Catalysis Today 185 (2012) 313317

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Catalysis Today
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Decarboxylation of microalgal oil without hydrogen into hydrocarbon for the
production of transportation fuel
Jeong-Geol Na, Jun Kyu Han, You-Kwan Oh, Jong-Ho Park, Tae Sung Jung, Sang Sup Han,
Hyung Chul Yoon, Soo Hyun Chung, Jong-Nam Kim, Chang Hyun Ko

Korea Institute of Energy Research, 102, Gajeong-ro, Yuseong-gu, Daejeon, 305-343, Republic of Korea
a r t i c l e i n f o
Article history:
Received 31 May 2011
Received in revised form22 July 2011
Accepted 9 August 2011
Available online 26 August 2011
Keywords:
Microalgae biorenery
Pyrolysis
Decarboxylation
Hydrotalcite
Hydrocarbon
a b s t r a c t
A catalytic decarboxylation process following pyrolysis was developed for the production of transporta-
tion fuels from microalgae. The pyrolysis of Chlorella sp. KR-1, which has a triglyceride content of 36.5%,
was carried out at 600

C to obtain feedstock oil for decarboxylation. The major compounds in the pyrol-
ysis oil were free fatty acids with carbon numbers of 16 and 18. Decarboxylation of the pyrolysis oil was
performed using a type of hydrotalcite (MG63) as a catalyst at temperatures of 350

C and 400

C. Due to
the selective reaction by MG63, hydrocarbons with carbon numbers of 15 and 17 were the most abundant
compounds in the liquid product. The product yield at a reaction temperature of 400

C was 78.6% and

the degree of oxygen removal was 78.0%. Inert or less active oxygenates for hydrotalcite, such as phenolic
compounds and fatty acid alkyl ester, may prevent the complete removal of oxygen. The diesel fraction
in the product obtained under the given reaction condition was 83.8%, whereas that of the pyrolysis oil
was 35.5%.
2011 Elsevier B.V. All rights reserved.
1. Introduction
During the past few decades, the rising concern over global
warming and the depletion of fossil fuels have motivated
researchers to seek fuel production from biomass. However, the
sustainable production of biofuels has been a subject of much
debate, as rst generation of biofuels, such as biodiesel and
bioethanol fromfood crops and oil seeds, would induce a negative
environmental impact as well as a competition against land use for
foods [1,2]. Therefore, muchattentionhas beenfocusedondevelop-
ingsecond-generationbiofuels producedfromnon-foodfeedstocks
suchas microalgae andforest products [3,4]. Microalgae have much
higher photosynthetic yields (38%) compared to terrestrial plants
as well as a higher potential for the direct CO
2
capture, as microal-
gae can be cultivated in a contained area [5,6]. Furthermore, many
microalgae species can accumulate substantial quantities of lipids
as much as 70% which can then be converted into various types
of fuels.
The conventional process of biofuel production from microal-
gal biomass consists of the extraction of lipids using an organic
solvent followed by a transesterication reaction. This technology
is relatively mature, having been demonstrated in the conver-
sion of vegetable oils into biodiesel. However, microalgal biomass

