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Corrosion Studies Of Raw And Treated Biomass-

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C2012-0001645

Corrosion Studies Of Raw and Treated Biomass-Derived Pyrolysis Oils

James R Keiser(1), Michael Howell, Samuel A Lewis, Sr and Raynella M Connatser

Oak Ridge National Laboratory
Oak Ridge, TN 37831

ABSTRACT

Rapid pyrolysis of biomass generates a liquid with properties that are particularly attractive for
production of hydrocarbons that could be substituted for liquid fuels derived from petroleum.
However, the high oxygen content of the biomass derived liquids presents a number of
problems because of the high water content and the considerable concentration of carboxylic
acids. Measurements of total acid number (TAN) of pyrolysis oil (bio-oil) samples show that
values in the 90-100 range are fairly common. This level of acidity has been shown to cause
corrosion problems that have to be addressed in the selection of structural materials that are
used in the production, subsequent processing, storage and transport of the pyrolysis oils.
Chemical analyses have been performed and laboratory corrosion studies have been conducted
in order to assess the aggressiveness of the raw pyrolysis oil from several sources as well as
the corrosion caused by a bio-oil that has been treated to reduce the acid and oxygen content.
Components of biomass pyrolyzers have also been fabricated from various candidate alloys,
and these components have been exposed for extended periods during operation of the
pyrolyzers. This paper will report on results of these analyses and corrosion studies.

Key words: corrosion, pyrolysis oil, bio-oil, biomass, formic acid, acetic acid, carboxylic acids,
hydrotreated pyrolysis oil

INTRODUCTION

Thermochemical processing of biomass can produce solid, liquid and/or gaseous products
depending on the temperature and exposure time used for processing. The liquid product,
known as pyrolysis oil or bio-oil, offers the potential of a replacement for imported petroleum,
but it also introduces other problems. As produced pyrolysis oil contains a significant amount of
oxygen, primarily as components of water, carboxylic acids, phenols, ketones and aldehydes.
As a result of these constituents, these oils are generally quite acidic with a Total Acid Number
(TAN) that can reach levels as high as 100. In light of this acidity, it is not surprising that bio-oil
------------------------
(1)
Author to whom correspondence should be addressed: keiserjr@ornl.gov or 865-574-4453

©2012 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole, must be in writing to NACE International,
Publications Division, 1440 South Creek Drive, Houston, Texas 77084. The material presented and the views expressed in this paper are solely those of the
author(s) and are not necessarily endorsed by the Association.
 has been reported to be corrosive to many common structural materials.1,2 Despite this
corrosive nature, these oils have a promising potential. If the more acidic components can be
removed from this bio-oil, it is expected that the oil could be blended with crude oil and
processed in existing petroleum refineries. The refinery products could be transported using
customary routes – pipelines, barges, tanker trucks and rail cars – without a need for
modification of existing hardware or construction of new infrastructure components – a feature
not shared by other alternate fuels like ethanol. Studies being conducted elsewhere are
developing methods, primarily some form of hydrotreating, to reduce this acidity by removing
most of the oxygen-bearing compounds.2,3

EXPERIMENTAL PROCEDURE

The current studies consist of characterization of samples of pyrolysis oil, both untreated and
treated, and then measurement of the corrosion rate of selected alloys in the same pyrolysis
oils. The characterization of the bio-oil included measurement of the acidity of the oil,
determination of the concentrations of carboxylic acids, and identification of the other major
components of the bio-oil.

Two types of metallic specimens were used in this study; flat corrosion coupons for
measurement of the general corrosion rate and U-bend samples which are held in a highly
stressed condition in order to determine the likelihood for stress corrosion cracking. Specimens
were fabricated from materials with a range of chromium concentrations, and this chromium
content was expected to be closely related to corrosion resistance. The alloys used in this
study are listed in Table 1 along with their nominal compositions. These materials were
selected because they are common structural materials and are candidates for construction of
systems for the production or subsequent treatment of pyrolysis oil. Carbon steel and 2¼ Cr-
1 Mo steel are relatively inexpensive alloys that are common structural materials for
environments that are relatively non-corrosive and are materials used at generally low to
moderate temperatures. The 300 and 400 series stainless steels contain sufficient levels of
chromium to provide corrosion resistance in considerably more aggressive, higher temperature
environments.

