SCC in Fuel Ethanol Update:

API White Paper Findings, Survey,

Modeling, Monitoring

Dr. R.D. Kane &

Dr. J.G. Maldonado
InterCorr International, Inc.
Houston, Texas USA
www.intercorr.com
 Background
 Denatured ethanol is used as a fuel
additive for the following reasons:
• Octane enhancer - performance
• Oxygenater – lower emissions
• Extender / Substitute
 It has been used for over 20 years.
 Over the past 10 years, there have
been several episodes of cracking
failure in refinery storage tanks and
piping systems exposed to ethanol.
 To date, approximately 12 cases of
SCC failures have been documented.
 There is speculation of other failures in
a pipeline, barge and rail car. Not
confirmed.
 There has been no reported cases of
SCC by the ethanol producers.
 Additionally, not all end-user refineries
have reported SCC either.
 There was a need for further analysis
of this problem.
Examples of SCC in Fuel Ethanol - 1

SCC in steel tank bottom. Note crack running parallel

to fillet weld in striker plate.
Examples of SCC in Fuel Ethanol - 2

Characteristics of SCC in steel exposed to fuel ethanol, showing

multiple crack initiations and through-thickness propagation in piping.
Examples of SCC in Fuel Ethanol - 3

SCC (produced in Fuel ethanol) in steel metallographically prepared

with grain boundary etch at 500X. Note intergranular cracking features.
 2003 Fuel Ethanol Timeline
 March White paper started
 April Literature review / limited
survey
 August Modeling & extended survey;
phone interviews started
 September Scoping of monitoring study;
Review API White Paper Proofs
 October Site visits & interviews
planned; Monitoring started
(to continue for up to 12
months)
 November Extended survey report
 API Publication 939D –
White Paper Highlights
 Misconceptions:
• Fuel Ethanol is NOT a “commodity”.
• SCC is NOT just a “West Coast” phenomenon.
• SCC does NOT take years to develop.
 Truths:
• High or variable stress is important in SCC.
• Corrosivity tends to increase with water and
decreased pHe – suggests important variables.
• SCC has been observed in the laboratory in field
fuel ethanol samples and in ethanol without
denaturants or inhibitors; using U-bends & SSR.
 API Publication 939D Highlights - 2
 More truths:
• There is evidence of out of specification fuel
ethanol.
• Highly stressed, non-PWHT welds appear
susceptible to SCC.
• SCC in fuel ethanol has many aspects common to
SCC of steel in other environments – ammonia,
CO-CO2, methanol.
• Remedial actions include coatings & PWHT.
 Gaps:
• The metallurgical & environmental variables in
SCC have not been quantitatively identified.
• The relationship between field failures and
laboratory tests has not been established.
 List of Parameters that may Influence the
Corrosion/SCC of Steel in Ethanol
Derived from Ethanol White Paper
Parameter Description
pHe pHe is a measure of the hydrogen ion concentration (acidity)
in a solution. Typically, lower pHe related to increased
corrosivity.
Total Sulfur Sulfur can be present in various forms including inorganic
sulfur components, sulfates and organic sulfur species.
Sulfur is a reactive specie and can promote corrosion and
pitting, particularly in aerated solutions.

Water Studies have indicated that water in alcohol can increase

corrosivity and over select ranges may increase susceptibility
to SCC. The hygroscopic nature of ethanol makes water
pick-up common.
Acidity as acetic acid Acetic acid is a common low level impurity in ethanol. It may
be related to soluble corrosion products and may increase
the aggressivity of the environment.

Sulfate Sulfates are an impurity in certain types of ethanol. Sulfate

residue has been reported in a storage tank exhibiting SCC.
 List of Parameters that may Influence the
Corrosion/SCC of Steel in Ethanol
Derived from Ethanol White Paper
Parameter Description
Chloride A low level impurity in ethanol. Chlorides act to
destabilize normally protective surface films on metals.
Oxygen Ethanol has almost an order of magnitude higher
solubility of oxygen than water which can readily
participate in corrosion reactions.
Temperature Research on SCC of steel in other corrosive
environments (including methanol) indicated that
temperature can substantially change the susceptibility
to SCC.
Steel Limited research on ethanol SCC indicates that the
near weld area of the base metal may have higher
susceptibility to SCC than the base metal away from
the weld.
Electrochemical Susceptibility of steels to SCC in many environments
Potential varies with potential.
 Modeling Activities:
Iron in H2O Potential-pH (Pourbaix Diagram)
Understanding SCC in
Fuel Ethanol, starts with
what we know about
iron in aqueous
solutions. corrosion

Corrosion (and SCC) of

steel is defined by the passivation
stability of Fe and its
corrosion products corrosion
in water (in combination
with other solution
constituents).
immune
We need similar
information for ethanol-
based solutions.
 Modeling Procedure
 InterCorr worked to build a thermodynamic
model of the fuel ethanol environment.
 Through a corrosion alliance with OLI System,
InterCorr used the OLI mixed (non-aqueous)
solvents model, which is directly applicable to
problems in fuel ethanol.
 Similar models to solve practical corrosion
engineering problems; Examples:
• a dehydrated gas stream containing water vapor, glycol-
water aqueous phase, CO2 and CH4,
• a heat exchanger involving microbiologically-influenced
corrosion (MIC) and application of various remedial
techniques.
Modeling in Fuel Ethanol: The Starting Point