Corresponding author. Tel.: +82 42 860 3132; fax: +82 42 860 3134.
E-mail address: chko@kier.re.kr (C.H. Ko).
differ from traditional oil seeds in terms of their physicochemi-
cal properties, such as the cell wall chemistry and the cell size.
These characteristics complicate the efcient extraction of lipids
[7]. Furthermore, FAME (fatty acid methyl ester) biodiesel created
by transesterication has several disadvantages, such as a high
cloud point and lowenergy content, limiting its wider use [8,9].
Here, we propose a new process scheme for a microalgae
biorenery involving the pyrolysis of microalgal biomass and the
catalytic deoxygenation of pyrolysis oil. Pyrolysis of microalgae
containing high contents of triglycerides can produce free fatty
acids, which are the starting materials for hydrocarbons and which
are fully compatible with conventional fuels. Pyrolysis has several
advantages over other conversion methods. For instance, it is a
rapid and simple process. There are several reports on the pyrolysis
of algae in the literature [1012].
In research related to the pyrolysis of biomass, large amounts of
oxygenates, including organic acids, were generated. These com-
pounds needed to be upgraded for application to transportation
fuels. Among the various methods of deoxygenation [1316], we
adopted decarboxylation in which the oxygen atoms in biomass
are removed in the formof carbon dioxide. As shown in Scheme 1,
the process does not require hydrogen and is therefore economi-
cally favorable, although the carbon-based yield is low due to CO
2
loss. In previous research by the authors [16], oleic acid was suc-
cessfully transformed into pure hydrocarbons with high selectivity
by means of catalytic decarboxylation over hydrotalcites without
hydrogen. Hydrotalcites are a double-layered hydroxide composed
0920-5861/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cattod.2011.08.009
314 J.-G. Na et al. / Catalysis Today 185 (2012) 313317
Scheme 1. Reaction routes for decarboxylation (a) and hydrodeoxygenation (b) of
free fatty acids.
Scheme 2. Experimental procedure.
of MgO and MgAl
2
O
4
. They are relatively stable compared to other
solid bases with sufcient decarboxylation activity [17].
In this study, the catalytic decarboxylation of pyrolysis oil from
Chlorella sp. KR-1 cells was carried out over hydrotalcite. The effect
of the reaction temperatures on the decarboxylation performance
was investigated and the compositional change in the reactant and
products during the reaction was observed. In addition, the liquid
products fromdeoxygenationwereanalyzedinorder toassess their
applicability as transportation fuels.
2. Experimental
The experimental procedures, including the pyrolysis of
microalgae, the deoxygenation reaction of the pyrolysis oil, and an
analysis of the reaction products, are displayed in Scheme 2.
2.1. Preparation of microalgal biomass
Chlorella sp. KR-1, a freshwater microalgae isolated near the
Youngwol region in Korea, was used in this work [6]. KR-1 samples
Table 1
Elemental composition of the microalgae.
C H O N S
wt% 56.6 8.9 28.0 2.3 0.4
Fig. 1. XRD pattern of hydrotalcite MG63.
for pyrolysis and deoxygenation were obtained by bubble-column
cultivation. The culture medium and conditions closely followed
methods available in the literature [18]. Microalgal cells were har-
vestedby centrifugation(3800g, 10min) andwashedwithdistilled
water (repeated twice). The cells were then dried in a freeze-dryer
(FD5512, IlShinBioBase Co., Korea) for four days or longer. The
triglyceride content in the KR-1 samples was analyzed by the mod-
ied direct transesterication method [18], and the triglyceride
content was found to be 36.5%. The elemental composition of the
microalgae obtained in this study is displayed in Table 1.
2.2. Pyrolysis of microalgae
Pyrolysis of the KR-1 sample was carried out in an autoclave
reactor (1L). Two hundred grams of microalgal cells were loaded
into the reactor and the reactor was then heated to 600

C by an
electric furnace. During the pyrolysis experiments, 60mL/min of
N
2
gas was supplied to the inside of the reaction vessel in order to
promote a shift of the liquid and gaseous products to a condenser
and a cold trap. The gaseous product was vented to the atmosphere
and the liquid vapor product was recovered as condensed pyrolysis
oil. The pyrolysis oil was separated into two phases (nonpolar light
and polar heavy fractions). The light phase was mainly composed
of free fatty acids, pure hydrocarbons and compounds containing
heteroatoms (Nor S). Volatile organic acids, aldehydes, ketones and
furanic compounds were abundant in the heavy phase. The light
fractions were used in the decarboxylation experiments.
2.3. Decarboxylation reaction
Hydrotalcites with a xed ratio of magnesiumoxide to the alu-
mina weight, MG63 (MgO:Al
2
O
3
=63wt%:27wt%, Sasol) were used
as a catalyst. The X-ray diffraction(XRD) patterninFig. 1shows that
MG63 has two separate phases of MgO and spinel MgAl
2
O
4
. The
surface area of MG63 as measured by N
2
adsorption was 120m
2
/g.
Decarboxylation tests were performed in a customized autoclave
reactor (100mL) operating in batch mode. A multi-blade impeller
was used to mix the liquid reactant and the solid catalyst. The
particle size of the catalysts was less than 45