It is anticipated that 50˚C would be the maximum temperature at which raw or untreated
pyrolysis oil would be stored or transported; consequently, the corrosion tests were conducted
at that temperature. One set of specimens was immersed in the pyrolysis oil and a second set
was exposed in the vapor space above the oil. In order to prevent, or at least minimize, ingress
of moisture and oxygen contaminants into the test environments, argon was used as a cover
gas on the test systems that are shown in Fig. 1. Specimens were initially exposed for about
250 hours at which point they were removed from the test system, cleaned, weighed and then
reinserted in the oil for a second 250 hour exposure. Following this second 250 hour exposure,
specimens were exposed for an additional 500 hours, resulting in a total exposure time of 1000
hours. Cleaning consisted of rinsing in acetone, but for the carbon steel specimens, cleaning
included removing a loosely adherent corrosion product from the surface of each of the
specimens. Two of the test systems are shown in Fig. 1, and the arrangement of specimens on
the standard glass sample holder are shown in Fig. 2.4

Table 2 lists the sources of the seven bio-oil samples that were studied, and all but the samples
from Sandia National Laboratories and Pacific Northwest National Laboratory would be
classified as the untreated product of fast pyrolysis of biomass. The sample from Sandia
National Laboratories was not produced under what are normally considered fast pyrolysis
conditions, but the pyrolysis temperature and liquid yield were not typical of a “slow pyrolysis”

©2012 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole, must be in writing to NACE International,
Publications Division, 1440 South Creek Drive, Houston, Texas 77084. The material presented and the views expressed in this paper are solely those of the
author(s) and are not necessarily endorsed by the Association.
 category. The producers of the oil suggested it be considered a product of a “transitional
pyrolysis” process.

The one sample of treated bio-oil that was tested in this project was provided by Pacific
Northwest National Laboratory. This bio-oil was reported to be a mixture of products from a
number of catalytic hydroprocessing tests using fast pyrolysis bio-oil as the feedstock. The
tests are typically performed in a two-stage hydroprocessing system wherein the bio-oil is first
catalytically hydrotreated at lower temperature, around 250°C, to “stabilize” it prior to entering
the higher temperature catalytic hydroprocessing, around 400°C, where the bio-oil is nearly
completely converted to cyclic hydrocarbon products with a residual oxygen content of <0.5
wt%. More information on the hydrotreating process can be found elsewhere.2,3

Heated autoclaves are available for corrosion studies at higher temperatures and/or pressures,
and these systems will be utilized for subsequent testing of fractions of treated bio-oil under
conditions that would be encountered during further processing of the raw pyrolysis oil.

In addition to the laboratory studies, short pipe sections of selected alloys have been welded
together and put into service as the transfer line on the exit of the National Renewable Energy
Laboratory’s (NREL) biomass pyrolysis system. These pipe sections were exposed to
temperatures estimated to be about 550°C, and they were returned to ORNL for examination
following their exposure.

EXPERIMENTAL RESULTS

Pyrolysis Oil Analyses

Seven samples of bio-oil were analyzed to determine the Total Acid Number (TAN), the
concentration of organic (carboxylic) acids and the major organic species. The results of these
analyses are shown in Table 2. The TAN is expressed as the milligrams of potassium
hydroxide required to neutralize the acids in one gram of bio-oil. A capillary electrophoresis
(CE) method was developed to separate the anions of both inorganic acids and organic acids
from the aqueous phase of the pyrolysis liquids. Separations were performed on a CE
instrument utilizing a 75 µm X 60 cm bare fused silica column 30 kV potential, reverse polarity,
and a 5 sec pressure injection. Indirect UV detection was performed at 233 nm because the
buffer system uses a pyridine-dicarboxylic acid electrolyte that absorbs at 233 nm. The pH of
the system was held at 5.4. This method achieved excellent separation of acids and anions
from chloride to C8 and higher carboxylic acids. Figure 3 shows one example of the results of
the electrophoresis characterization of the water soluble extract that was used to determine the
concentration of the organic acids.

Gas chromatography and mass spectroscopy were used to identify the major species in some
of the bio-oil samples. The major peak in the chromatogram was identified as one or more
aldohexoses. Aldohexoses are the basic building blocks of cellulose. Their presence indicates
that the pyrolysis process broke down the cellulose, but didn’t necessarily convert the
constituent sugars to other products.

