Fuel 200 (2017) 146–152

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Fuel
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Full Length Article

Efficient renewable fuel production from sewage sludge using a

supercritical fluid route
Hermawan Prajitno a, Hassan Zeb a, Jongkeun Park b, Changkook Ryu b, Jaehoon Kim a,b,⇑
a
SKKU Advanced Institute of Nanotechnology (SAINT), Sungkyunkwan University, 2066, Seobu-Ro, Jangan-Gu, Suwon, Gyeong Gi-Do 16419, Republic of Korea
b
School of Mechanical Engineering, Sungkyunkwan University, 2066, Seobu-Ro, Jangan-Gu, Suwon, Gyeong Gi-Do 16419, 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

Non-catalytic, non H2 sewage sludge

liquefaction was held in supercritical
fluids.

High bio-oil yields of 87.8 wt% and
HHV of 34.6 MJ kg1 were achieved.

The presence of water increases the
conversion up to 96% and HHV up to
37.3 MJ kg1.

Ester and nitrogenated compounds
were the major compounds in the
bio-oil.

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

Article history: Conversion of sewage sludge into fuel was investigated using a catalyst- and external hydrogen-free
Received 20 November 2016 supercritical fluid route. When dried sewage sludge was treated in supercritical ethanol, an extremely
Received in revised form 17 March 2017 high bio-oil yield of 87.8 wt% and a remarkable higher heating value (HHV) of 34.6 MJ kg1 were
Accepted 19 March 2017
obtained. The possibility of using non-dried sewage sludge as a fuel source was tested using various alco-
Available online 27 March 2017
hol–water mixtures; the presence of water resulted in an almost complete (96%) conversion and high
HHVs of 36.8 and 37.3 MJ kg1 for methanol–water (3:7, v/v) and ethanol–water (3:7, v/v) mixtures,
Keywords:
respectively. The main chemical compounds in the bio-oils were found to be esters and nitrogenated spe-
Sewage sludge
Liquefaction
cies. Plausible reaction mechanisms for sewage sludge conversion in each supercritical fluid are
Bio-oil discussed.
Supercritical fluid Ó 2017 Elsevier Ltd. All rights reserved.
Non-dry sludge

1. Introduction sludge represents a very promising candidate for the production of

Owing to its significant organic matter content (e.g., carbohy-
drates, proteins, lipids, and nucleic acids), with an energy content
comparable to that of typical biomass (12–20 MJ kg1) [1], sewage
⇑ Corresponding author at: School of Mechanical Engineering and SKKU
Advanced Institute of Nanotechnology (SAINT), Sungkyunkwan University, 2066,
Seobu-Ro, Jangan-Gu, Suwon, Gyeong Gi-Do 16419, Republic of Korea.
E-mail address: jaehoonkim@skku.edu (J. Kim).
alternative fuels for electricity and transportation [2]. Various ther-
mochemical approaches have been investigated for utilizing the
organic matter contained in sewage sludge [3–5]. Even though an
appreciable amount of bio-oil can be obtained by pyrolysis (50–
80 wt% on a dry ash-free basis) [6], the approach requires an
energy-intensive drying pretreatment of wet sewage sludge with
a water content of up to 80 wt%. The considerable energy con-
sumption of such drying processes makes pyrolysis less attractive
for practical scale applications.