Quality Specification for Fuel Ethanol per ASTM D4806

Property Units Specificatio ASTM
n Designation
Ethanol %v min 92.1 D5501
Methanol %v max 0.5 --
Solvent-Washed Gum mg/100 ml 5.0 D381
max
Water Content %v max 1.0 E203
Denaturant Content %v min 1.96 D4806
%v max 4.76
Inorganic Chloride Content ppm (mg/L) 40 (32) E512
max
Copper Content mg/kg max 0.1 D1688
Acidity as acetic acid %m (mg/L) 0.007 (56) D1613
pHe -- 6.5-9.0 D6423
Appearance Visibly free of suspended or precipitated
contaminants (e.g. clear & bright)
Ethanol Case 3 – Max (Cl-; 50 ppm O2)

corrosion
corrosion

passivation
passivation

corrosion
corrosion

immune
immune
 Preliminary Findings
 Within ASTM (Min./Max/) Specification for Fuel Ethanol
the stability diagram does not change appreciably.
 This results in a phase boundary between the active
corrosion and Fe2O3 from pH 4 through 9 (range of
interest).
 System conditions could place the system on this
phase boundary (i.e. active/passive condition) which
could support SCC.
 Work still in progress evaluating other variables and
how to interpret pH vs pHe on these diagrams.
 Monitoring of SCC in Fuel Ethanol

 The goal of this task is to evaluate SCC in

fuel ethanol in plant service environments.
 Highly stresses, welded U-bend specimens
will be employed.
 The task will involve:
• 30 sets of 3 U-bend specimens for “passive”
monitoring for broad covers with minimal
interruption and personnel involvement.
• 2 sets of 3 U-bend specimens for “active”
(online) monitoring in two locations which have
had recent indications of SCC in fuel ethanol.
 Passive Monitoring of SCC in Fuel Ethanol
with U-Bends Specimens

0.75””

1.0”” Mounting Plate – Carbon steel

Bolt Loaded U-bend Specimen
AISI A36, A516-70 or A53GrB
Nut – Carbon steel
Weld Threaded Rod – Carbon steel

1.5”

2.5”
5.0”
 Passive Monitoring Procedures
 One set of three U-bends to be provided for up to 30
monitoring locations.
 A site may have more than one set of U-bends (e.g. low
and high in tank).
 Concepts include:
• Tethering U-bends from cable through gage hole with cable
affixed to gage hole lid
• Locate U-bends in “filter pot” or air eliminator.
 Visual examination of U-bends on 1 to 3 month intervals for
minimum of 12 months.
 Return U-bends to InterCorr after 12 months for detailed
evaluation.
 Interested in participating in API ethanol monitoring
program, contact: R.D. Kane – rkane@intercorr.com
 Active Monitoring of SCC in Fuel Ethanol
with U-Bends Specimens

Three wire
Conax Fitting Steel Fixture
U-bend
Specimens

Weld

Three specimens become

Potted Wires
WE, RE and AE in electro-
chemical probe
Real-Time, Online SCC Monitoring
Configuration of remote corrosion monitoring systems differ from one
installation to the next. But, it can be delivered in various configurations
compatible with remote field or plant operations (up to Class I, Div 2 Group
B, C & D):

Hardwire to PC: Radio Communications:

485, Max. 1200ft

C Radio separation
C
232, 232,
Max. 20ft Max. 20ft

Probe

Remote Monitoring Unit

Power & Communications
Radio Transmitter
 Active Monitoring Procedures
 Similar to passive monitoring except:
 Visual inspection interval not determined.
 Utilize electrochemical parameters to assess
general and localized corrosion, and SCC
tendencies “real-time” as fuel ethanol varies with
loading and unloading operation.
 SmartCET electrochemical monitoring to include:
• Linear polarization resistance (LPR)
• Harmonic distortion analysis (HDA) to assess B value
and its influence on LPR corrosion rate
• Electrochemical Noise (EN) to assess localized corrosion
(SCC) tendencies; with Pitting Factor and various other
statistical parameters related to potential and current
fluctuations versus time.
 Summary
 Fuel ethanol SCC white paper is complete –
API Publication 939D.
 Initial indications suggest that water, aeration, pHe,
potential may be critical factors….other factors may
also play a role in determining electrochemical
potential and/or supporting local anodic attack.
 Initial modeling work indicates that
stability/instability of oxide films that can support
local attack may play a role in SCC.
 Development of monitoring plan is complete.
 The program will include “passive” monitoring with
up to 30 sets of welded, U-bend specimens, and
identification of 2 locations for “active” (real-time)
monitoring: rkane@intercorr.com to join.