Fuel 182 (2016) 154160

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Fuel
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Full Length Article

Storage performance of bio-oil after hydrodeoxygenative upgrading with

noble metal catalysts
Shinyoung Oh a, Hang Seok Choi b, Ung-Jin Kim c, In-Gyu Choi a, Joon Weon Choi d,
a
Department of Forest Sciences and Research Institute for Agriculture and Life Science, Seoul National University, 599 Gwanak-ro, Gwanak-gu, Seoul 151-921, Republic of Korea
b
Department of Environmental Engineering, Yonsei University, Wonju 220-710, Gangwondo, Republic of Korea
c
Department of Plant & Environmental New Resources, College of Life Science, KyungHee University, Yongin-si, Kyunggi-do 446-701, Republic of Korea
d
Graduate School of International Agricultural Technology and Institute of Green-Bio Science and Technology, Seoul National University, Pyeongchang 232-916, Gangwon-do,
Republic of Korea

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Upgraded heavy oil (HDO with Pd/C,

Ru/C and Pt/C) was stored for
12 weeks.

Properties of heavy oil were hardly
varied during storage period.

Hydrodeoxygenative process may
effectively improve the stability of
bio-oil.

Degree of unsaturation showed that
heavy oil retained stability during the
storage.

a r t i c l e i n f o a b s t r a c t

Article history: The aim of this study was to investigate the improvement in bio-oil stability via hydrodeoxygenation
Received 26 February 2016 (HDO) with noble metal catalysts. The bio-oil produced by fast pyrolysis was subjected to the
Received in revised form 7 April 2016 hydrodeoxygenative upgrading process with Pd/C, Ru/C, or Pt/C at 300 C for 60 min with 3 MPa H2 pres-
Accepted 9 May 2016
sure. Upgraded bio-oil (heavy oil) was stored in sealed glass bottles at 23 C for 2, 4, 8, or 12 weeks.
Available online 26 May 2016
The major properties (water content, viscosity, and acidity) of heavy oils after storage and the chemical
features (elemental composition and functional groups) of phenol polymers in the aged heavy oil were
Keywords:
characterized.
Bio-oil
Hydrodeoxygenation
Most properties of the aged heavy oil were maintained at the initial levels during the storage period,
Storage stability which indicates that the oil properties were stabilized by HDO. The water content slightly increased from
Noble metal catalyst 0.32.1 wt% to 2.33.5 wt% during the storage, but the viscosity and acidity of the oil hardly changed.
Fast pyrolysis Chemical compositions of low-molecular weight compounds in the aged heavy oils were slightly modi-
fied during storage. A slight increase in molecular weight was also observed and was attributed to partial
repolymerization of phenol polymers in the heavy oil during storage. Overall, this study suggests that
HDO upgrading effectively improves the stability of bio-oil properties.
2016 Elsevier Ltd. All rights reserved.

Corresponding author.
E-mail address: cjw@snu.ac.kr (J.W. Choi).