http://dx.doi.org/10.1016/j.fuel.2017.03.061
0016-2361/Ó 2017 Elsevier Ltd. All rights reserved.
 H. Prajitno et al. / Fuel 200 (2017) 146–152
On the other hand, liquefaction, in which a suitable solvent is
used for extracting and/or decomposing the organic matter present
in sewage sludge, has several advantages over pyrolysis, as a dry-
ing pretreatment is not necessary and lower temperatures can thus
be used. So far, several studies have investigated the liquefaction of
sewage sludge in sub- or supercritical water (subH2O or scH2O,
respectively) [7]. The calorific value of bio-oil shows a moderate
increase upon raising the temperature of the gasification regime
to 500 °C using external molecular hydrogen or a catalyst
(e.g., K2CO3, Ca(OH)2, Ba(OH)2, Na2CO3, NaOH, FeSO4, FeS, Raney
Ni, FeSO4, MoS2, and sewage sludge-based activated carbon)
[2,7–11]. For example, a high calorific value of 39.1 MJ kg1 was
obtained in the presence of an activated carbon catalyst based on
sewage sludge [10]. Use of organic solvents such as methanol
[12], ethanol [5,11–13], acetone [12], tetralin [14], and 2-
methyltetrahydrofuran (MeTHF) [14] instead of water has been
shown to improve the yield and properties of bio-oil to some
degree. Even though previous studies have demonstrated the sig-
nificant potential of sewage sludge liquefaction for the production
of liquid fuels, the use of external molecular hydrogen, heteroge-
neous catalysts, and expensive chemicals (e.g., tetralin and MeTHF)
increases the processing costs, which prevents the practical scale
implementation of liquefaction for the production of bio-oil. In
order to improve the energy efficiency of the sewage sludge con-
version process, methods based on the wet sewage sludge dis-
charged from wastewater treatment plants could represent a
valid feed. Despite the potential value of non-dried sewage sludge
as a feed in supercritical alcohol-based conversion processes, the
only published study on these systems [11] was negatively affected
by the use of expensive ethanol and reported a low bio-oil yield
(38 wt%).
In this study, we investigate the feasibility of utilizing the lique-
faction of wet sewage sludge in supercritical methanol and ethanol
(scMeOH and scEtOH, respectively) for the high-yield production
of bio-oil with high calorific values and low acidity. In order to
study the fundamental liquefaction behavior of sewage sludge in
different solvents (water, methanol, and ethanol), dried sewage
sludge was liquefied under various operating conditions (involving
different temperatures, residence times, and concentrations). Then,
the feasibility of using non-dried sewage sludge as a fuel source
was tested using a methanol–water or ethanol–water mixture as
the liquefaction solvent. Previously, we demonstrated that scEtOH
in the absence of water could depolymerize highly recalcitrant lig-
nin into high-yields of bio-oil [15]. The favorable physical proper-
ties of supercritical fluids (high diffusivity and density, low
viscosity, and rapid rates of mass and heat transfer), as well as
the unique reactivity of supercritical alcohols (e.g., in situ hydrogen
donation [16,17], alkylation [18,19], hydroxyalkylation [20,21],
deoxygenation [22,23], and esterification [24]), resulted in a high
bio-oil yield of 87.8 wt% with a high calorific value of 34.6 MJ kg1
from the liquefaction of dried sewage sludge in scEtOH under opti-
mized conditions. On the other hand, a moderate bio-oil yield of
51.0 wt% with a comparable calorific value of 34.1 MJ kg1 was
obtained in supercritical methanol (scMeOH). When a 3:7 (v/v)
methanol–water mixture with low methanol content was used, a
moderate yield of bio-oil (52.5 wt%) with a high calorific value
(36.8 MJ kg1) could be achieved without using external hydrogen
and catalysts. These values are comparable to those previously
reported for catalytic liquefaction using dried sewage sludge and
organic solvents (entries 4, 5, 7, 9, and 11 in Table S1, Supporting
Information) [5,11–14]. Unlike these previous studies, the present
work focuses on alcohol–water mixtures as liquefaction solvents:
we assess the feasibility of using an economically viable solvent
and removing the expensive drying pretreatment in order to
achieve the high-yield production of bio-oils with excellent
properties.
147
2. Experimental
2.1. Materials
Sewage sludge slurry was collected from a wastewater treat-
ment plant located in Suwon, South Korea. The slurry was initially
dried at 105 °C for 12 h, followed by tests performed to assess the
reactivity of three supercritical fluids (water, methanol, and etha-
nol) and the effect of water content associated with the use of alco-
hol–water mixtures. Table S2 lists the properties of the dried
sewage sludge. The combustion behavior of the dried sewage
sludge is illustrated in Fig. S1. HPLC-grade methanol, ethanol,
Ò
and acetone were purchased from Honeywell Burdick and Jackson
(USA). Deionized water (HPLC grade) was purchased from Wako
Pure Chemical Industries, Ltd. (Japan). High-purity nitrogen
(99.99%), used for purging the reactor, was purchased from JC
Gas Company (South Korea).
2.2. Liquefaction procedure
Liquefaction experiments were conducted in a stirred SUS 316
reactor with an inner volume of 140 mL. The reactor was equipped
with a magnetically driven stirrer (HM-3200, Hanwoul Engineer-
ing Inc., South Korea). The temperature of the reactor was con-
trolled using a heat furnace and cartridge heaters inserted in the
reactor wall. The solvent filling ratio in the reactor was fixed to
50 vol%. After loading the sewage sludge and solvent, the reactor
was sealed and flushed three times with N2 to remove residual
air, followed by pressurization with N2 at 1 MPa. The mixture
was stirred at 500 rpm inside the reactor and heated to the target
temperature at an average heating rate of 15 °C min1. The time
required for heating and cooling was not included in the reaction
time. Fig. S2 shows the protocol employed for the separation of
gas, liquid, and solid products after liquefaction. A detailed descrip-
tion of the separation protocol is given in the Supporting
Information.
2.3. Product analysis and characterization
The yields of bio-oil, gas products, and solid residue were calcu-
lated using Eqs. (1)–(3), respectively. The labels ‘‘dafb” and ‘‘db”
used in the equations stand for ‘‘dry ash-free basis” and ‘‘dry basis”,
respectively.
Weight of bio  oilðdafbÞ
Bio  oil yieldðwt%Þ ¼  100
Weight of sewage sludgeðdafbÞ
ð1Þ
Weight of produced gas
Gas yield ðwt%Þ ¼  100 ð2Þ
Weight of sewage sludgeðdafbÞ
Weight of solid residue
Solid residue yieldðwt%Þ ¼  100
Weight of sewage sludgeðdbÞ
ð3Þ
Weight of sewage sludgeðdafbÞ  weight of coke
Conversionð%Þ ¼
Weight of sewage sludgeðdafbÞ
 100
ð4Þ
The yield of coke formed during liquefaction was determined
by combustion of the organic species remaining in the solid resi-
due using thermogravimetric analysis (TGA). Fig. S3 shows typi-
cal TGA profiles of the dried sewage sludge, bio-oil, and solid
residue.
148 H. Prajitno et al. / Fuel 200 (2017) 146–152

