stood by a double or full containment type tank and should be purchased with a maximum
through material selection of the secondary con- yield stress of approximately 65 ksi
tainment. (450MPa).
Full containment tanks are the best solution for 4. Weld material and procedures should be
controlling vapor releases due to internal overfill- selected to match the base metal strength
ing and leaks from the inner tank. properties and to maintain low hardness.
Consequences of a primary tank failure can be re- 5. Internal surface inspection should include
duced or eliminated by reducing the rate of vapor WFMT of all shell, bottom welds, and
generation from the spilled liquid. While the den- temporary attachment areas.
sity of pure anhydrous ammonia is lighter than air, 6. Vertical shell butt welds should be in-
anhydrous ammonia will combine with available spected by the UT method in API 620 Ap-
atmospheric moisture forming aqueous ammonia pendix U in place of the normal RT
and will likely include entrained liquid droplets. method.
As the cloud forms, the aqueous ammonia vapor
could become heavy enough to remain close to the 7. A corrosion allowance of approximately
ground. Thus, it is important to contain vapor re- 1/16” (1.5mm) should be considered for
leases or to keep them to a very slow rate. primary liquid containing shell plates to fa-
cilitate grinding out ASCC found during
inspections.
Typical Ammonia Tank Design Parameters
8. All shell nozzles should be thermally post-
Appendix A contains typical tank design parame- weld heat treated.
ters. Values exceeding those listed are possible
9. Insert type fittings should be minimized to
but not typical. The table is intended to provide
eliminate restraint type residual stresses
guidance for initial selection of an ammonia tank.
caused by installation methods.
10. The inner tank should be hydrostatically
Recommendations
tested to its full design liquid level.
The following recommendations will reduce the 11. The tank should be purged to a target of
potential for ammonia stress corrosion cracking 0.5% oxygen content prior to introducing
and will facilitate the application of RBI methods liquid ammonia during commissioning.
to increase inspection periods.
12. Tank foundation heating system should be
1. A full containment configuration provides designed for 100% redundancy and should
the lowest risk solution. The tank can be allow for element replacement.
built with the insulation between tanks or
external to the outer tank. If the later is
selected, annular space drains are needed
to drain off aqueous ammonia formed in
the early months after tank erection.
2. The material selected and production weld
testing should have higher toughness than
required by API 620 R to facilitate RBI.

2007 307 AMMONIA TECHNICAL MANUAL

 Appendix A

Tank Design Parameters

Typical Tank Design Parameters

Anhydrous Ammonia
Gross Capacity 10,000 to 50,000 MT
Design Pressure 1.0 to 4 psi
o
Design Metal Temperature -35 F
o
Operating Temperature -28 F
Boil-off (Single wall Tank) 0.025 to 0.05 % Gross Contents / Day
Boil-off (Double wall Tank) 0.015 to 0.04 % Gross Contents / Day

VAPOR VAPOR LIQUID HEAT OF

SPECIFIC HEAT
MOLECULAR BOILING PT DENSITY DENSITY at DENSITY at VAPORIZATION
FLUID at 59 F & 1 atm
WEIGHT at 1 atm at 70 F & 1atm BOILING POINT BOILING POINT at BOILING PT
(BTU/lb-F)
(lb/cu ft) (lb/cu ft) (lb/cu ft) (BTU / lb)

-28.03 F
Ammonia 17.032 0.523 0.0432 0.0556 42.58 588.6
-33.35 C
Nitrogen 0.0724

AMMONIA TECHNICAL MANUAL 308 2007

 Appendix B
References
1. Australian Standard 2022-1983, Anhydrous 9. Guidance for the Large Scale Storage of
Ammonia –Storage and Handling Fully Refrigerated Anhydrous Ammonia in
2. Stress Corrosion Cracking of Different the UK, 1997
Steels in Liquid and Vaporous Ammonia, L. 10. Risk Based Assessment of a 25,000 Ton
Lunde and R. Nyborg, Institute for Energy Ammonia Tank, by D. Daly, Cytec, et al,
Technology, Norway, published in Vol. 43, Presented at the 46th Annual Safety in Am-
No. 11, Nov. 1987 issue of Corrosion - monia Plants and Related Facilities Sympo-
NACE. sium, Montreal, Canada, Sept. 2001
3. Large-Scale Ammonia Spill Tests by H. C. 11. Recommendations for safe and Reliable In-
Goldwire, Jr., Lawrence Livermore National spection of Atmospheric, Refrigerated Am-
Laboratory, CEP April 1986. monia Storage Tanks, European Fertilizer
4. Stress Corrosion in a 12K Tonnes Fully Re- Manufacturers Association, 2002
frigerated Ammonia Tank by J. R. Byrne 12. API Standard 653: Addendum Nov., 2005,
and F. E. Moir, Vulcan Engineering (UK) Tank Inspection, Repair, Alteration, and Re-
and R. D. Williams, BASF Chemicals, Ltd. construction.
(UK), presented at the 1988 Ammonia
13. EN 14620 Parts 1 through 5: 2006, Design
Safety Symposium, August 1988, Denver,
and Manufacture of Site Built, Vertical, Cy-
CO.
lindrical, Flat-Bottomed Steel Tanks for the
5. Inspection of an Anhydrous Ammonia At- Storage of Refrigerated, Liquefied Gases
mospheric Storage Tank, by Syed B. Ali and with Operating Temperatures between 0 oC
Robert E. Smallwood, American Cyanamid, and -165 oC.
presented at the 1990 Ammonia Symposium,
AIChE Conference, San Diego, CA (AIChE
Paper 989).
6. Stress Corrosion Cracking of Carbon Steel
Storage Tanks for Anhydrous Ammonia, by
L. Lunde and R. Nyborg, Institutt for Ener-
giteknikk, Norway, presented at The Fertil-
iser Society in London, 17 October, 1991.
7. Measures for Reducing SCC in Anhydrous
Ammonia Storage Tanks, by R Nyborg, and
L. Lunde, AIChE Ammonia Symposium, Pa-
per 1e, 1994
8. Stress Corrosion in Ammonia Storage-
Vessels and its prevention, by J. Brozda, The
Welding Institute, Welding International,
Vol. 9, No 5, 1995.

2007 309 AMMONIA TECHNICAL MANUAL