http://dx.doi.org/10.1016/j.fuel.2016.05.044
0016-2361/ 2016 Elsevier Ltd. All rights reserved.
 S. Oh et al. / Fuel 182 (2016) 154160
1. Introduction
Liquid fuel is required to have homogeneous and stable proper-
ties during storage or at the generation facility. One alternative
energy source, bio-oil, is considered to be a promising fuel for
power generation systems and combined heat and power systems
[13]. However, the large amounts of volatiles and many reactive
oxygenated compounds including acids, aldehydes, sugars, and
alcohols in bio-oil produce a glue-like material when stored for
extended periods at ambient temperature, which leads to instabil-
ity [47]. Moreover, polymerization, esterification, and etherifica-
tion of these compounds can increase the viscosity of the bio-oil
during storage, resulting in injection problems when used as a bio-
fuel [1]. Therefore, maintenance and improvement of the proper-
ties and stability of biofuels are the main factors regarding their
introduction into the market [8]. Catalytic treatments have been
pursued to improve the composition of bio-oil. Many previous
studies have investigated various upgrading processes, including
hydrodeoxygenation (HDO), to significantly improve the stability
of bio-oil [915]. In general, HDO is a low-hydrogen consumption
process compared with other hydroprocesses as well as a method
for manufacturing a more useful product from bio-oil [16]. Fur-
thermore, the process is effective in stabilizing pyrolytic lignin,
which makes up approximately 20% of bio-oil, and in enhancing
bio-oil stability with supercritical ethanol [17,18]. Thus, modifica-
tion of pyrolytic lignin and oxygenated compound during storage
might be accomplished for assessing bio-oil stability.
Diebold [8] presented diverse chemical reactions expected to
occur in bio-oil via the catalytic reaction, but these reactions also
occurred in the absence of catalysts when bio-oil was stored at
room temperature for a long time. Chemical reactions such as
esterification of acids with alcohols, aldehyde polymerization,
hydration of aldehydes or ketones with water, hemiacetal or acetal
formation between aldehydes and alcohols, resin formation from
aldehydes and phenols, olefin condensation, oxidation of alcohols
and aldehydes to form carboxylic acids, and oxidative esterification
of aldehydes were suggested to occur in bio-oil during storage
[7,8]. These reactions are involved in property changes such as vis-
cosity. Maintaining a lower viscosity is important for atomization
and injection. Therefore, studies have been performed to experi-
mentally demonstrate the occurrence of the above reactions
[7,19]. As the storage effect of upgraded oil had not been generally
proposed, in this study, the improved stability of bio-oil after
hydrodeoxygenative upgrading was investigated. For this purpose,
heavy oil, bio-oil upgraded via the hydrodeoxygenative process,
was distributed in glass bottles and stored at 23 C for 2, 4, 8, or
12 weeks. After storage, characterization of the stored heavy oil
properties and the amounts of pyrolytic lignin were analyzed.
2. Material and methods
2.1. Hydrodeoxygenation upgrading of crude bio-oil
Crude bio-oil was produced from miscanthus biomass (Miscant-
hussinensis) using a fluidized-bed reactor [20]. Hydrodeoxygena-
tion upgrading of crude bio-oil was performed at 300 C for
60 min under 3 MPa H2 pressure with three different noble metal
catalysts (Pd/C, Ru/C, and Pt/C). After the reaction, the four main
products gas, char, and two immiscible liquids [aqueous phase
(light oil) and organic phase (heavy oil)] were obtained and heavy
oil was subjected to an aging test. Details of the hydrodeoxygena-
tion process and heavy oil properties were reported in a previous
study [20].
155
2.2. Aging tests of heavy oil
2.2.1. Storage of heavy oil
Previous studies have suggested that bio-oil has a low thermal
stability, and an increase in temperature had a similar effect on
bio-oil viscosity as storage [21,22]. However, thermal aging of oil
might involve other properties or depend on the composition.
Therefore, for stability testing, heavy oil was stored under fixed
conditions (23 C, 20% relative humidity) for 2, 4, 8, or 12 weeks.
Heavy oils (obtained with HDO catalysts of Pd/C, Ru/C, or Pt/C)
were weighed (25 g), placed in glass vials for each storage period,
and tightly sealed with a plastic cap. Since bio-oil obtained from
pine and oak wood showed stable viscosity for 60 days [7], heavy
oils were stored for 3 months (84 days) to assess the role of aging
on the stability of the oil. The weight of heavy oil was measured
every two weeks for the first month and then monthly for the
remainder of the storage period in order to determine the amount
of lost volatile compounds.
2.2.2. Physicochemical properties
Typical physicochemical features of aged heavy oil including
water content, pH, TAN (total acid number), and viscosity were
measured after 2, 4, 8, or 12 weeks of storage in order to investi-
gate the effect of HDO on heavy oil stability. Karl-Fischer titration
(Titro Line KF, Schott Instruments, Germany), and a capillary-type
viscometer and ViscoClock (Schott Instruments) at 40 C were used
to measure the water content, and viscosity of aged heavy oil,
respectively. Also, the total acid number (TAN) of aged heavy oil
was measured by an ASTM D664 method. Elemental analysis of