Weight of solid residueðdafbÞ

Coke yield ðwt%Þ ¼  100 ð5Þ
Weight of sewage sludgeðdafbÞ
The elemental analysis of dried sewage sludge and bio-oil was
conducted using a Vario EL Cube elemental analyzer equipped with
a TCD detector (Elementar Analysensysteme GmbH, Germany). The
higher heating values (HHVs) of the dried sewage sludge and bio-
oil were calculated from the elemental analysis results according
to the DIN 51900 standard (Eq. (6)).

1 ð34C þ 124:3H þ 6:3N þ 19:3S  9:8OÞ

HHV ðMJ kg Þ ¼ ð6Þ
100
In Eq. (6), C, H, N, S, and O represent the weight percentages of
carbon, hydrogen, nitrogen, sulfur, and oxygen, respectively,
obtained from the elemental analysis.
The total acid number (TAN) was measured via titration of bio-
oil with 0.1 M KOH in isopropyl alcohol (IPA) using a Metrohm 877
Titrino plus instrument (Metrohm Ltd., Switzerland). The TAN was
calculated using Eq. (7), according to the ASTM D664–11a test
procedure.

ðA  BÞ  M  56:1
TAN ðmg KOH g1 Þ ¼ ð7Þ
W
In Eq. (7), A is the volume of KOH in the IPA solution used to
titrate bio-oil up to the last inflection end point (mL), B is the blank
titration volume (mL), M is the alcoholic KOH solution concentra-
tion (mol L1), and W (g) is the mass of bio-oil. The water content
was determined by Karl Fischer titration using a Metrohm 877
Titrino plus instrument. The total inorganic content in the dried
sludge, bio-oil, and solid residue was analyzed using a Q50 thermo-
gravimetric analyzer (TA Instruments, USA) in air at temperatures
ranging from 30 to 800 °C. The concentrations of inorganic materi-
als were determined using an X-ray fluorescence (XRF) S4 Bruker
spectrometer (Bruker AXS GmbH, Germany). Gas
chromatography-mass spectrometry (GC–MS) was employed to
characterize the bio-oil composition using an Agilent 7890 N GC
and Pegasus high-throughput (HT) time-of-flight (TOF)-MS system
(Leco, USA). A detailed description of the GC-TOF/MS analysis is
given elsewhere [25]. All gases produced were qualitatively and
quantitatively analyzed using a Perkin Elmer Clarus 600 GC-
Model Arnel 1115PPC refinery gas analyzer (RGA) (Perkin Elmer,
USA). The details of the RGA-GC analysis have been provided else-
where [26].

3. Results and discussion

Fig. 1. Effects of supercritical fluids on (a) product yields, (b) H/C and O/C ratios in
the van Krevelen diagram, and (c) gas composition. WSO: water-soluble oil.
3.1. Effect of supercritical fluids on sewage sludge liquefaction

Fig. 1 shows the effect of supercritical fluids on the liquefaction

of sewage sludge tested at 400 °C, 9.1 wt%, and 30 min. These reac-
tion conditions were chosen based on screening tests of the reac-
tion parameters, as shown in Figs. S4–S8 and Tables S3–S5.
ScEtOH resulted in a significantly higher bio-oil yield (87.8 wt%)
compared to scMeOH (51.0 wt%) and scH2O (22.0 wt%). In addition,
scEtOH led to a lower coke yield (6.5 wt%) compared to scMeOH
(8.6 wt%) and scH2O (13.4 wt%). The bio-oil produced using scEtOH
exhibited a low O/C ratio of 0.09 (Fig. 1b) and a high HHV of
34.6 MJ kg1 (Table 1), clearly indicating that, as a solvent, scEtOH
strongly favors the liquefaction of dried sewage sludge. The better
performance of scEtOH can be attributed to at least two effects.
First, the mechanisms of liquefaction in supercritical alcohols and
scH2O are quite different; the unique hydrogen-donating ability
of supercritical alcohols can retard repolymerization and conden-
sation of reaction intermediates at around 400 °C, while scH2O
often results in enhanced coke formation and gasification, thereby
decreasing the bio-oil yield [27]. Thus, a lower bio-oil yield at
400 °C than at 300 °C is often obtained when high-temperature
water is used as the biomass liquefaction solvent [28,29]. To inves-
tigate the possibility of obtaining a high bio-oil yield at the lower
temperature, tests were carried out using subH2O at 310 °C, and
the results are listed in Table S4. The bio-oil yield obtained in
subH2O (41.6 wt%) was approximately two times higher than that
observed in scH2O (22.0 wt%). However, the O/C ratio and HHV
were significantly lower for the bio-oil produced in subH2O (0.21
and 31.5 MJ kg1, respectively) than in scH2O (0.08 and
36.5 MJ kg1, respectively). A second possible cause for the supe-
rior overall performance of scEtOH compared to scMeOH is that
the former resulted in the production of a significantly lower
amount of light hydrocarbons (LHCs), which could not be recov-
ered by the separation process employed in this work. In fact,
while the LHC amounts produced in scEtOH and scMeOH were
2.2 and 36.0 wt%, respectively, the total oil yields (bio-oil + LHCs)
in the two supercritical fluids were very similar to each other
 H. Prajitno et al. / Fuel 200 (2017) 146–152 149

