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UNIVERSITATEA PETROL-GAZE DIN PLOIETI

FACULTATEA DE INGINERIE MECANIC I ELECTRIC


INGINERIA EXPLOATRII OPTIMALE A UTILAJULUI PETROLIER
METODOLOGIA CERCETRII TEORETICE I EXPERIMENTALE

STUDIU DE CAZ
Bio-Oil Properties and Effects on Containment
Materials

ef lucr. dr. ing. Doina PETRESCU

PLOIETI
2015

Masteranzi:
Marian-Valentin MITREA
Ionu-Florentin SANDU

Bio-Oil Properties and Effects on Containment


Materials
(Proprietile bio-combustibilului i efectele sale
asupra materialelor n care se depoziteaz)
Ionu-Florentin SANDU

Marian-Valentin MITREA
Universitatea Petrol-Gaze din Ploieti

REZUMAT
Lichidele obinute din biomas ofer un potenial pentru transformare n combustibili
lichizi cum ar fi benzina, cherosenul, motorina i pcura. Totui, bio-combustibilii, creai prin
oricare dintre numeroasele procese, conin concentraii importante de ap i compui organici
n componena crora se afl oxigen. Acizii carboxilici constituie o parte semnificativ din
combustibilii care conin oxigen i acesti compui, n special acizii formic i acetic, fac biocombustibilii destul de acizi. Daca acizii carboxilici nu sunt nlturati, bio-combustibilul poate
crea probleme de coroziune pentru materialele folosite n construirea sistemelor utilizate n
producia, procesarea, transportul i stocarea acestuia.
Au fost dezvoltate tehnici care mbuntesc caracteristicile bio-combustibililor i
studii de laborator legate de coroziune, fcute att cu pri organice, ct i acvifere, pentru a
evalua coroziunea substanelor obinute din biomas. Pe lng aceasta, mostrele au fost
expuse n sisteme de lucru i componentele acestor sisteme, mpreun cu mostrele expuse, au
fost examinate pentru a evalua msura degradrii. Rezultatele acestor studii de caracterizare
vor fi descrise i se vor face recomandri pentru materiale suficient de rezistente n aceste
medii.
Cuvinte cheie: Bio-combustibil, coroziune, acizi carboxilici, acid formic, acid acetic,
cromatografia gazelor, electroforez capilar.

ABSTRACT
Biomass derived liquids offer a potential for conversion into liquid fuels such as
gasoline, jet fuel, diesel, and fuel oil. However, the bio-oils, whether produced by any of a
number of processes, contain significant concentrations of water and oxygen-containing
organic compounds. Of the oxygenates, carboxylic acids constitute a significant fraction, and
these compounds, primarily formic and acetic acids, make bio-oil quite acidic. Unless the
carboxylic acids are removed, bio-oil presents corrosion issues for materials used to construct
the systems used for production, processing, transport and storage of the bio-oil.
Techniques have been developed to improve characterization of the bio-oils, and
laboratory corrosion studies have been conducted with both the organic and aqueous fractions
to assess the corrosivity of the biomass-derived materials. In addition, samples have been
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exposed in operating systems, and components of these systems, as well as the exposed
samples, have been examined to assess the extent of degradation. The results of these
characterization studies will be described and recommendations for materials sufficiently
resistant to these environments will be provided.
Key words: Bio-oil, corrosion, carboxylic acids, formic acid, acetic acid, gas
chromatography, capillary electrophoresis.