carbon, hydrogen, and nitrogen was carried out with a LECO
CHNS-932 analyzer. From the elemental analysis, the atomic H/C
and O/C ratios were calculated; the degree of unsaturation was cal-
culated using the following equation.
Degree of unsaturation Cm 1  Hm  Nm=2
where Cm, Hm, and Nm are the molar quantities of carbon, hydro-
gen and nitrogen, respectively. The degree of unsaturation was not
affected by the oxygen content. The higher heating value (HHV) was
calculated by Sheng and Azvedos formula [23].
The average molecular weight of heavy oil before and after
aging was measured using a GPC max instrument (ViscotekRImax,
Viscotek, UK) coupled with a UVVis detector (VE3210, Viscotek)
equipped with a PLgel 5 lm MIXED-C column (300  7.5 mm,
Varian, Inc.) and a PLgel 5 lm guard column (50  7.5 mm, Varian,
Inc.). Each 2 mg sample was dissolved in 2 ml tetrahydrofuran
(THF) and filtered through a 0.5 lm hydrophobic syringe filter to
remove insoluble solids. Polystyrenes with masses ranging
between 580 Da and 3250 kDa were used as standards to create
a calibration curve.
2.2.3. Identification of low-molecular weight components
To investigate the modification of low-molecular weight com-
ponents (micro-molecules) in heavy oil during storage, qualitative
and quantitative analyses of micro-molecules in heavy oil were
performed using GC/MS. For this analysis, 50 ll internal standard
(fluoranthene 25 mg/ml acetone) was added to 450 ll oil for quan-
titative analysis. The amount of micro-molecules in heavy oil dur-
ing the storage period was calculated using the following equation.
Amount of compoundsmg=ml oil
Rf  Acompound =AI:S  MI:S  V oil  Y heavy oil =100;
where Rf (response factor) depends on the type of compound;
Acompound and AI.S are the area of the compounds and the area of
the internal standard (I.S.), respectively; MI.S is the amount of added
I.S. (mg), Voil is the quantity of oil used in the analysis (ml), and
156 S. Oh et al. / Fuel 182 (2016) 154160
Yheavy oil/100 is the yield of heavy oil. The yield of heavy oil varied
with HDO catalyst and did not change during the storage period.
Analysis with an Agilent 7890A coupled with a 5975C mass selec-
tive detector (MSD) and a flame ionization detector (FID) equipped
with a DB-5 capillary column (60 m  0.25 mm  0.25 lm) was
used for separation of micro-molecules in oils with a split ratio of
1:20. The oven temperature was maintained at 50 C for 5 min, fol-
lowed by heating at a rate of 3 C/min to 280 C, which was main-
tained for 20 min. The injector and FID detector temperatures were
250 C and 300 C, respectively. Each peak was identified by compar-
ison with the NIST (National Institute of Standards and Technology)
mass spectra data library and previously reported data [24,25].
2.2.4. Analysis of phenol polymer in aged heavy oil
Lignin-like polymers in the heavy oil (pyrolytic lignin in the
crude bio-oil), the main reason for bio-oil instability, were
extracted from the original heavy oil and 12 week-aged heavy oil
using the method of Scholze and Meier [26] and were labeled as
phenol polymer (PP) and aged phenol polymer (APP), respec-
tively. The name of these polymers were used in conjunction with
a particular catalyst, such as Pd-PP or Pd-APP. The essential prop-
erties of APP were compared with PP extracted from heavy oil
before storage. Elemental analysis was conducted using the same
method as mentioned above. Essential functional groups (OMe
and phenol-OH groups) of PP and APP were determined according
to the methods of Baker [27] and Mnsson [28], respectively. The
average molecular weights of aged heavy oil were measured
using a GPC max instrument (ViscotekRImax, Viscotek, UK), as
Fig. 1. An overview of the whole experimental scheme. (The mass balances of products were indicated average values based on 1 kg biomass treatment.)
mentioned above. The overall experimental process is presented
in Fig. 1.
3. Results and discussion
3.1. Changes in the properties of heavy oil during storage
The physical properties of bio-oil changed undesirably during
storage [19]. However, the HDO reaction improved the bio-oil
quality by lowering its viscosity, acidity, and water content. More-
over, the process might also enhance the stability of bio-oil via
removal of reactive compounds (levoglucosan, furfural, acetic acid,
and unsaturated compounds) as well as promote decomposition of
phenol polymers. Especially, Pt/C was effective to enhancing stabil-
ity of oil with reducing of phenol polymers, while Pd/C was good at
de-moisturization. Among the three noble metal catalysts, Pt/C has
more resistant to deactivation than Ru/C, and Pd/C during the reac-
tion [20,29]. The physical properties of heavy oil varied depending
on the catalyst used in the HDO process. Thus, in this study, we
investigated the changes in physical properties including water
content, pH, viscosity, elemental composition, and chemical com-
position to elucidate how HDO influences oil storage stability.
According to a previous study, bio-oil separates into a water
phase and a viscous sludge phase [30]. In contrast with bio-oil,
there were no visual changes in the heavy oil during the storage
period. To test these changes, the heavy oils were weighed before
and after storage. None of the samples lost more than 0.4 wt% of
volatiles, and no substantial volatile loss was noted over the
12 week storage period.
 S. Oh et al. / Fuel 182 (2016) 154160 157