Table 1
Product yields and bio-oil properties obtained from liquefaction at 400 °C for 30 min with a biomass concentration of 9.1 wt%.

Entry Solvent Alcohol/water ratio (v/v) P (MPa) Solid residuea C H N S O HHV (MJ kg1)
(wt%) (wt%)
3 scMeOH 10:0 36.5–39.7 32.7 72.3 8.3 5.8 0.4 12.4 34.1
11 scMeOH–scH2O 7:3 37.2–40.2 31.4 72.1 9.0 5.4 0.7 11.4 35.0
12 scMeOH–scH2O 5:5 36.8–39.3 29.8 74.3 9.0 4.9 1.0 9.0 36.1
13 scMeOH–scH2O 3:7 34.9–36.3 30.2 76.0 9.1 5.1 0.8 9.1 36.8
10 scH2O 0:10 36.5–39.7 42.6 75.6 8.6 5.5 3.2 8.0 36.5
9 scEtOH 10:0 28.5–32.2 32.0 71.5 7.2 5.0 1.2 8.2 33.0
14 scEtOH–scH2O 7:3 33.6–36.2 31.4 71.0 9.2 5.7 1.1 10.1 35.2
15 scEtOH–scH2O 5:5 34.8–37.1 31.1 71.8 8.8 5.5 1.3 10.9 35.0
16 scEtOH–scH2O 3:7 33.6–35.9 29.1 75.5 9.4 5.3 1.7 8.0 37.3
10 scH2O 0:10 36.5–39.7 42.6 75.6 8.6 5.5 3.2 8.0 36.5
a
On a dry basis.

(Fig. 1a), indicating that cracking is significantly more activated in 100

the case of scMeOH. A more sophisticated separation process of the (a)
90
LHCs from the residual solvent would lead to a higher yield of bio-

GC-MS relative peak area (%)

80
oil using scMeOH. An important issue to address prior to the large- Others
Nitrogenated
scale implementation of the present sewage sludge conversion 70
Hydrocarbon
process is the higher cost of ethanol, which is typically over two 60 Aromatic
Oxygenated
times more expensive than methanol. The very low yield of bio- 50 Phenol
oil in scH2O and subH2O is attributed to the formation of relatively Ester
40 Acid
large amounts of coke and highly water-soluble (or hydrophilic) Ketone
organic species, which could not be recovered by extraction using 30 Aldehyde
Alcohol
ethyl acetate (Fig. S2b). 20
The main gases produced from liquefaction in scH2O were CO2 10
and CO, indicating that decarboxylation and decarbonylation are
0
the predominant pathways for deoxygenation (Fig. 1c). Dehydra- scMeOH scEtOH scH2O
tion is another well-known deoxygenation mechanism during
Solvent
hydrothermal liquefaction [30]. The bio-oil recovered after extrac-
tion with ethyl acetate exhibits a very low oxygen content of 8.0 wt 50 2.0
%, a low O/C ratio of 0.08 (Fig. 1b), and a high calorific value of (b)
36.5 MJ kg1.
40 1.6
As shown in Fig. 2a and Fig. S6, and detailed in Table S5, the
TAN (mg KOH g oil)

Ash content in bio-oil (wt%)