INTRODUCTION
For both economic and environmental reasons, there is a major effort around the globe
to make greater use of renewable energy resources. Almost certainly, a variety of renewable
resources will be utilized, and biomass is expected to be a significant contributor in many
parts of the world including the United States. Many processing approaches are being utilized,
including combustion of unprocessed biomass as well as biomass that has been treated to
produce a gaseous, liquid or solid fuel. Each processing method has advantages and
disadvantages, and many studies are underway to overcome the disadvantages and improve
the efficiency of each of these processes. One issue that is common to all the processing
methods is the degradation, generally through corrosion, of the vessels and other components
that are used to contain the processes.
One of the current authors has published several papers addressing the corrosion issues
that have been encountered in production of a gaseous product whether by gasification or
steam reforming. Several of the current authors have published a number of reports describing
studies to address materials in fast pyrolysis or other means to produce a biomass-derived
liquid. These reports describe the analytical techniques developed and used to identify the
corrosive components in the biomass-derived liquids. Laboratory corrosion studies have also
been conducted by the authors to determine the effect of bio-oils on selected alloys typically
used to construct chemical processing systems. The unavailability of appreciable quantities of
some bio-oils as well as the concern that tests conducted with a limited volume of bio-oil
could be influenced by depletion of the corrosive component have led to efforts to expose
samples in biomass processing systems as well as to examination of components from
operating systems.
In an effort to obtain sufficient quantities of bio-oil for corrosion testing as well as for
thorough chemical analysis, fractions of biomass-derived oils were acquired from Iowa State
University (ISU). Two biomass sources were used for production of these bio-oils: red oak
and corn stover. The ISU pyrolysis system separates the biomass-derived products into several
different boiling point fractions. These various fractions have been analyzed and corrosion
tests conducted with the same fractions (when sufficient quantities were available). In
addition, a transfer line from the pyrolysis system has been destructively examined and
corrosion samples are being exposed in the freeboard of the pyrolyzer. This paper describes
some of the analytical techniques and analysis results, as well as the results of the laboratory
corrosion studies. The results from examination of the transfer line, as well as a component
from another liquefaction system, will be described.
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Bio-oil Characterization
Bio-oil produced at ISU from fast pyrolysis of red oak and corn stover was chemically
analyzed by Gas Chromatography/ Mass Spectroscopy (GC/MS). Additional details on the
nature and processing steps of the supplied samples have been previously reported.7 The
column was an HP-5MS (5% Phenyl)-methylpolysiloxane column, 0.25mm inner diameter,
0.25 m film thickness, and 30m length. The carrier gas was ultra high purity helium
(99.9995%) with a constant flow rate of 1.0mL/min. The oven temperature was programmed
at 30C for 2 minutes, followed by a temperature ramp to 200C at a rate of 10/minute,
ending with a temperature hold at 200C for 10 minutes. A filtered, neat liquid sample with a
volume of 1 L was injected onto the column with a split ratio of 1:100 at an injector
temperature of 250C. The MS was set to scan the m/z range from 10 to 300 operating in the
electron ionization mode. Peak identification was accomplished using the GCMS Chemstation
Data Analysis software and by comparing mass spectra to the National Institute of Standards
and Technology 08 mass spectral library.
Borrowing from the petroleum energy industry, new approaches were developed for
accommodating polarity and oxygenation. In order to glean meaningful quantification of total
acid number (TAN) from many pyrolysis oil sample matrices, which are immiscible with the
nonpolar carrier solvent proscribed in ASTM D664, modifications were applied to that
method, henceforth referred to as ModTAN. These modifications include the use of high sonic
energy aqueous extraction techniques and preparation of a hydrophilic titration solvent. In
order to speciate the compounds, specifically the organic acids, present in the bio-oils, two
parallel sample preparations and subsequent analyses are used. First, capillary electrophoresis
(CE) in an indirect ultraviolet detection mode is used to separate the anions (conjugate bases
to the organic acids) produced at high pH during the ModTAN titrations. In parallel, acidified
samples are extracted in a non-polar solvent system for separation of the now-neutral organic
acids via gas chromatography with mass spectrometric detection in the electro-ionization
sampling mode (GC/EI-MS). Finally, in exploratory work to identify some of the apparently
larger molecular weight organic acids in the basic CE runs, that separation approach is
coupled to a mass spectrometer in the chemical ionization mode (CE/CI-MS).

Laboratory Corrosion Studies


Laboratory corrosion studies have been conducted and are continuing with red oak and
corn stover-derived pyrolysis oils to evaluate the corrosion behavior of candidate structural
materials. The majority of the laboratory studies have been conducted with as-produced biooil that was exposed at 50C. The 50C test temperature was selected because that is likely to
be the maximum temperature at which as-produced bio-oil would be transferred or stored, and
because the bio-oils have limited stability at higher temperatures.
The tests at 50C with the bio-oil consist of exposing two types of samples of five
different alloys for a total of 1,000 hours with the samples being removed from the oil and
examined after 250, 500 and 1,000 hours of exposure. Both general corrosion coupons and U5

bend stress corrosion cracking coupons of carbon steel, 2Cr-1Mo steel, 409 stainless steel,
304L stainless steel and 316L stainless steel are used in all tests. Nominal compositions of
these alloys are given in Table 1.
Alloy
Carbon steel
2Cr-1Mo
steel
409 stainless
steel
304L
stainless
steel
316L
stainless
steel