3.1.1. Water content Table 2

Changes in the physical properties of the heavy oil during the Physicochemical features of heavy oil obtained from hydrodeoxygenative upgrading
of bio-oil in the presence of Ru/C catalyst during various storage period.
storage period are shown in Tables 13. Significant changes were
observed in the properties of heavy oils, including water content Storage period (week) Bio- Heavy oil Ru/C
and viscosity, which was the most problematic feature during oil
0 2 4 8 12
bio-oil storage. For example, an excessive amount of water gener- Water content (wt%) 17.7 2.1 2.5 2.3 2.2 3.5
ally led to corrosiveness and phase separation during aging. How- (0.2)a (0.0) (0.3) (0.1) (0.1)
ever, the HDO process decreased the water content in bio-oil from TAN (mg KOH/g oil) 164.8 95.4 89.2 88.4 88.1 87.0
17.7 to 0.32.1 wt% in heavy oil via de-moisturization [29]. The (0.2) (0.1) (0.1) (0.2) (0.1)
Average molecular 419 694 998 1102 1179 1072
water content in heavy oil increased an average of 0.2%/week
weight (Mw)
(Pd/C), 0.1%/week (Ru/C) and 0.2%/week (Pt/C) over the 12 week
Elemental analysis (wt%)
period. This increase was faster within the first 2 weeks for Pd/C
C 40.2 58.3 59.0 59.0 59.4 59.6
and Pt/C and after 8 weeks with Ru/C, and the water content after H 7.5 8.3 9.0 9.0 9.1 9.3
storage (2.3, 3.5, and 3.4 wt%, respectively) was still lower than N 0.2 0.2 0.2 0.2 0.2 0.2
that of bio-oil (23.6 wt% water content after 10 weeks) [19]. The Ob 52.2 33.1 31.8 31.8 31.3 30.9
HHV (MJ/kg)c 18.2 23.8 24.5 24.5 24.6 24.8
increase in water content suggests the occurrence of reactions gen-
erating water, such as esterification, acetalization, polycondensa- a
Standard deviation.
b
tion, and alcohol addition [31]. Water formation reactions were Calculated by difference.
c
predominant in the initial stage for Pd/C and Pt/C and in the later High heating value was calculated following formula, HHV(MJ/kg) = 1.3675
+ (0.3137  C) + (0.7009  H) + (0.0318  O).
stages for Ru/C.