compositions of the bio-oils produced using supercritical alcohols
-1

and scH2O were quite different. Although it is very difficult to iden-
tify a well-defined reaction mechanism for each type of solvent,
because the feed was composed of complex sewage sludge, several
reactions could be proposed based on the different chemical spe-
cies observed in the GC-TOF/MS analysis.
(1) The percentage area of the GC-TOF/MS peak (area%) corre-
sponding to phenolic compounds produced in scH2O
(27.2%) was significantly greater than that observed in
scMeOH (7.8%) and scEtOH (6.2%). The formation of phenolic
compounds in scH2O is attributed to the carbohydrate frac-
tion of the sewage sludge. A series of reactions, such as
hydrolysis, dehydration, diene formation, and Diels–Alder
cycloaddition, result in the formation of phenolic com-
pounds from carbohydrates [31]. Furthermore, the high
amount of phenolic compounds formed in scH2O con-
tributed to the high TAN value observed (35.5 mg KOH g–1,
Fig. 2b).
(2) When scMeOH was used, methylated phenols (2,3-
dimethylphenol and 2,4,6-trimethylphenol) were the main
phenolic compounds obtained, while ethylated phenols (4-
ethylphenol and 3,4-diethylphenol) were obtained from liq-
uefaction in scEtOH, demonstrating the C-alkylation ability
of scMeOH and scEtOH [18,32].
(3) When scH2O was used, almost no ester compounds were
formed, suggesting that the bio-oil could contain some
amount of acidic species. However, the area% corresponding
to acid species in the bio-oil was very small (1.5%), and was
30 1.2
20 0.8
10 0.4
0 0.0
scMeOH scEtOH scH2O
Solvents
Fig. 2. Effects of supercritical fluids on (a) bio-oil composition and (b) TAN
reduction and ash content.
attributed to the hydrophilicity of short-chain acids, which
results in these species residing preferentially in the water
phase.
(4) The area% corresponding to ester species formed in scMeOH
was greater (33.2%) than that measured in scEtOH (17.0%),
indicating that scMeOH is more active in the esterification/
transesterification reactions. A similar trend has been
observed in previous studies, which reported high yields of
fatty acid esters when scMeOH was used [24,33].
(5) When scEtOH was used, short-chain monoalcohols (e.g.,
1-butanol, 2-ethyl-1-butanol, 1-hexanol, and 2-hexanol)
were formed; these compounds were not detected in the
bio-oils produced in scMeOH and scH2O. The formation of
150 H. Prajitno et al. / Fuel 200 (2017) 146–152

these monoalcohols may be due to the reduction of acidic products. This observation is consistent with previous studies of
species associated with the enhanced hydrogen donor abil- the liquefaction of biomass in alcohol (methanol or ethanol)–water
ity of scEtOH at 400 °C. mixtures; for example, the use of a 50 wt% methanol–50 wt% water
mixture resulted in higher yields of bio-oil (65 wt%) and higher
3.2. Liquefaction in supercritical alcohol–water mixtures conversions (>95%) from woody biomass compared to a single sol-
vent, which led to a bio-oil yield of 23 wt% and a conversion of 42%
In the previous section, we examined the conversion process of [34]. After treatment with microalgae, 40 vol% ethanol in water
dried sewage sludge under different operating conditions and in was found to be the optimal mixture composition, resulting in a
different supercritical fluids. Although high yields of bio-oils with bio-oil yield of 65 wt% and a conversion of 98% [35]. At methanol
high calorific values can be obtained using scMeOH and scEtOH, contents greater than 30 vol%, the yield of bio-oils obtained using
the possibility of using dried sewage sludge in commercial scale methanol–water mixtures did not significantly change (51–53 wt
plants is rather limited, due to the very high energy costs of the %). On the other hand, in ethanol–water mixtures, the bio-oil yield
drying process, which reduces the energy efficiency of the conver- increased from 22.0 wt% (pure scH2O) to 87.8 wt% (pure scEtOH)
sion of sewage sludge to fuel. In this section, to investigate the fea- with increasing ethanol content. Again, this result can be attribu-
sibility of using non-dried dewatered sludge cake, typically ted to the larger amount of recoverable fractions produced using
released from wastewater treatment plants, various mixtures with scEtOH.
different alcohol/water ratios were employed as the supercritical No clear trends emerged from the gas-phase analysis of the var-
medium. Compared with liquefaction using pure alcohol or pure ious mixture ratios (Fig. S9), due to the complex nature of the alco-
water, the use of alcohol–water mixtures resulted in higher con- hol–water mixtures used as liquefaction solvent. In addition to the
versions and lower coke formation (Fig. 3 and Table 1). For exam- gases obtained from the sewage sludge, some fraction of the alco-
ple, in methanol–water mixtures with volume ratios between 7:3 hols can be decomposed into gaseous products during liquefaction.
and 3:7, the conversion of organic species in sewage sludge ranged Compared with liquefaction using pure alcohol, the presence of
from 96.3% to 94.1%, indicating almost complete conversion to the water further increased the H/C ratio, resulting in increased HHVs
liquid and gas phases; these values were greater than those of up to 36.8 and 37.3 MJ kg1 in the case of 3:7 (v/v) methanol–
obtained using pure scMeOH (91.4%) and pure scH2O (86.6%). Sim- water and ethanol–water mixtures, respectively (Figs. 3c-d and
ilar results were obtained from liquefaction using ethanol–water Table 1). Hence, the use of a supercritical alcohol–water mixture
mixtures with ratios ranging between 7:3 and 3:7. Whereas the as the liquefaction solvent appears as an effective strategy for
synergistic effect of the alcohol–water mixture retarding coke for- obtaining bio-oils with higher yields and calorific values.
mation is not evident at this stage, the modified physical properties The chemical composition of the bio-oils produced at various
and reactivity of the alcohol–water mixtures under supercritical alcohol–water ratios is shown in Figs. 4a and b and detailed in
conditions may result in the conversion of higher amounts of the Table S6, while Fig. S10 shows representative chromatograms.
organic matter contained in sewage sludge to liquid and gas Upon increasing the alcohol content, the area% corresponding to