Table 1. Nominal Compositions of Alloys Used for Corrosion Studies


Fe (wt%)
Cr (wt%)
Ni (wt%)
Mo (wt%)
Mn (wt%)
Balance
---------1.0
Balance
2.25
---1.0
0.4

C (wt%)
0.13
0.1

Balance

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----

----

0.3

0.015

Balance

18.3

9.0

----

1.7

0.02

Balance

16.4

10.2

2.1

1.6

0.02

As described in three previous publications,3-5 one set of samples is immersed in the


bio-oil and a second set is exposed in the vapor space above the oil. A water-cooled
condensing column on the test system and a very slow flow of argon cover gas are used to
prevent loss of very much, if any, volatile material. Pictures of two of the test systems and
typical samples are shown in Figure 1.

Figure 1. Pictures of two of the test systems and typical samples

Because these systems require about 2 liters of bio-oil for each test, the need for this
quantity of liquid has prevented testing of some of the fractions because insufficient quantities
were produced. Therefore, only chemical characterization studies could be conducted.
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Sample and Component Examinations


Samples exposed in the corrosion tests as well as samples exposed in operating systems
and components of such systems were thoroughly examined to determine the extent of
degradation, and if possible, the cause of the degradation. The U-bend samples exposed in the
laboratory corrosion tests as well any component in which cracking is a concern are subjected
to a dye penetrant inspection to look for any evidence of cracking on the side of the samples
subjected to a tensile stress. If a significant corrosion scale is present on a sample, the scale is
collected and examined using X-ray diffraction. This technique was used to identify iron
formate as the compound present on the surface of a few carbon steel and 2Cr-1Mo steel
samples as was reported in previous publications.4-6 Following these nondestructive studies,
cross sections are generally cut from the metallic samples for examination of the surface
condition and the subsurface microstructure with the light microscope to help determine the
extent and mechanism of reaction with the environment. If more sophisticated tools are
needed, these sections are examined with the scanning electron microscope and if a more
detailed elemental analysis is needed, the electron microprobe would be employed.

RESULTS
Bio-oil Characterization
Results of measurement of the acidity (ModTAN) and the concentration of carboxylic
acids for the fractions produced by pyrolysis of red oak and corn stover are shown in Table 2.
Table 2. Results of ModTAN and Acid Concentration Measurements on Bio-oil
Produced by Pyrolysis of Red Oak and Corn Stover
ModTAN
Formate content (ppm)
Acetate content (ppm)
Red Oak fraction 1
131.6
299.3
9603.5
Red Oak fraction 2
70.6
2062.4
4857.4
Red Oak fraction 3
149.9
1609.5
20567.2
Red Oak fraction 4
143.7
2568.4
33231.7
Red Oak fraction 5
97.9
Not Available
Not Available
Corn Stover fraction 1
47.0
515.9
4384.9
Corn Stover fraction 2
78.3
503.1
7546.6
Corn Stover fraction 3
133.7
1834.5
16749.5
Corn Stover fraction 4
124.6
Not Available
10607.9
Corn Stover fraction 5
79.3
Not Available
13318.8

These results show that fractions 3 and 4 (the lower boiling point fractions) have
relatively high acidity, and this can be attributed to the high concentrations of formic and
acetic acids.
For the recovery method used in the ISU pyrolysis system, bio-oil is recovered as a
series of stage fractions (SF) with distinct chemical properties using a system of condensers
with controlled coolant temperatures and electrostatic precipitators. Samples included 5
fractions identified as SF1 to SF5.
Stage fractions 1 and 2 were tar like and nearly solid at room temperature. These
fractions contain the higher molecular weight sugars (levoglucosan) and high molecular
weight organic molecules and were deemed unsuitable to be analyzed by the GC/MS method
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described above. Stage fractions 3 and 4 were liquid at room temperature and had a pungent,
smoky odor. Stage fraction 5 was primarily the aqueous phase and was highly acidic, but it
could not be analyzed by GC/MS. To simplify the reporting of the compounds identified in
the bio-oil, the compounds were separated into eight groups based on the distinguishing
properties. These groups are: acids, aldehydes, alcohols, ketones, furans, phenols,
monomethoxyphenols, and dimethoxyphenols.
Figure 2 illustrates the relative concentration of each group of organic molecules present
in stage fractions 3 and 4 for the red oak samples.