Laboratory Corrosion Studies

As noted previously, the metallic specimens were prepared from common structural materials
with corrosion resistance in acidic environments ranging from poor to very good. In general, the
more corrosion-resistant alloys contain greater concentrations of chromium, and the cost of
these materials increases somewhat proportionately. Characterization of the effects of
exposure on the alloys was primarily accomplished by determining weight change after 250, 500

©2012 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole, must be in writing to NACE International,
Publications Division, 1440 South Creek Drive, Houston, Texas 77084. The material presented and the views expressed in this paper are solely those of the
author(s) and are not necessarily endorsed by the Association.
 and 1000 hours of exposure. The carbon steel and 2¼ Cr-1 Mo steel specimens developed a
significant corrosion product, and the loosely adherent portion of the corrosion product was
removed from the specimen surface and analyzed using X-ray diffraction.

In six of the seven environments, the carbon steel and 2¼ Cr-1 Mo steel samples experienced
very significant weight changes after the shortest exposure time. Losses ranged from a few
percent to as much as 23% in 250 hours, and losses reached as much as 35% in some
samples after 500 hours. Expressed in terms of sample thinning, assuming weight loss would
continue at a constant rate, calculated corrosion rates were several mm/year for these two
materials and as much as a mm/year for some of the 409 stainless steel samples. In many
cases there were significant differences in the corrosion rate of samples exposed in the liquid
versus the vapor space above the liquid; generally, the samples exposed in the liquid corroded
considerably faster than those in the vapor space. There was reasonably good agreement
between the calculated corrosion rates of the coupons and the U-bend samples. Table 3 shows
corrosion rates calculated for samples exposed 500 hours. To even be considered for service
as a structural material, corrosion rates would need to be less than 0.25 mm/y (0.010 in/y). Of
the materials tested, only the 304L and 316L stainless steel meet that criterion.

Corrosion Product Characterization

A reaction product was observed on the surface of the carbon steel and 2¼ Cr-1 Mo steel, and
this layer was removed from several samples exposed in each of the six untreated pyrolysis
oils. X-ray diffraction was used to identify the compounds present in the reaction product, and
iron formate hydrate was the dominant component as shown in the pattern displayed in Fig. 4.
This appears to be a product from reaction of the metallic sample with formic acid in the
pyrolysis oil. Iron formate would have hydrolyzed when the samples were exposed at room
temperature in moist air.

Although the dominant (crystalline) component of the corrosion product is a result of reaction
with formic acid, there are many other, higher molecular weight organic acids present in the bio-
oil. It is quite possible that some of these other acids would be more aggressive at higher
temperatures and some corrosion could occur with the stainless steels. Future tests will be
conducted at higher temperatures with partially treated oils; the untreated oils begin to
polymerize at temperatures not much above the 50°C test temperature so higher temperature
corrosion tests with untreated oils are not feasible.

Examination of Stress Corrosion Cracking Samples

Although the authors are not aware of any reports of stress corrosion cracking of metallic
materials in pyrolysis oil, it was considered prudent to address this possibility especially
considering the reports of cracking of pipes and tanks used for ethanol service.5 Exposure of U-
bend specimens was the most convenient approach to addressing this concern.

It was unexpected to find through-wall cracking in carbon steel and 2¼ Cr-1 Mo steel specimens
after only 250 and 500 hours of exposure. Three cracked U-bend specimens are shown in Fig.
5, and a micrograph of a cross section of one of the cracked specimens is shown in Fig. 6. Of
particular interest are the many deep penetrations shown in the cross sections which indicate
multiple crack initiation sites. When the stress was relieved as the first crack penetrated the
sample wall, the other cracks stopped advancing and corrosion proceeded to attack the walls of
the cracks in the same manner as the outer surface of the sample. Clearly, further study of
stress corrosion cracking in pyrolysis oil is warranted.

©2012 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole, must be in writing to NACE International,
Publications Division, 1440 South Creek Drive, Houston, Texas 77084. The material presented and the views expressed in this paper are solely those of the
author(s) and are not necessarily endorsed by the Association.
 Field Corrosion Studies
The welded pipe sections as exposed by NREL are shown in Fig. 7a, and the pipe sections
returned from NREL are shown in Fig. 7b. Each alloy was sectioned and examined
metallographically to determine the relative extent of its reaction with the environment.
Micrographs of each of the five exposed alloys are shown in Fig. 8, and it can be seen that most
materials underwent some reaction with the hot pyrolysis oil.

CONCLUSIONS

Samples of pyrolysis oil from seven different sources have been characterized to determine
some properties including Total Acid Number and concentration of carboxylic acids. These
studies showed four of the six samples had significant concentrations of formic and acetic acids
as well as some higher molecular weight carboxylic acids. Only the catalytically
hydroprocessed bio-oil had a nearly insignificant acid content.