100 100
Yield (wt%) and conversion (%)

Yield (wt%) and conversion (%)

90 90 Conversion
Conversion
80 (a) 80 (b)
70 70 Bio-oil
60 60
Bio-oil
50 50
40 LHCs + WSO 40
30 30 LHCs+WSO
20 20
Coke Coke
10 10
Gas products
0 Gas products 0
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100
Methanol (v%) Ethanol (v%)

2.0 2.0
1.8
Oil (c) 1.8 Oil (d)
1.6 Biomass 1.6 15
11 12 Biomass
16
1.4 13 1.4 14
Peat 10
10 3 Peat
1.2 1.2
9
H/C

H/C

1.0 Lignite R 1.0 Lignite R

Coal Coal R Dried Sewage Sludge
0.8 R Dried Sewage Sludge 0.8
3 Bio-oil_scMeOH 9 Bio-oil_scEtOH
0.6 10 Bio-oil_scH2O 0.6 10 Bio-oil_scH2O
0.4 11 Bio-oil_7/3 v/v scMeOH/H2O 0.4 14 Bio-oil_7/3 v/v scEtOH/H2O
Anthracite 12 Bio-oil_5/5 v/v scMeOH/H2O 15 Bio-oil_5/5 v/v scEtOH/H2O
0.2 0.2 Anthracite
13 Bio-oil_3/7 v/v scMeOH/H2O 16 Bio-oil_3/7 v/v scEtOH/H2O
0.0 0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
O/C O/C

Fig. 3. Effects of methanol-to-water ratio and ethanol-to-water ratio on (a, b) product yields and (c, d) on H/C and O/C ratios in the van Krevelen diagram. WSO: water-soluble
oil.
 H. Prajitno et al. / Fuel 200 (2017) 146–152 151

100 100
GC-MS relative peak area (%)
90
(a) 90
(b)
80 Others 80

GC-MS relative peak area (%)

Nitrogenated Others
70 Hydrocarbon 70 Nitrogenated
Aromatic Hydrocarbon
Oxygenated 60 Aromatic
60
Phenol Oxygenated
Ester Phenol
50 50
Acid Ester
Ketone Acid
40 Aldehyde
40 Ketone
Alcohol Aldehyde
30 30 Alcohol
20 20
10 10
0 0
0 30 50 70 100 0 30 50 70 100
Methanol (v%) Ethanol (v%)
60 2.0 70 2.0
(c) (d)
50 60

Ash content in bio-oil (wt%)

Ash content in bio-oil (wt%)

1.6 1.6
TAN (mg KOH g oil)

TAN (mg KOH g oil)

50
40
-1

-1
1.2 1.2
40
30
30
0.8 0.8
20
20
0.4 0.4
10 10

0 0.0 0 0.0
0 30 50 70 100 0 30 50 70 100
Methanol (v%) Ethanol (v%)

Fig. 4. Effects of methanol-to-water ratio and ethanol-to-water ratio on (a, b) bio-oil composition and (c, d) on TAN reduction and ash content.

