CORROSION: IS IT A THREAT TO PIPELINING BIOETHANOL?

Dr. Russell D. Kane

iCorrosion LLC
2318 Huldy Street
Houston, Texas 77019
russ.kane@icorr.net

INTRODUCTION

Much of the experience with pipelining conventional hydrocarbon-based fuels is based on years of
research, testing, and is supported by substantial manufacturing and service experience. Due to the
relative recent nature of some alternative fuels and their scale-up to mass production, these fuels may be
potentially variable and present corrosion issues that need to be handled during research, development,
scale-up in an effort to reduce in-service problem once in commercial production and transportation.
This paper describes the rapid development of fuel grade ethanol (FGE) and potential challenges to its
transportation via pipelines.

BACKGROUND

The projected trends for production of FGE for use in automobile engines as a gasoline oxygenate,
extender or replacement is shown in Figure 1.1 This trend shows a nearly ten-fold increase in world
production of FGE over the next 20 years. In recent years, the USA has exceeded long-time producer
Brazil as the leader in bioethanol production (See Figure 2).2 The anticipated growth of the use of FGE
ethanol in ethanol fuel blends will eventually exceed the capability to deliver this product via
conventional channels (e.g. tanker trunk, rail car and barge) and delivery of FGE by pipeline has been
initiated in the USA.

Just as significant, a recent survey of FGE storage and handling experience in the USA conducted by the
American Petroleum Institute (API), documented over 30 failures attributed to ethanol stress corrosion
cracking (eSCC) in steel tanks, piping, pipeline and related equipment in FGE over the period 1990
through 2010.3-5 If not properly understood and mitigated in the near term, failures and leaks in pipelines
and associated equipment due to eSCC pose a threat to being a serious detriment to attaining future
ethanol demands. This paper will review current research findings and industry experience on eSCC in
fuel ethanol.

Historically, FGE has been produced in two forms. It is not sold with zero water content. In the U.S., it
contains up to 1 percent water and other constituents as mentioned in the ASTM D4806 standard.6
Denatured ethanol with less than about 0.5 percent water is considered “anhydrous ethanol”. Ethanol
with higher water content (up to 5-7 percent) is usually referred to as “hydrated ethanol”. Such hydrated
ethanol is uncommon in the United States but has been used as a fuel in Brazil. The Brazilian
automotive market has evolved over time to include flex-fuel vehicles that can run on hydrous FGE or
“gasohol” (gasoline, anhydrous ethanol blends) depending on market conditions, which for at least the
past decade has favored the latter.
ETHANOL SCC FIELD SURVEY

In 2003, the survey of field experience was initiated by this author as part of a multi-part development
effort by the American Petroleum Institute (API) Refining Committee, Subcommittee on Corrosion and
Materials. This study was initiated because of a growing number of experiences with failures of steel
equipment in FGE service that needed to be examined and critically reviewed and to provide an
assessment of the potential economic impact of this problem to the petroleum industry.

In April 2003, a “white paper” based on this initial study was published by API as Technical Report
939-D in September 2003.7 It revealed that documented failures of steel equipment in fuel ethanol were
conclusively associated with a phenomenon known in the corrosion community as stress corrosion
cracking (SCC) caused by the interaction of tensile stress and localized corrosion of the steel in FGE
(See Figure 3). The causative agent (ethanol itself or one of its constituents) was not readily apparent.
Since this initial survey, substantial research has been undertaken to further understand the phenomenon
of ethanol SCC (eSCC) of steel equipment in FGE.

Including the results from the entirety of the API ethanol SCC surveys (2003 through 2010), over 30
occurrences of eSCC in steel equipment have been documented (one involving a pipeline) and
categorized by equipment/application type are indicated below5:
 Tank floor plates seam welds – 7 cases
 Tank floor/sidewall fillet welds – 3 cases
 Tank sidewall 1st course butt weld – 3 cases
 Tank floating roof seam welds – 3 cases
 Tank nozzle – 1 case
 Tank roof springs – 2 cases
 Shop built tank in E85 service – 1 case
 Facilities piping/fittings – 8 cases
 Facilities piping/supports – 2 cases
 Pipeline – 1 case
 Ancillary equipment handling equipment – 2 case

Many of these instances of failures and leaks involved multiple occurrences of eSCC. All but one case
was in service exposed to FGE. The one case not in FGE took place in E85 (an ethanol fuel blend with
85% FGE) and was complicated by the presence of pitting to the tank that occurred while in prior waste
oil service. Time to failure of steel equipment by eSCC ranged from 3 months to over 10 years from the
date when the equipment was placed in FGE or ethanol fuel blend service. The reasons for this apparent
disparity may be related to specific conditions of stress (residual and applied), plastic deformation of the
steel, and severity of the ethanolic environment with respect to eSCC.

Cracks in steel equipment have been characterized metallurgically as primarily intergranular (cracks
propagating between metallic grains) and brittle in nature (See Figure 4), which is in contrast to the
normal ductile behaviour of steels found in normal pipelines and tanks. However, in some cases, mixed
mode (transgranular / intergranular) failures have been noted arising from eSCC.