3.1.2. Acidity Table 3

Physicochemical features of heavy oil obtained from hydrodeoxygenative upgrading
The acidity of heavy oil was strikingly reduced after the HDO
of bio-oil in the presence of Pt/C catalyst during various storage period.
reaction, due to the conversion of acids, like acetic acid, in bio-oil
into other compounds during HDO [29]. TAN of heavy oil changed Storage period (week) Bio- Heavy oil Pt/C
oil
slightly during the 12 weeks. For example, heavy oil obtained from 0 2 4 8 12
Ru/C decreased in acidity from 95.4 mg KOH/g oil to 87.0 mg KOH/ Water content (wt%) 17.7 1.3 2.9 3.0 3.4 3.4
g oil. HDO with Pd/C and Pt/C was more effective in stabilizing the (0.4)a (0.2) (0.2) (0.2) (0.0)
bio-oil acidity. The acidity of heavy oil decreased from 60.4 to TAN (mg KOH/g oil) 164.8 73.2 73.0 73.8 72.8 70.9
56.1 mg KOH/g oil (Pd/C) and 73.2 to 70.9 mg KOH/g oil (Pt/C) dur- (0.1) (0.3) (0.1) (0.0) (0.2)
Average molecular 419 762 749 771 830 867
ing the 12 weeks of storage. The level of TAN observed in heavy oil
weight (Mw)
resulted from phenolic hydroxyl groups in lignin derivatives [32].
Elemental analysis (wt%)
Moreover, the decrease in acidity after storage might reflect re- C 40.2 57.8 58.0 58.7 59.4 59.4
polymerization of monomeric compounds, which was ascertain- H 7.5 8.6 9.0 9.0 9.1 9.3
able from the average molecular weights of heavy oil and phenol N 0.2 0.0 0.0 0.1 0.1 0.2
b
polymers (Tables 13 and 5). O 52.2 33.5 33.0 32.2 31.4 31.2
c
HHV (MJ/kg) 18.2 23.9 24.2 24.4 24.6 24.8
a
Standard deviation.
3.1.3. Viscosity b
Calculated by difference.
Fig. 2 shows the change in viscosity of heavy oil after various c
High heating value was calculated following formula, HHV(MJ/kg) = 1.3675
storage periods. The HDO reaction reduced the viscosity of the + (0.3137  C) + (0.7009  H) + (0.0318  O).
bio-oil from 30 cSt to 24 cSt. Additionally, the rate of viscosity
increase in heavy oil ranged from 0.1 cSt/week (Pd/C and Ru/C)
to 0.0 cSt/week (Pt/C) during the storage periods, while that of during storage was due to olefin condensation, polymerization,
bio-oil was 1.1 cSt/week [19,29]. The increase in bio-oil viscosity phase separation, coke formation, evaporation of volatiles, and oxi-
dation. These reactions were accelerated by acids, aldehydes, and
sugars, such as levoglucosan, and nitrogen-containing compounds
Table 1 in bio-oil that catalyze these reactions and increase the viscosity
Physicochemical features of heavy oil obtained from hydrodeoxygenative upgrading
of bio-oil in the presence of Pd/C catalyst during various storage period.
[7,30,33]. However, the HDO process converted acetic acid, vanil-
lin, furfural, and levoglucosan into esters via ring opening, hydro-
Storage period (week) Bio- Heavy oil Pd/C genation, decarbonylation, and dehydration [29]. The process also
oil
0 2 4 8 12 removed acetic acid and converted the unstable pyrolytic lignin
Water content (wt%) 17.7 0.3 1.1 1.1 1.1 2.3 structure into stable phenol polymers via depolymerization,
(0.0)a (0.0) (0.0) (0.0) (0.1) hydrogenation, dehydroxylation, and demethoxylation. Addition-
TAN (mg KOH/g oil) 164.8 60.4 60.3 60.8 59.3 56.1 ally, both bio-oil and heavy oil contained low levels of nitrogen,
(0.5) (0.1) (0.4) (0.1) (1.1)
demonstrating the minor role of this element in the viscosity
Average molecular 419 791 986 1071 1105 1147
weight (Mw) increase. The stable viscosity of heavy oil during storage is thought
to be due to the lack of reactants for the above reactions.
Elemental analysis (wt%)
C 40.2 55.7 55.5 55.5 55.7 55.1
H 7.5 9.0 9.0 9.0 9.0 9.0
3.1.4. Molecular weight
N 0.2 0.1 0.1 0.2 0.4 0.4
Ob 52.2 35.2 35.4 35.3 34.9 35.6
The average molecular weight (Mw) of aged heavy oil is pre-
HHV (MJ/kg)c 18.2 23.5 23.5 23.5 23.5 23.4 sented in Tables 13. Heavy oil had an immaterial increase in aver-
a
age molecular weight upon aging. Before storage, the Mw of heavy
Standard deviation.
b
Calculated by difference.
oil was 694791 Da, which increased slightly after storage and sta-
c
High heating value was calculated following formula, HHV(MJ/kg) = 1.3675 bilized after 2 weeks. For the first 2 weeks, the Mw of heavy oil
+ (0.3137  C) + (0.7009  H) + (0.0318  O). increased 195 or 304 Da (from 791 to 986 Da for Pd/C; from 694
158 S. Oh et al. / Fuel 182 (2016) 154160

Table 4
Quantitative analysis of low molecular weight components in heavy oil after 4, 8 and 12 weeks (23 C, RH: 20%).