the ester compounds increased, while that corresponding to phe- 4. Conclusions

nolic compounds decreased. This behavior is quite straightforward
to interpret, as discussed in the previous section. Relatively higher In this study, a noncatalytic, external hydrogen-free supercriti-
amounts of acidic species were produced from liquefaction using cal fluid route was developed for converting sewage sludge
30–50 vol% scMeOH and 50–70 vol% scEtOH, which resulted in into high yields of liquid bio-oil with high calorific value. The
high TAN values of 46–65 mg KOH g1 (Figs. 4c and d). The forma- conversion behavior was thoroughly investigated in different
tion of acidic species is attributed to the fragmentation of cellulose supercritical fluids (scH2O, scMeOH, and scEtOH, as well as
(carbohydrate) into aldehyde and ketone compounds [36], fol- scMeOH–scH2O and scEtOH–scH2O mixtures) under various reac-
lowed by oxidation in the presence of water. In the case of tion conditions, and the clear advantages of using supercritical
scMeOH–H2O mixtures, upon decreasing the methanol content, alcohols were demonstrated. The unique in situ hydrogen-
the area% corresponding to the acidic species and the TAN value donating ability and esterification, alkylation, and deoxygenation
increased, while the area% corresponding to the ester species reactivity associated with supercritical alcohols resulted in
decreased (Fig. 4a), indicating that the degree of esterification increased bio-oil yield, suppressed coke formation, led to oxygen
depends on the amount of methanol. The lower esterification abil- removal, and enhanced the calorific value of the bio-oil. The con-
ity of scEtOH may result in higher TAN values and an increased version of dried sewage sludge in scEtOH resulted in an extremely
area% corresponding to acidic species for the bio-oil produced with high bio-oil yield of 87.8 wt% and a high HHV of 34.6 MJ kg–1. The
the scEtOH–H2O mixture, compared with that obtained from the feasibility of employing wet sewage sludge as source material was
scMeOH–H2O mixture with the same alcohol/water ratio (50– tested using alcohol–water mixtures as the liquefaction solvent.
70 vol%). Upon decreasing the ethanol content from 50 to 30 vol Almost complete (96%) sewage sludge conversion was obtained
%, the TAN value abruptly decreased from 64.5 to 21.1 mg KOH using a mixture of 30 vol% methanol in water, with a bio-oil yield
g1 and the area% corresponding to the acidic species decreased of 52.5 wt% and a high HHV of 36.8 MJ kg1. Fatty acid methyl and
from 15.2 to 2.9%, which can probably be attributed to the clear ethyl esters, as well as nitrogenated compounds, were the main
separation between the water and oil phases at low ethanol con- chemical species present in the bio-oils produced by liquefaction
tents (Fig. S11). As short-chain acids (i.e., propanoic and butanoic using supercritical alcohols. The present results indicate that the
acid) are more hydrophilic, they prefer to remain in the water non-catalytic and hydrogen-free conversion of wet sewage sludge
phase rather than in the oil phase. On the other hand, with 50– using supercritical alcohol–water mixtures described in this work
70 vol% ethanol, the less distinct phase separation between the represents a very promising strategy for developing an economi-
two phases may result in the transfer of some short-chain acids cally viable process to upgrade sewage sludge into fuel.
into the oil phase.
152 H. Prajitno et al. / Fuel 200 (2017) 146–152
Acknowledgments
This study was supported by the New & Renewable Energy Core
Technology Program (Grant Nos. 20143030090940 and
20143030100980) of the Korea Institute of Energy Technology
Evaluation and Planning (KETEP) financed by the Ministry of Trade,
Industry, and Energy of the Republic of Korea. Additional support
from a National Research Foundation of Korea (NRF) grant funded
by the Korean government (MSIP) (Grant No. NRF-
2016R1A2B3008800) is also gratefully acknowledged.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.fuel.2017.03.061.
References
[1] Parikh J, Channiwala SA, Ghosal GK. A correlation for calculating HHV from
proximate analysis of solid fuels. Fuel 2005;84:487–94.
[2] Malins K, Kampars V, Brinks J, Neibolte I, Murnieks R, Kampare R. Bio-oil from
thermo-chemical hydro-liquefaction of wet sewage sludge. Bioresour Technol
2015;187:23–9.
[3] Manara P, Zabaniotou A. Towards sewage sludge based biofuels via
thermochemical conversion – A review. Renew Sustain Energy Rev
2012;16:2566–82.
[4] Fytili D, Zabaniotou A. Utilization of sewage sludge in EU application of old and
new methods-a review. Renew Sustain Energy Rev 2008;12:116–40.
[5] Huang H-J, Yuan X-Z, Zhu H-N, Li H, Liu Y, Wang X-L, et al. Comparative studies
of thermochemical liquefaction characteristics of microalgae, lignocellulosic
biomass and sewage sludge. Energy 2013;56:52–60.
[6] Fonts I, Gea G, Azuara M, Ábrego J, Arauzo J. Sewage sludge pyrolysis for liquid
production: a review. Renew Sustain Energy Rev 2012;16:2781–805.
[7] Wang Y, Chen G, Li Y, Yan B, Pan D. Experimental study of the bio-oil
production from sewage sludge by supercritical conversion process. Waste
Manag 2013;33:2408–15.
[8] Xu C, Lancaster J. Conversion of secondary pulp/paper sludge powder to liquid
oil products for energy recovery by direct liquefaction in hot-compressed