Figure 2. Relative concentration of organic compounds identified in red oak bio-oil stage fractions
determined by GC/MS.

Figure 3 illustrates the relative concentration of each type of organic molecules present
in stage fractions 3 and 4 for the corn stover samples. The bio-oil derived from red oak
feedstock appeared to be more acidic than the corn stover and would be expected to be
slightly more corrosive to metallic components. The red oak bio-oil has a fairly even
distribution of compounds amongst the different organic groupings. The bio-oil derived from
the corn stover had a fairly even distribution of compounds among the grouping with the
exception of having an elevated phenolic content in both stage fractions 3 and 4. There does
not appear to be a significant difference between the chemical content of the stage fractions 3
and 4 for both the red oak and corn stover samples.

Figure 3. Relative concentration of organic compounds identified in corn stover bio-oil stage fractions
determined by GC/MS.

Laboratory Corrosion Studies


The bio-oils whose characterization was described in the previous section were also
used in corrosion tests to obtain some indication of their relative corrosion behavior. Because
the available quantity of some of the oils was limited, some fractions had to be combined to
have a sufficient amount of oil to conduct the studies. Results of the corrosion rate
calculations based on weight change of the corrosion samples are shown in Table 3.
Table 3. Calculated Corrosion Rates (mm/year) after 500 Hour Exposure for Samples Exposed in Bio-oil
Produced from Fast Pyrolysis of Red Oak and Corn Stover
Bio-Oil
Carbon steel
2Cr-1Mo steel
409 stainless
304L stainless
316L stainless
Coupon
U-bend
Coupon
U-bend
Coupon
U-bend
Coupon
U-bend
Coupon
U-bend
Immersed in oil
Red
2.96
2.90
2.45
2.61
0.44
0.90
<0.01
<0.01
<0.01
<0.01
Oak #3
& #4
Corn
3.41
3.31
4.97
5.20
3.00
1.76
<0.01
<0.01
<0.01
<0.01
Stover
#3 & #4
Suspended above oil
Red
0.90
1.04
1.61
1.46
0.06
0.08
<0.01
<0.01
<0.01
<0.01
Oak #3
& #4
Corn
1.25
1.25
1.48
1.71
0.20
0.20
<0.01
<0.01
<0.01
<0.01
Stover
#3 & #4

These results indicate the combination of the 3 and 4 fractions is very corrosive to
carbon steel, 2Cr-1Mo steel and 409 stainless steel, particularly for samples immersed in the
bio-oil. The carbon steel and 2Cr-1Mo steel samples suspended above the surface of the oil
experienced corrosion rates far in excess of what could be tolerated for structural components
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expected to be usable for 5 or 10 years. Corrosion tests with the other bio-oil fractions are
planned.

Corrosion Sample and Component Examinations


A short section of 316L stainless steel pipe (shown in Figure 4) from the outlet of the
ISU pyrolyzer was examined to determine the extent of interaction with the vapor leaving the
pyrolyzer at a temperature of at least 500C.

Figure 4. Section of stainless steel pipe from pyrolyzer outlet line

The metallographic examination of the cross section of the pipe section showed some
shallow attack and roughening of the surface (Figure 5).

Figure 5. Micrograph showing condition of surface of pyrolyzer outlet line

The replacement spool piece shown in Figure 6 has been fabricated and provided to ISU
for installation in their system. This spool piece contains short sections of four different
stainless steel type alloys, and this will provide a means for comparison of the performance of
the four alloys.

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Figure 6. Spool piece provided for exposure in the Iowa State University pyrolysis system and fabricated
with sections of four different stainless steel alloys

Another examination that gave very interesting results was conducted on a cracked
316L stainless steel tube fitting from another facility. This fitting was exposed to abnormal
conditions as part of a gasification process that resulted in nonstandard conditions. Chlorinecontaining residue was found in the catalyst as a byproduct of the manufacturing process. This
excessive residue is postulated to have resulted in significant production of HCl. Figures 7-8
show cross-section electron probe microanalysis (EPMA) elemental maps using both energy
dispersive X-ray analysis (EDS) and wavelength dispersive X-ray analysis (WDS) of a region
where extensive cracking had occurred. Scaling attack on the order of 10 microns thick was
observed (Figure 7).

Figure 7. Cross-section backscatter mode image of a 316L stainless steel port connector at a hydrotreater
exit tube after an early trial of a gasification operation process that resulted in nonstandard conditions.

