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Bioresource Technology 237 (2017) 108121

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Co-liquefaction of spent coffee grounds and lignocellulosic feedstocks


Linxi Yang a, Quan (Sophia) He a,, Peter Havard a, Kenneth Corscadden a, Chunbao (Charles) Xu b,
Xuan Wang b
a
Department of Engineering, Faculty of Agriculture, Dalhousie University, Truro, Nova Scotia B2N 5E3 Canada
b
Institute for Chemicals and Fuels from Alternative Resources (ICFAR), Faculty of Engineering, Western University, London, ON N6A 5B9 Canada

h i g h l i g h t s

 Co-liquefaction of spent coffee grounds and lignocellulosic feedstocks.


 Lquefaction conditions: 250 C, feedstock combination ratio 1:1 and 5% NaOH as a catalyst.
 In co-liquefaction of SCG and CS, the oil yield was increased by 20.9%.

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

Article history: Co-liquefaction of spent coffee grounds (SCG) with paper filter (PF), corn stalk (CS) and white pine bark
Received 9 December 2016 (WPB) respectively, was examined in subcritical water for bio-crude oil production. The optimum reac-
Received in revised form 17 February 2017 tion temperature was 250 C, and the mixing biomass ratio was 1:1. SCG and CS was identified to be the
Accepted 18 February 2017
best feedstock combination with a significant positive synergetic effect in the co-liquefaction process
Available online 21 February 2017
with 5% NaOH as a catalyst. The yield of bio-crude oil was increased by 20.9% compared to the mass aver-
aged yield from two feedstocks, and the oil quality was also improved in terms of viscosity and relative
Keywords:
molecular mass. A negative effect presented in the co-liquefaction of SCG/WPB. The resulting bio-crude
Spent coffee grounds (SCG)
Co-liquefaction
oils were characterized by elemental analyzer, GCMS, GPC and viscometer, indicating that mixing feed-
Bio-crude oil stock in the co-liquefaction process also influenced the higher heating value (HHV), viscosity, molecular
Synergistic effect mass and chemical composition of bio-crude oil.
Lignocellulose feedstocks 2017 Elsevier Ltd. All rights reserved.

1. Introduction technology faces several challenges, including low yield (generally


in the range of 2060%) and quality issues (corrosive, viscous/high
In world facing concerns over global warming and fossil fuel density, acidic, unstable and low HHV etc.) of the resulting bio-
depletion, it is essential to seek renewable and environmentally crude oil, and high capital investment in reaction/separation sys-
sustainable energy alternatives to our current energy production tems (Elliott et al., 2015; Huang and Yuan, 2015; Toor et al.,
practices. Biomass is a renewable source that is able to produce liq- 2011). Research has been conducted for the production of bio-
uid fuels. It is carbon-neutral and geographically wider available crude oil from a variety types of biomass such as forest/agriculture
than other sources, and thus provides a secure, independent and residues (Feng et al., 2014; Liu et al., 2013; Xu and Lad, 2008; Zhu
localized energy supply (Nigam and Singh, 2011; Peterson et al., et al., 2014; Zhu et al., 2015a,b), food processing waste (Pavlovic
2008; Singh et al., 2016). et al., 2013), animal manure (Theegala and Midgett, 2012), munic-
Hydrothermal liquefaction (HTL) is a thermochemical process, ipal/sewage waste (Huang et al., 2014), and recently macro/
in which the bio-polymeric structure of biomass is broken down microalgae (Biller and Ross, 2011; Singh et al., 2015). Most of
into liquid, gas and solid fractions in sub/supercritical water or research has been revolving around investigating the effects of
organic solvent medium. HTL has advantageous over other ther- reaction parameters (temperature, catalyst and solvent etc.) on
mochemical processes in that it can directly transform wet bio- the yield and quality of the bio-crude oil.
mass into energy-dense product (bio-crude oil) and thus The nature of biomass feedstock, i.e., different composition of
eliminate the energy intensive pre-drying processes. However, this cellulose, hemicellulose, lignin, lipid and protein, also has signifi-
cant impact on the yield and quality of the bio-crude oil. The objec-
Corresponding author. tive of HTL is to obtain as much as biocrude and minimize solid
E-mail address: quan.he@dal.ca (Quan (Sophia) He).
residues. The quality of bio-crude oil can be characterized by its

http://dx.doi.org/10.1016/j.biortech.2017.02.087
0960-8524/ 2017 Elsevier Ltd. All rights reserved.
L. Yang et al. / Bioresource Technology 237 (2017) 108121 109