water. Water Res 2008;42:1571–82.
[9] Zhang L, Xu C, Champagne P. Energy recovery from secondary pulp/paper-mill
sludge and sewage sludge with supercritical water treatment. Bioresour
Technol 2010;101:2713–21.
[10] Zhai Y, Chen H, Xu B, Xiang B, Chen Z, Li C, et al. Influence of sewage sludge-
based activated carbon and temperature on the liquefaction of sewage sludge:
yield and composition of bio-oil, immobilization and risk assessment of heavy
metals. Bioresour Technol 2014;159:72–9.
[11] Li H, Yuan X, Zeng G, Huang D, Huang H, Tong J, et al. The formation of bio-oil
from sludge by deoxy-liquefaction in supercritical ethanol. Bioresour Technol
2010;101:2860–6.
[12] Huang H-J, Yuan X-Z, Li B-T, Xiao Y-D, Zeng G-M. Thermochemical liquefaction
characteristics of sewage sludge in different organic solvents. J Anal Appl
Pyrolysis 2014;109:176–84.
[13] Leng L, Yuan X, Shao J, Huang H, Wang H, Li H, et al. Study on demetalization of
sewage sludge by sequential extraction before liquefaction for the production
of cleaner bio-oil and bio-char. Bioresour Technol 2016;200:320–7.
[14] Lemoine F, Maupin I, Lemée L, Lavoie JM, Lemberton JL, Pouilloux Y, et al.
Alternative fuel production by catalytic hydroliquefaction of solid municipal
wastes, primary sludges and microalgae. Bioresour Technol 2013;142:1–8.
[15] Riaz A, Kim CS, Kim Y, Kim J. High-yield and high-calorific bio-oil production
from concentrated sulfuric acid hydrolysis lignin in supercritical ethanol. Fuel
2016;172:238–47.
[16] Ross DS, Blessing JE. Alcohols as H-donor media in coal conversion. 1. Base-
promoted H-donation to coal by isopropyl alcohol. Fuel 1979;58:433–7.
[17] Ross DS, Blessing JE. Alcohols as H-donor media in coal conversion. 2. Base-
promoted H-donation to coal by methyl alcohol. Fuel 1979;58:438–42.
[18] Takebayashi Y, Hotta H, Shono A, Yoda S, Furuya T, Otake K. Noncatalytic
ortho-selective methylation of phenol in supercritical methanol: the
mechanism and acid/base effect. Ind Eng Chem Res 2008;47:704–9.
[19] Kishida N, Kamitanaka T, Fusayasu M, Sunamura T, Matsuda T, Osawa T, et al.
Ring-methylation of pyrrole and indole using supercritical methanol.
Tetrahedron 2010;66:5059–64.
[20] Nakagawa T, Ozaki H, Kamitanaka T, Takagi H, Matsuda T, Kitamura T, et al.
Reactions of supercritical alcohols with unsaturated hydrocarbons. J Supercrit
Fluids 2003;27:255–61.
[21] Kamitanaka T, Hikida T, Hayashi S, Kishida N, Matsuda T, Harada T. Direct
addition of supercritical alcohols, acetone or acetonitrile to the alkenes
without catalysts. Tetrahedron Lett 2007;48:8460–3.
[22] Budi Nursanto E, Nugroho A, Hong S-A, Kim SJ, Yoon Chung K, Kim J. Facile
synthesis of reduced graphene oxide in supercritical alcohols and its lithium
storage capacity. Green Chem 2011;13:2714–8.
[23] Seo M, Yoon D, Hwang KS, Kang JW, Kim J. Supercritical alcohols as solvents
and reducing agents for the synthesis of reduced graphene oxide. Carbon
2013;64:207–18.
[24] Warabi Y, Kusdiana D, Saka S. Reactivity of triglycerides and fatty acids of
rapeseed oil in supercritical alcohols. Bioresour Technol 2004;91:283–7.
[25] Prajitno H, Insyani R, Park J, Ryu C, Kim J. Non-catalytic upgrading of fast
pyrolysis bio-oil in supercritical ethanol and combustion behavior of the
upgraded oil. Appl Energy 2016;172:12–22.
[26] Susanti RF, Dianningrum LW, Yum T, Kim Y, Lee BG, Kim J. High-yield
hydrogen production from glucose by supercritical water gasification without
added catalyst. Int J Hydrogen Energy 2012;37:11677–90.
[27] Brand S, Hardi F, Kim J, Suh DJ. Effect of heating rate on biomass liquefaction:
Differences between subcritical water and supercritical ethanol. Energy
2014;68:420–7.
[28] Brand S, Susanti RF, Kim SK. Lee H-s, Kim J, Sang B-I. Supercritical ethanol as an
enhanced medium for lignocellulosic biomass liquefaction: Influence of
physical process parameters. Energy 2013;59:173–82.
[29] Toor SS, Reddy H, Deng S, Hoffmann J, Spangsmark D, Madsen LB, et al.
Hydrothermal liquefaction of Spirulina and Nannochloropsis salina under
subcritical and supercritical water conditions. Bioresour Technol
2013;131:413–9.
[30] Peterson AA, Vogel F, Lachance RP, Froling M, Antal JMJ, Tester JW.
Thermochemical biofuel production in hydrothermal media: a review of
sub- and supercritical water technologies. Energy Environ Sci 2008;1:32–65.
[31] Williams PT, Onwudili J. Composition of products from the supercritical water
gasification of glucose: a model biomass compound. Ind Eng Chem Res
2005;44:8739–49.
[32] Horikawa Y, Uchino Y, Sako T. Alkylation and acetal formation using
supercritical alcohol without catalyst. Chem Lett 2003;32:232–3.
[33] Demirbas A. Studies on cottonseed oil biodiesel prepared in non-catalytic SCF
conditions. Bioresour Technol 2008;99:1125–30.
[34] Cheng S, D’cruz I, Wang M, Leitch M, Xu C. Highly efficient liquefaction of
woody biomass in hot-compressed alcoholwater co-solvents. Energy Fuels
2010;24:4659–67.
[35] Chen Y, Wu Y, Zhang P, Hua D, Yang M, Li C, et al. Direct liquefaction of
Dunaliella tertiolecta for bio-oil in sub/supercritical ethanol–water. Bioresour
Technol 2012;124:190–8.
[36] Russell JA, Molton PM, Landsman SD. Chemical comparisons of liquid fuel
produced by thermochemical liquefaction of various biomass materials.
Miami, Florida. In: 3rd Miami International Conference on Alternative
Energy Sources.