Compound Amount (mg/ml heavy oil)

Pd/C Ru/C Pt/C
Storage period (weeks)
0 4 8 12 0 4 8 12 0 4 8 12
Phenol
Phenol 0.3 1.0 0.8 1.0 0.8 0.7 0.8 0.6 0.6 0.5 0.6 0.3
2-Methyl-phenol 0.5 0.9 0.8 0.3 0.6 0.6 0.4 0.5 0.5
4-Methyl-phenol 0.5 0.8 0.6 0.5 0.8 0.6 0.6 0.2 0.4 0.4
Guaiacol 3.9 3.3 3.1 3.0 3.2 3.2 3.3 2.9 2.6 2.1 2.1 1.7
2,4-Dimethyl-phenol 0.1 0.1 0.2 0.2 0.1 0.1 0.2 0.1 0.1
4-Ethyl-phenol 2.7 3.2 3.0 2.3 0.3 0.3 0.3 1.8 0.0 0.1 0.2 1.7
4-Methyl-guaiacol 2.5 2.1 1.9 2.1 1.6 1.8 1.4 1.4 2.7 2.0 2.2 1.1
2-Propyl-phenol 1.9 0.3 0.6
4-Ethyl-guaiacol 2.9 3.1 3.1 2.1 2.1 2.1 1.8 3.1 2.6 2.6 2.0
Syringol 0.7 0.9 0.8 1.4 0.9 0.9 0.9 0.8 0.7 0.7 0.7 0.5
4-Propyl-guaiacol 2.4 2.2 2.0 2.4 1.5 1.4 1.2 1.2 1.7 1.5 1.7 1.3
Sum of phenols 15.5 17.7 16.9 15.8 11.7 11.7 11.3 10.5 12.2 10.5 11.1 8.6
Ketone
2-Methyl-cyclopentanone 0.2 0.4 0.7 0.9 0.4 0.4 1.1
2-Ethyl-cyclopentanone 1.7 0.5 0.5 1.5 1.7 1.1
2,5-Hexanedione 0.3 0.3 0.4 0.4 0.6 0.7 0.4 0.4
2-Ethyl-2-cyclopentenone 0.2 0.2 0.5 0.5 1.7 1.5
2,3-Dimethyl-2-cyclopentenone 2.3 1.3 1.1 2.0 0.5 1.0 1.0 0.4 0.4 0.4
Sum of ketones 4.7 1.3 2.0 2.0 1.4 1.9 2.1 1.2 3.7 4.2 2.9 2.2
Total 20.1 19.2 19.1 17.7 12.9 13.5 13.4 11.5 15.9 14.7 14.0 10.6

35
Table 5 Bio-oil [19]
Characteristics of macromolecules extracted from bio-oil, heavy oil, and aged heavy 30 Pd/C
oil.
Ru/C
Viscosity (cSt)