C. The tempera-
ture was measured with a K-type thermocouple. In a typical batch
J.-G. Na et al. / Catalysis Today 185 (2012) 313317 315
Fig. 2. Boiling point distribution of the pyrolysis oil and soybean oil.
experiment, 25.0g of microalgal pyrolysis oil and 1.25g of catalysts
(reactant:catalyst =20:1) were placed in the reactor. The hydrotal-
cite catalysts were activated for 3h at 550

C in an air atmosphere
before use. After loading the reactant and catalyst, the reactor was
ushed with nitrogen in order to remove the remaining oxygen.
Then, the reactor was heated to the designated temperature (350
and 400

C, respectively) and maintained for 3h at that temper-

ature. The stirring speed was maintained at 100rpm during the
reaction. The reactor was subsequently cooled to room temper-
ature. The liquid products were collected after ltering the solid
phase catalyst.
2.4. Analysis of products
An elemental analysis of the oxygen concentration in the liquid
products was conductedusing a FlashEA112series device (Thermo
Fisher Scientic). The distribution of the boiling point range of the
liquid products was determined by HP 6890 gas chromatography
(Agilent, USA) using a simulated distillation method (SIMDIS), as
described in ASTMD 2887. The liquid products in the experiments
were analyzed via HP 6890 gas chromatography coupled with a HP
5973N mass spectrometer (Agilent, USA). Detailed GC/MS operat-
ing conditions and procedures can be found in Na et al. [16].
3. Results and discussion
3.1. Pyrolysis of Chlorella sp. KR-1
The yield of the liquid products during pyrolysis at 600

C was
about 55.3%, while that of the light fraction in the liquid products
was about 64.2%. The free fatty acid content of the light fraction
analyzed by GC-FID was about 45%. Considering that the triglyc-
eride content of the KR-1 sample in this study was 36.5%, 46% of
the triglycerides could be extracted in the form of free fatty acids
by pyrolysis. For comparison, we extracted lipids from the KR-1
sample by hexane, but the yield was extremely low(<2%). The low
extraction yield with a nonpolar solvent can be attributed to sturdy
cell wall structure of the KR-1 sample. Difculty in the extraction
of products was also noted in other cases involving microalgae [7].
Fig. 2 displays the boiling point distribution of the pyrolysis oil
and soybean oil. Soybean oil was selected as a typical material for
mixture with various types of triglycerides. Due to the thermal
treatment, the boiling point distributionof the pyrolysis oil is much
Table 2
Composition change of the free fatty acids (carbon numbers of 16 and 18, C16 and
C18) and linear hydrocarbons (carbon numbers of 15 and 17, C15 and C17) before
and after decarboxylation according to the GC/MS peak area.
Pyrolysis
oil
Decarboxylated
oil
Free fatty acids C16 21.65 0
C18 17.28 0
Linear hydrocarbons C15 4.97 9.32
C17 4.11 19.32
Table 3
Yield and degree of oxygen removal of the reaction product depending on the cata-
lysts and reaction temperatures.
Catalyst Reaction
Temperature (

C)
Yield (%) Degree of Oxygen
Removal (%)
Blank 400 86.2 64.0
MG63 350 82.3 76.5
MG63 400 78.6 78.0
lower than that of soybean oil. The lower boiling point implies that
pyrolysis oil has a lower molecular weight compared to soybean
oil. Although the boiling point distribution graph does not provide
precise information for each chemical a heat treatment at 600

C is
likely todecompose the microalgal biomass intosmaller molecules.
Although the pyrolysis process reduced the boiling point of the
reactant, this feed oil maintained a higher boiling point than diesel
considering the boiling point distribution of diesel (180350

C).
The mass portion of diesel in this pyrolysis oil was 35.5%. The mass
portion having a boiling point range between 350 and 400