Corrosion studies were conducted with these pyrolysis oil samples to determine their corrosivity
toward potential structural materials. Metallic specimens were exposed immersed in the oil as
well as in the vapor space above the oil with the oil at a temperature of 50˚C which was
considered to be the maximum temperature the bio-oil would reach during storage and
transport. Weight change calculations showed significant weight loss occurred in the carbon
steel and the 2¼ Cr-1 Mo samples for all exposures except for the samples exposed in the
hydroprocessed bio-oil. A hydrated iron formate corrosion product was identified on the surface
of these specimens that showed significant weight loss. Calculated corrosion rates for these
alloys were much more than could be tolerated in any system that was expected to last for
years. The stainless steel specimens showed minimal weight change.

Some specimens were exposed with one surface under a tensile stress to determine if stress
corrosion cracking would be an active mechanism. Cracks were found in some of the less
expensive, lower chromium content alloys leading to the conclusion that stress corrosion
cracking is likely to be an active mechanism under some circumstances.

ACKNOWLEDGEMENTS

The authors acknowledge the contributions of Adam Willoughby and John Storey in conducting
these studies, Hu Longmire for metallographic examination, Roberta Meisner for the X-ray
diffraction examinations and Stephen Pawel for reviewing this paper. Contributions of the
pyrolysis oils by the six facilities are greatly appreciated. Research sponsored by the U.S.
Department of Energy, Office of the Biomass Program, under contract DE-AC05-00OR22725
with UT-Battelle, LLC.

REFERENCES

1. Mohan, D., Pittman, C.U., Steele, P.H., “Pyrolysis of Wood/Biomass for Bio-Oil: A Critical
Review”, Energy & Fuels, 20, 3, pg 848-89, 2006.

2. Elliott, D.C., “Historical Developments in Hydroprocessing Bio-oils”, Energy & Fuels, 21, 3,
pg 1792-1815, 2007.

3. Elliott, D.C., Hart, T.R., Neuenschwander, G.G., Rotness, L.J., and Zacher, A.H., “Catalytic
Hydroprocessing of Biomass Fast Pyrolysis Bio-oil to Produce Hydrocarbon Products,
Environmental Progress &* Sustainable Energy, 28(3), 441-449.

©2012 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole, must be in writing to NACE International,
Publications Division, 1440 South Creek Drive, Houston, Texas 77084. The material presented and the views expressed in this paper are solely those of the
author(s) and are not necessarily endorsed by the Association.
 4. Keiser, J.R., Bestor, M.A., Lewis, S.A., Sr and Storey, J.M. “Corrosivity of Pyrolysis Oils”
published in Proceedings of the 2011TAPPI PEERS Conference, October 2-5, 2011, Portland,
OR.

5. Kane, R.D., Maldonado, J.G., Klein, L.J., “Stress Corrosion Cracking In Fuel Ethanol: A
Newly Recognized Phenomenon”, Paper No. 04543, Corrosion 2004, New Orleans, LA, March
28-April 1, 2004.

Table 1
Nominal concentration of alloys used in corrosion studies

Alloy Fe (%) Cr (%) Ni (%) Mo (%) Mn (%) C (%)

Carbon steel Balance -- -- -- 1.0 0.13
2¼ Cr- 1 Mo steel Balance 2.25 -- 1.0 0.4 0.1
409 stainless steel 87 11 -- -- 0.3 0.015
304L stainless steel 70 18.3 9.0 -- 1.7 0.02
316L stainless steel 69 16.4 10.2 2.1 1.6 0.02

Table 2
Properties of pyrolysis oil used in these studies

Source of pyrolysis oil Total Acid Formic acid Acetic acid Biomass feed
Number (TAN) concentration concentration stock
(ppm) (ppm)
National Renewable 86 2400 19000 Oak
Energy Laboratory (NREL)
University of 108 7756 40668 Mixed hardwoods
Massachusetts (UMASS)
Technical Research 66 6490 7778 Forest residue
Centre of Finland (VTT)
Sandia National 14 Wood
Laboratories (SNL)
Anonymous 68

USDA Agricultural 58.5 Switchgrass

Research Center (USDA)
Pacific Northwest National 0.23
Laboratory (PNNL)*

*Catalytically hydroprocessed fast pyrolysis bio-oil

©2012 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole, must be in writing to NACE International,
Publications Division, 1440 South Creek Drive, Houston, Texas 77084. The material presented and the views expressed in this paper are solely those of the
author(s) and are not necessarily endorsed by the Association.
 Table 3
Calculated corrosion rates in mm/year based on 500 hours of exposure at 50°C in
pyrolysis oil from 7 sources. The calculations are based on the assumption that material
would be removed in a fairly uniform manner.