Stress is a most dominant factor in SCC in fuel grade ethanol. Cracking has been reported in the region
around non-PWHT welds, areas of stress concentration (fillet welds at lap seams and tack weld with
external or internal supports) and other highly stressed components (roof springs). Flexural loading
common in tank bottoms, roof springs and potentially other locations may also promote eSCC. Sharp
stress concentrations, local plasticity, and tank loading and/or unloading events may impart locally high
stresses and dynamic stresses that increase the likelihood of eSCC and need to be avoided in design and
fabrication of ethanol handling systems.

One occurrence of a steel pipeline exhibiting eSCC was documented in the API work. The pipeline was
not a major cross country line, but a short segment used for transport of FGE and other hydrocarbon
products between a west coast terminal and a refinery over a distance of several miles. Reports were that
the location of eSCC was in a bend that resulted in plastic deformation and high stress in the pipeline,
which is characteristic of locations where eSCC has typically been found to occur.

While some out-of-specification ethanol was found (particular concern is now with chloride
contamination that appears to lead to accelerated cracking), eSCC has occurred in FGE that appears to
conform to applicable national standards.7-8 Further work is needed in this area to examine the extent of
this effect in producing field failures.

Cracking has occurred in steel equipment dedicated to handling domestic (USA) ethanol and in
equipment handling ethanol from both domestic and foreign sources. All SCC failures documented thus
far (with one exception) were in domestic (USA) facilities; one still under investigation appears to have
arisen in Europe, but where the FGE came from a source in the USA. Despite long service history in
Brazil with anhydrous and hydrated FGE, there has been no evidence identifying eSCC in ethanol
handling systems in Brazil (with bioethanol made from sugar cane versus corn-based ethanol in the US).

SCC failures were for the most part in fuel ethanol distribution systems in mid-stream storage facilities,
and at end-user ethanol/gasoline storage and blending locations. No eSCC failures have been reported
thus far associated with FGE at ethanol manufacturing facilities or after the FGE is blended with
conventional gasoline (E10).

A variety of remedial actions are being used to resist SCC of steel equipment in ethanol service, which
include application ethanol resistant internal coatings in storage tanks and use of PWHT and stress relief
in piping systems. Industry guidelines for identification, repair, and mitigation of cracking of steel
equipment in FGE service have now been developed and a set to be adapted to handle the needs of
pipeline operations.9

ON-GOING RESEACH AND DEVELOPMENT FOR PIPELINES

The abovementioned remedial measures for eSCC are not generally compatible with pipeline systems.
Other techniques are being developed, and through on-going research, have shown promise for eSCC
mitigation in pipeline operations. They include: deaeration of FGE or use of chemical additions that
increase pHe of FGE, scavenge dissolved oxygen in FGE, or inhibit the onset of eSCC.

Figure 5 shows a summary of the eSCC crack growth rates for ethanolic environments involving
chemical additives. Low values of crack growth rate are preferred and the best case is to have no crack
growth (0 mm/s). The tests were performed with sodium sulfite (SoS), ethylene glycol dimethyl ether
(EGDME), 2-metyoxyethanol (2-MOE), diethanolamine (DEA), hydrazine (HYD), and ethylene glycol
(EG) in the concentration range between 100 to 1000 ppm.10-11

Crack growth rates for ethanol SCC obtained using SSR methods typically show crack growth rates in
the range of 1 x 10-6 to 4 x 10-6 cm/sec. Other studies have shown that for borderline conditions, crack
growth rates may be as low as 10-8 cm/sec. The overall range of rates suggests that the time to failure of
operating equipment is in the range of months not years for susceptible conditions, but that conditions of
marginal susceptibility may require exposure periods of years.12 In laboratory SCC tests, threshold stress
intensities for ethanol SCC range from 35 to 60 ksi(inch)-1/2 and vary with the composition of the
ethanolic environment.12 This range is higher than commonly found for other environmental cracking
mechanisms and is consistent with the field experience which has shown that all systems do not exhibit
eSCC, but that cracking is often associated with designs and equipment with high tensile stresses and
plastic deformation of the steel.

GOING FORWARD

Keep in mind that only the most salient technology and findings, as currently understood, are
summarized here. Ethanol SCC is an area of active research on multiple fronts and evolving toward
development more data and guidelines for pipeline applications. Much of this work is focusing on a
more in depth understanding of the applicable cracking mechanisms, effects of residual stresses, welding
crack growth rates and threshold stress intensities for eSCC and on the influences of important
environmental variables of deaeration, inhibition and ethanol composition.

For example, recent studies have shown the effects of blending of FGE with gasoline as may be
experienced in pipeline transmixtures that can occur naturally when batching FGE with gasoline. As
shown in Figure 6, no eSCC was observed in gasoline (E10 blends), but eSCC susceptibility increased
rapidly with increasing ethanol concentration for E20 (20% ethanol – 80% gasoline) and higher blends.
E30 (30% ethanol – 70% gasoline) was nearly as potent an SCC agent as neat FGE (E95). Additionally,
no eSCC has been observed in FGE-gasoline blends with less than 1% oxygen in the cover
atmosphere.11

As the database on eSCC builds from laboratory research and field experience surveying, the
understanding of the mechanisms of this SCC phenomenon has increased and techniques to potentially
mitigate the normal corrosive action of ethanolic service environments are now being developed. Further
research and studies are still in progress and will be used to increase the integrity and reliability of
pipeline systems for transportation of FGE and ethanol fuel blends.