EPMA mapping indicated that the scale primarily consisted of chromium-silicon rich
oxide, but that it also contained S, Cl, and P species. Extensive cracking attack was also
observed (Figure 8), extending hundreds of microns into the 316L alloy.

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Figure 8. Cross-section backscatter mode image (top) of a 316L stainless steel port connector at a
hydrotreater exit tube after an early trial of a catalytic hydrothermal gasification operation process that
resulted in nonstandard conditions. Corresponding elemental maps of the cracked region marked by the
red square (approximate map area) are shown in the bottom images. Black/blue is lowest level of element
and red/yellow is highest level in maps.

The EPMA mapping indicated that this cracking was associated with preferential
penetration of O, S, K and Cl species deep within the cracks. Further EPMA analysis at a
crack tip region showed O, S and Cl at the tip, associated with possible local enrichment of
Cr, Si, Ni, and Ca. It should be noted that such attack is not expected from typical operation of
hydrothermal processing.

CONCLUSIONS
Analysis of bio-oil fractions produced from red oak and corn stover showed the red oakderived fractions had higher concentrations of carboxylic acids than comparable samples from
corn stover.
Corrosion tests at 50C showed the combination of fractions 3 and 4 was very corrosive
to carbon steel, 2Cr-1Mo steel and 409 stainless steel. The 300 series stainless steel samples
showed negligible corrosion rates.
Examination of a 316L stainless steel outlet line removed from service in the ISU
pyrolyzer after an estimated 50 hours showed roughening of the surface and shallow,
localized attack that appeared to be progressing along some microstructural feature, possibly
grain boundaries. A spool piece has been fabricated using short sections of four different
alloys and shipped to ISU for installation on the pyrolysis system to compare the performance
of these four alloys in this high temperature bio-oil environment.
A 316L stainless steel fitting that was subjected to off-normal conditions was found to
have extensive cracking that had the features of chloride stress corrosion cracking. Both
chlorine and sulfur were found at the tips of the finest cracks. The conditions to which this
fitting was exposed would not be expected during normal service, but this failure does
emphasize that a deviation from normal conditions can lead to catastrophic results.

CONCLUZII
Analizele fcute pe fraciile de bio-combustibil obinute din stejar rou i coceni de
porumb au artat c prile de stejar rou aveau concentraii mai mari de acizi carboxilici
dect mostrele comparabile din coceni de porumb.

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Testele de corozine efectuate la temperatura de

50 C

au artat c amestecarea

fraciilor 3 i 4 a fost foarte coroziv asupra oelului-carbon, a oelului cu 2Cr-1Mo i a


oelului inoxidabil 409. Mostrele de oel inoxidabil din seriile 300 au artat grade de
coroziune neglijabile.
Verificarea unei evi de evacuare de la un pirolizator al Universitii din Iowa,
confecionat din oel inoxidabil 316L, scoas din folosin dup aproximativ 50 de ore, a
artat o cretere a rugozitii suprafeei i stratului superficial al materialului, un atac localizat
care pare s avanseze de-a lungul unei zone microstructurale, posibil pe limita dintre cristale.
Un mosor a fost fabricat folosind seciuni scurte din patru aliaje diferite i a fost trimis la
Universitatea din Iowa pentru instalare pe sistemul de piroliz, pentru a compara
performanele acestor patru aliaje n mediul cu bio-combustibil la temperatur ridicat.
Un racord din oel inoxidabil 316L exploatat n condiii speciale a dezvoltat crpturi
ale materialului care aveau trsturi asemntoare cu cele ale coroziunii sub tensiune sub
aciunea clorului. Att clorul ct i sulful au fost gsite la vrfurile celor mai fine crpturi.
Condiiile la care acest racord a fost expus nu pot fi ntlnite n timpul func ionrii normale,
dar aceast defectare evideniaz faptul c o abatere de la condiiile normale de func ionare
poate duce la rezultate catastrofale.
ACKNOWLEDGEMENTS
The efforts of Steve Pawel and Michael Lykins in reviewing this document are
appreciated. Adam Willoughby conducted the corrosion experiments with the bio-oil, and
Tyson Jordan performed the light microscopy examination of the samples. Funding for this
project was provided by the U.S. Department of Energys Energy Efficiency and Renewable
Energys Bioenergy Technologies Office.
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