C1018 carbon 2¼ Cr-1 Mo 409 stainless 304L stainless 316L stainless

steel steel steel steel
Coupon U-bend Coupon U-Bend Coupon U-bend Coupon U-bend Coupon U-bend
NREL pyrolysis oil 0.9 2.4 0.2 0.2 0.1 ----- 0.0 ----- 0.0 0.0
Liquid
NREL pyrolysis oil 0.2 1.1 0.1 0.1 0.0 ----- 0.0 ----- 0.0 0.0
Vapor

Univ of Mass 2.6 2.4 3.3 3.3 0.6 0.6 0.0 0.0 0.0 0.0
pyrolysis oil-Liquid
Univ of Mass 2.9 1.7 2.3 1.7 0.6 0.0 0.0 0.0 0.0 0.0
pyrolysis oil-Vapor

VTT pyrolysis oil 2.8 3.1 4.0 4.2 0.7 0.0 0.0 0.0 0.0 0.0
Liquid
VTT pyrolysis oil 0.3 0.9 0.7 1.0 0.1 0.2 0.0 0.0 0.0 0.0
Vapor

SNL pyrolysis oil 0.5 0.4 1.2 0.1 0.8 0.1 0.0 0.0 0.0 0.0
Liquid
SNL pyrolysis oil 0.1 0.2 0.2 0.1 0.0 0.0 0.0 0.0 0.0 0.0
Vapor

Unidentified 2.6 0.2 2.4 2.6 0.0 0.0 0.0 0.0 0.0 0.0
pyrolysis oil-Liquid
Unidentified 0.6 0.1 1.4 1.2 0.0 0.0 0.0 0.0 0.0 0.0
pyrolysis oil-Vapor

USDA pyrolysis oil 0.6 0.6 1.4 1.5 0.8 0.8 0.0 0.0 0.0 0.0
Liquid
USDA pyrolysis oil 0.1 0.3 0.3 0.4 0.0 0.0 0.0 0.0 0.0 0.0
Vapor

PNNL processed 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
oil-Liquid & Vapor

NREL = National Renewable Energy Laboratory

Univ Mass = University of Massachusetts
VTT = Technical Research Centre of Finland
SNL = Sandia National Laboratories
Anonymous = Unidentified source of pyrolysis oil
USDA = United States Department of Agriculture’s Agricultural Research Service
PNNL = Pacific Northwest National laboratory

©2012 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole, must be in writing to NACE International,
Publications Division, 1440 South Creek Drive, Houston, Texas 77084. The material presented and the views expressed in this paper are solely those of the
author(s) and are not necessarily endorsed by the Association.
 Figure 1: Test systems used for Figure 2: Samples on holder used in
corrosion studies corrosion studies

Figure 3: Results of electrophoresis characterization of a typical pyrolysis oil sample

Figure 4: Corroded carbon steel sample and X-ray diffraction analysis of surface deposit
identifying it as iron formate hydrate

©2012 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole, must be in writing to NACE International,
Publications Division, 1440 South Creek Drive, Houston, Texas 77084. The material presented and the views expressed in this paper are solely those of the
author(s) and are not necessarily endorsed by the Association.
 Figure 5: Cracked U-bend samples Figure 6: Cross section of
cracked 2¼ Cr -1 Mo sample

a)

b)

Figure 7: a) Alloy spool pieces sent to National Renewable Energy Laboratory for
exposure in their biomass pyrolysis system, b) Section returned after exposure in
pyrolysis system

©2012 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole, must be in writing to NACE International,
Publications Division, 1440 South Creek Drive, Houston, Texas 77084. The material presented and the views expressed in this paper are solely those of the
author(s) and are not necessarily endorsed by the Association.
 Figure 8: Cross sections of pipe sections that were exposed in the NREL pyrolysis
system showing evidence of attack on the ID of the pipe sections; top row, L to R 310
stainless steel and 316 stainless steel; middle row, L to R 347 stainless steel and Alloy
800H; and bottom Alloy 825.

©2012 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole, must be in writing to NACE International,
Publications Division, 1440 South Creek Drive, Houston, Texas 77084. The material presented and the views expressed in this paper are solely those of the
author(s) and are not necessarily endorsed by the Association.

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