25
Lignin Elemental analysis (wt Average molecular Functional
Pt/C
fragment %) Weight (Dalton) groups (%)
20
C H N Oa Mw Mn PDIb Phe- OCH3
OH 15
*
PL 65.0 6.4 0.6 27.8 1065 544 2.0 6.8 11.6 10
(0.6) (1.1)
**
Pd PP 74.8 6.9 0.6 17.7 1165 659 1.8 4.0 1.7 5
(0.5)c (0.3)
***
Pd APP 74.9 6.9 0.7 17.5 1561 818 1.9 1.1 1.3 0
(0.0) (0.0) 0 2 4 6 8 10 12
Ru PP 75.2 6.6 0.6 17.6 1174 708 1.7 4.0 0.2 Storage period (week)
(0.5) (0.0)
Ru APP 75.7 6.6 0.7 17.0 1408 718 2.0 1.0 0.1 Fig. 2. Variation of viscosity during 12 weeks storage period.
(0.0) (0.0)
Pt PP 75.6 7.9 0.6 15.9 818 576 1.4 1.9 1.0
(0.5) (0.2)
Pt APP 75.9 8.0 0.7 15.4 947 647 1.5 0.8 1.1
tion, dehydroxylation, and decomposition [29]. These reactions
(0.0) (0.0) decreased the reactivity of PP; thus, the dimerization and trimer-
a
ization reactions scarcely occurred during aging. According to
Calculated by difference.
b Cioffi et al. [34], free radicals are associated with polymerization,
Polydispersity index (PDI) means the value of Mw/Mn.
c
Standard deviation. which is known as the Trommsdorff effect. Moreover, the GPC
*
Pyrolytic lignin (macromolecules in bio-oil). chromatogram of heavy oil presented smooth peak, which was dif-
**
Phenol polymer (macromolecules in heavy oil). ferent from that of free radical polymerization [35]. As a result,
***
Aged phenol polymer (macromolecules in aged heavy oil).
HDO reduced the incidence of radicals and stabilized lignin frag-
ments in bio-oil, preventing such reactions during storage.
to 998 Da for Ru/C catalyst) and then gained 161 Da (Pd/C) or 74 Da
(Ru/C) over the remaining storage period. The initial increase (195 3.1.5. Atomic H/C and O/C ratios
or 304 Da) was equivalent to the addition of one or two monomeric The atomic H/C and O/C ratios for the original and aged heavy
phenolic compounds. According to previous research, oligomer oils obtained from different HDO catalysts are presented in Fig. 3.
polymerization apparently progresses via sequential dimerization Conversion and removal of unstable acid, aldehyde, sugar, and
or trimerization reactions [5]. Therefore, the increase in Mw in water reduce the O/C ratio of heavy oil. Since the elemental analy-
these heavy oils might result from dimerization and trimerization sis and calculated atomic ratios include the water content of heavy
reactions. The Mw of heavy oil hydrodeoxygenated with Pt/C oil, the H/C ratio of heavy oil was lower than that of bio-oil, despite
increased by a total of 105 Da over 12 weeks, which was less than the hydrogenation conditions. Compared with bio-oil (1.0), the
those of Pd and Ru heavy oils. As mentioned in previous research, atomic O/C ratio was effectively reduced via the HDO reaction
Pt/C was effective in enhancing the stability of pyrolytic lignin (PL) (0.4), The H/C ratio was reduced by 1.81.9 (compared with that
in bio-oil via conversion to phenol polymer (PP) by demethoxyla- of bio-oil; 2.2) due to de-moisturization and dehydration. Heavy
 S. Oh et al. / Fuel 182 (2016) 154160 159

2.3 heavy oil storage. For instance, heavy oil obtained from Ru/C treat-
ment showed very small changes in micro-molecules. The total
2.2 amount of micro-molecules decreased from 20.14 to 17.74 mg/ml
for Pd heavy oil, from 12.93 to 11.54 mg/ml for Ru heavy oil, and
Atomic H/C ratio

2.1 from 15.86 to 10.61 mg/ml for Pt heavy oil. As mentioned above,
aldehydes and sugars in bio-oil, which affect viscosity during stor-
2.0 age, were converted into esters or ketones during the HDO process.
Compared with the notable reduction in untreated bio-oil stability
1.9 [19], the results with heavy oil indicated that HDO improved bio-
oil stability. Related to the average molecular weight of heavy oil,
1.8 a slight decrease in the amount of low molecular weight com-
pounds might be due to dimerization or trimerization reactions.
1.7
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1
Atomic O/C ratio
3.3. Changes in phenol polymer after storage
Fig. 3. Van Krevelen diagram of bio-oil and heavy oils after 12 weeks storage.

The yields of lignin fragments in heavy oil (PP: phenol polymer

30 extracted from heavy oil before storage, APP: phenol polymer
0 week 12weeks extracted from heavy oil after storage) before and after storage
25 are described in Fig. 4. Ru- and Pt-PP yielded almost the same
amounts of APP (9.0 and 6.0 wt%, respectively), while Pd-PP
20 increased from 9.3 to 12 wt%. According to a previous study, PL
Yield (%)