C of the
pyrolysis oil is expected to consist of palmitic acid (bp 352

C), oleic
acid (bp 360

C), and stearic acid (bp 383

C).
As shown in Fig. 3, the GCMS chromatogram of the pyroly-
sis oil identies its individual components. Various types of fatty
acids and long-chain hydrocarbons are the major components.
Fatty acids, such as palmitic acid, oleic acid, and stearic acid, may
have come fromthe decomposition of triglycerides. The long-chain
hydrocarbons of pentadecane and heptadecane appeared to be the
product of the subsequent fatty acid decarboxylation process. The
peak area analysis in Table 3 also supports that fatty acids with
carbon numbers of 16 and 18 (C16 and C18) and hydrocarbons
with carbon numbers of 15 and 17 (C15 and C17) were the most
abundant species in the pyrolysis oil.
Interms of hydrocarbonproductionbydeoxygenation, pyrolysis
oil is likely to have a positive effect. The pyrolysis of microal-
gae biomass enhanced the accessibility of the reactants toward
catalytic active sites during the deoxygenation process because
triglycerides with a high molecular weight were decomposed into
free fatty acids with a lowmolecular weight. Furthermore, the par-
tial decarboxylation of fatty acids by the thermal treatment had
produced some portion of hydrocarbons. Thus, the pyrolysis of
microalgae is expectedtoreduce the burdenof catalytic decarboxy-
lation.
3.2. Catalytic decarboxylation of the pyrolysis oil
According to an analysis of pyrolysis oil, the major target com-
ponents in pyrolysis oil for deoxygenation are not triglycerides
but free fatty acids. To perform deoxygenation of the pyrolysis
oil, MG63, a hydrotalcite, and its corresponding reaction condi-
tions were selected based on previous research on the topic of the
decarboxylation of oleic acid [16].
Table 3 displays the decarboxylation activity of MG63 for the
pyrolysis oil obtained fromthe microalgae depending on the reac-
tion temperatures. Compared to a blank test involving a simple
thermal treatment without a catalyst, the existence of the catalyst
316 J.-G. Na et al. / Catalysis Today 185 (2012) 313317
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00
1
2
3
4
5
6
7
8
9
10 11
(a)
(b)
Fig. 3. GC/MS chromatogramof the pyrolysis oil (a) and the reaction product (b) at 400

C (1: decane; 2: undecane; 3: dodecane; 4: tridecane; 5: tetradecane; 6: pentadecane;

7: hexadecane; 8: heptadecane; 9: palmitic acid; 10: oleic acid; 11: stearic acid).
Fig. 4. Boiling point distribution of the reaction products.
enhanced the degree of oxygen removal. The oxygen content of the
microalgal oil was 10.2wt%. The decrease in the oxygen content in
the reaction product indicated the activity of deoxygenation. The
activity of deoxygenation of MG63 at 400

C was slightly higher

than that at 350

C. Considering the oxygen removal ratio only, a

reaction temperature between 350 and 400

C had no signicant
effect. The liquid yield decreased as the degree of deoxygenation
increased because oxygen was removed in the form of CO or CO
2
via decarbonylation or decarboxylation.
Fig. 4 describes the boiling point distribution of the reactant
(pyrolysis oil) and the products depending on the reaction con-
ditions. Catalytic deoxygenation may turn fatty acids with high
boiling points into their corresponding hydrocarbons with rela-
tively low boiling points. Consequently, the mass portion of the
product whose boiling point ranges from 180 to 350

C increased.
The portions of the product in the diesel range with reaction tem-
peratures of 350

C and 400

C were 67.6 and 83.8%, respectively.

Although the degrees of the deoxygenation of MG63 at both reac-
tion temperatures (350

C and 400

C) were nearly identical, the

boiling point distribution of the reaction product at each temper-
ature was quite different. As the reaction temperature increased
from 350

C to 400

C, the high boiling point portion of the prod-

uct (>350

C) decreased from26% to 11%. Through decarboxylation,

Fig. 5. Distribution of linear hydrocarbons in the pyrolysis oil and the reaction
product at 400