(pyrolytic lignin; 13.3 wt%) increased approximately 1.8-fold

15
10
5 of heavy oil (Tables 13). Therefore, polymerization (actually
0 PP and lignin-derived monomers (micro-molecules). Essential
Pyrolytic lignin Pd PP
Fig. 4. Change of macromolecules yield during the storage period.
oil obtained from Pd/C and Pt/C demonstrated an increased atomic
O/C ratio of heavy oil of Ru/C (from 0.4 to 0.5), while neither the O/
C nor H/C ratio of the other heavy oils of Pd/C and Pt/C changed
during storage.
3.2. Changes in micro-molecule composition during 12 weeks of aging
Low-molecular weight compounds in the original and aged
heavy oil were analyzed using GC/MS and were identified by com-
parison with the NIST Mass Spectral Library (Table 4). The major
peaks of the gas chromatogram after storage were qualitatively
almost identical with those of the original heavy oil. Some of the
peak areas varied with storage time. Generally, the amount of com-
pounds slightly decreased, but the variation was not significant for
(24.3 wt%) after 10 weeks of storage [19].
The difference between Mw values before and after storage ran-
ged from 129 to 396 Da. A similar trend was observed with the Mw
dimerization and trimerization) was slightly pronounced between
Ru PP Pt PP functional groups of phenolic hydroxy and methoxy are known
as two of the more reactive sites in the lignin structure. The
amounts of these functional groups in PP and APP are described
in Table 5. In the case of phenolic hydroxyl groups, which are
involved in hemiacetal and acetal formation, the amount decreased
from 4.0 to 1.01.1 wt% (Pd- and Ru-PP) and from 1.9 to 0.8 wt%
(Pt-PP). However, the oxygen level did not change after storage.
This result suggests that condensation or esterification instead of
acetal and hemiacetal formation might have occurred. The content
variation of methoxy groups differed with HDO catalyst. The meth-
oxy groups were reduced from 1.7 to 1.3 wt% for Pd-PP, while the
amounts stayed the same for Ru-PP and Pt-PP (0.2 and 1.0 wt%,
respectively). The properties were differed from PP and APP, their
structural discrepancies (yield, molecular weight and functional
groups) were less than for PL and APL (aged pyrolytic lignin)
[19]. Therefore, it appears that the stability of biofuel can be
enhanced via HDO treatment.

4.5
0 week (Oil) 12 weeks (Oil) 0 week (Macromolecule) 12 weeks (Macromolecule)
4
Degree of unsaturation

3.5

2.5

1.5

0.5

0
Bio-oil Pd Ru Pt

Fig. 5. Degree of unsaturation for oil and macromolecules before and after the storage period.
160 S. Oh et al. / Fuel 182 (2016) 154160
3.4. Degree of unsaturation
The degree of unsaturation was obtained by carbon, hydrogen,
and nitrogen analysis. Fig. 5 shows that the degree of unsaturation
of heavy oil presented no notable changes (from 1.11.4 to 1.31.9)
during storage; that of PP also remained unchanged (Pd-PP: 3.8;
Ru-PP: 4.0; Pt-PP: 3.4). Compared with the degree of unsaturation
of lignin (5.42) [36], that of PP in this study was lower (3.44.0),
indicating a more stable state via HDO treatment with supercritical
ethanol. This finding accounts for the hydrogenation and dealkyla-
tion of side chains and the stability improvement achieved through
the use of HDO. These reactions reduce double bonds, enhance sta-
bility, and decrease the degree of unsaturation. Although there
were structural modifications during storage (Table 5), they
appeared not to affect the degree of unsaturation.
4. Conclusions
In this study, the effect of storage on heavy oil properties was
assessed. After hydrodeoxygenative upgrading of bio-oil with sev-
eral catalysts (Pd/C, Ru/C, or Pt/C), heavy oil was obtained. Heavy
oil was stored at 23 C in 20% humidity for 12 weeks, and the
essential physicochemical properties including water content, vis-
cosity, and acidity were almost unchanged during storage. Accord-
ing to the increase in the Mw, and decrease and of the monomer,
some reactions such as condensation or polymerization might be
occurred. In particular, the principal and problematic property of
viscosity was maintained due to the lack of sugars and aldehydes
in heavy oil. The yield and properties of PP were modified to a les-
ser extent than those of PL. Based on the degree of unsaturation,
heavy oil and PP are more stable than bio-oil and PL.
Acknowledgements
This research was supported by the Global Ph.D. Fellowship
Program through the National Research Foundation of Korea
(NRF) funded by the Ministry of Education, Science and Technology
(Project No. 2014H1A2A1018117).
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