C with MG63.
transportationfuels cantherefore be obtainedwiththe proper oxy-
gen content and boiling point range.
As predictedbythe boilingpoint distributionshowninFig. 4, the
GC/MS analysis (Table 2) indicated that the fatty acids were com-
pletely converted to hydrocarbons by the decarboxylation process.
Most of the C18 fatty acids were converted to their corre-
sponding C17 hydrocarbons. However, the C16 fatty acids turned
into different types of hydrocarbons. The distribution of the linear
hydrocarbons shown in Fig. 5 demonstrates that the C17 hydrocar-
bons were the most abundant compounds after decarboxylation
reaction, although the C15 hydrocarbons were the richest in the
pyrolysis oil. The increase in the portion of C13 and C14 hydro-
carbons indicates that the C16 fatty acids were converted not only
to C15 hydrocarbons by decarboxylation but also to C14 and C13
hydrocarbons by decarboxylation and subsequent cracking. The
changes in the major compounds before and after catalytic decar-
boxylation are summarized in Table 4.
The deoxygenation activity of MG63 for pyrolysis oil is slight
lower than that for oleic acid (a model reactant). This difference in
the degree of oxygen removal may have stemmed fromthe impu-
rities in the pyrolysis oil. When used as a model reactant, oleic acid
is a rened chemical with a minimum purity level of 80%. Thus,
J.-G. Na et al. / Catalysis Today 185 (2012) 313317 317
Table 4
Major compounds in pyrolysis oils and decarboxylated oil: Identication and quantication were performed according to the GC/MS and GC/MS peak areas.
Pyrolysis oil Decarboxylated oil (with MG63 at 400

C)
Heavy fraction Light fraction (feed oil for decarboxylation)
Compounds GC/MS peak area (%) Compounds GC/MS peak area (%) Compounds GC/MS peak area (%)
Acetic acid 29.10 Palmitic acid 21.26 Heptadecane 14.80
3-Pyridinol 5.94 Oleic acid 10.64 Pentadecane 8.50
Acetone 4.40 Stearic acid 6.45 Tridecane 4.30
Levoglucosan 3.29 Pentadecane 4.23 Tetradecane 4.29
6-Methyl-3-pyridinol 2.74 8-Heptadecene 2.50 Dodecane 3.16
2-Pyrrolidinone 2.66 Pentadecanenitrile 2.47 Undecane 2.10
Propanoic acid 2.53 Heptadecane 1.61 Hexadecane 1.95
2,5-Pyrrolidinedione 1.83 Hexadecaneamide 1.60 8-heptadecene 1.66
2-Cyclopenten-1-one 1.69 Toluene 1.11 Hexadecanenitrile 1.51
2-Methyl-3-pyridinol 1.62 1-Tetradecene 0.97 Decane 0.98
previous research was able to measure the pure catalytic activity
of MG63 for oleic acid [16]. However, the pyrolysis oil used in this
study is a mixture of fatty acids, hydrocarbons and various impu-
rities. In fact, oxygenated compounds, such as phenols and fatty
acidalkyl esters, mostlyremainedunchanged. Phenolic compounds
such as phenol and cresol contain oxygen atoms in their molecu-
lar structures as a hydroxyl group. As the major oxygen removal
mechanism of hydrotalcite (MG63 in this study) was decarboxy-
lation, MG63 is not effective for the deoxygenation of phenolic
compounds. In the case of fatty acid alkyl esters, steric hindrance
by an alkyl group attached to the carboxyl group may reduce the
activity of MG63.
4. Conclusions
In an effort to produce transportation fuels from microalgal
biomass, the catalytic decarboxylation of microalgae pyrolysis oil
was carriedout usinghydrotalciteas acatalyst. Pyrolysis of Chlorella
sp. KR-1 successfully produced feedstock oil, which is mainly com-
posed of free fatty acids and hydrocarbons and suitable for catalytic
decarboxylation. The hydrotalcite catalyst displayed reasonable
levels of activity for the decarboxylation of pyrolysis oil. Speci-
cally, the diesel fraction in the liquid increased drastically because
C16 and C18 free fatty acids were converted to C15 and C17
hydrocarbons respectively with selective decarboxylation. Com-
plete oxygen removal was not achieved, most likely due to inert
or less active oxygenates for hydrotalcite, such as phenolic com-
pounds and fatty acid alkyl ester. Based on these results, pyrolysis
followed by catalytic decarboxylation present a viable option for
the embodiment of a biorenery combining the efcient and eco-
nomic dewatering characteristics of microalgae.
Acknowledgement
This work was supported by the Korea Institute of Energy
Research.
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