higher heating values (HHV), viscosity, density, acidity, stability, with other available biomass would definitely improve the eco-
molecular weight distribution, O/C or H/C ratios and chemical nomic viability. In addition, the lipid containing feedstock was
compositions etc. Depending on downstream application, specific reported to have positive impact on the oil production when co-
chemical composition and properties might be favorable. Most of liquefied with lignocellulose biomass (e.g., swine manure and
studies examined the lignocellulose-based feedstocks which con- aspen wood). The FFA in the feedstock acted as a hydrogenating
tain a high content of lignin with low levels of lipid and protein. agent in the liquefaction process to suppress the secondary-
The yields of bio-crude oils derived from this category of feed- decomposition of oil fragments and further enhance the oil yield
stocks are low (2036%) with the HHVs in the range of 20 and oil quality (less viscosity and low acidity) (Xiu et al., 2010,
36 MJkg1 (Liu et al., 2013; Xu and Lad, 2008; Zhu et al., 2015a, 2011).
b). Pedersen et al. used glucose, xylose and lignin as representa- This paper explores the co-liquefaction of SCG with a number of
tives of individual components and investigated the reaction path- lignocellulosic feedstock, i.e., paper filter (PF), corn stalk (CS) and
ways and chemical composition of bio-crude. It was proposed that white pine bark (WPB). The objective is to obtain possible synergistic
glucose and xylose generated biocrude rich in cyclopentenones and effects between these feedstocks, which might increase the yield of
lignin led to oxygenated aromatics. (Pedersen and Rosendahl, the bio-crude oil and thus improve overall economic viability of
2015). The results held the promise of controlling the properties hydrothermal liquefaction. In addition, establishment of correlation
of bio-crude oil through feedstock composition, however, a predic- between feedstock combination and the quality of bio-crude oil
tion on relationship between feedstock and bio-crude was not fully would provide valuable information for feedstock selection based
established. Recently, microalgae have become a popular feed- on the downstream use and/or refining of bio-crude oil. It is also
stock. It was reported that algal feedstocks rich in lipid and protein expected that this explorative study could invite more research
improved the oil yield (5580%). (Biller et al., 2011; Huang and effort in this emerging and promising topic, co-liquefaction.
Yuan, 2015; Teri et al., 2014). Biller et al. examined six model com-
pounds and found that in terms of bio-crude oil yield, a general
2. Experimental
trend was in the order of lipid > protein > carbohydrate. The yield
of a mixture could be predicted by a linear additive behavior of
2.1. Materials and their properties
individual component such as protein, lipid and carbohydrate for
some microalgae strains but not true for others. The behavior of
Spent coffee grounds, Paper filter, corn stalk and white pine
each chemical components in HTL was not just simply additive.
bark were selected as representatives of lignocellulosic biomass
Teri et al. conducted liquefaction of protein, polysaccharides and
with different contents in holocellulose, lignin, protein and extrac-
lipid alone and in mixtures. They also observed that in some cases,
tives (e.g., SCG with a significant amount of extractives/lipid; PF
biocrude yield from feedstock mixture was very close to the mass-
with high content of holocellulose; WPB with a high amount of lig-
averaged yield from the individual compounds. However, for some
nin). The wet SCG were collected from Tim Hortons, Truro, Canada.
combinations, the yield of mixture exceeded the mass-averaged
The PF typically used for coffee filtering were purchased from Dol-
yield calculated from pure compound. This result was of great
larama, London, Canada, and were crushed and grounded. The CS
interest and provided the evidence that blending feedstock did
and WPB were provided by a local sawmill in Northwestern Ontar-
influence the oil product yield. Co-liquefaction of different feed-
io, Canada. These feedstocks were air dried, and ground into parti-
stocks therefore has potential to increase oil yield, control product
cles sieved through a 20 mesh sieve (0.841 mm) as shown in Fig. 1,
distribution and make full use of all kinds of biomass waste avail-
then oven-dried at 105 C in air for several days. All of the dried
able. A few other attempts at co-liquefaction have been reported,
samples were kept in sealed plastic bags and stored in a refrigera-
including aspen wood with glycerol (Pedersen et al., 2015, 2016),
tor at 4 C. The chemicals used included acetone and NaOH, all CAS
paper-mill sludge with waste newspaper (Zhang et al., 2011),
reagent grade, purchased from the Sigma-Aldrich and were used as
swine manure with crude glycerol (Xiu et al., 2011; Ye et al.,
received.
2012), swine manure with algal biomass (Chen et al., 2014), sew-
The proximate analysis, elemental content and chemical com-
age sludge with teacake (Zhai et al., 2015), microalgae with ligno-
positions of each dried feedstock are presented in Table 1. Volatile
cellulose biomass (Gai et al., 2015), microalgae with synthetic
matters were determined by thermogravimetric analysis TGA
polymer (Pei et al., 2012; Yuan et al., 2009) and macro algae with
(Pyris 1, Perkin Elmer) in N2, heated to 800 C at 10 Cmin1, then
microalgae (Jin et al., 2013). Some of these studies did observe that
kept at 800 C for 15 min. The volatile matters were calculated by
co-liquefaction enhanced the yield and altered the properties of
the weight loss below 200 C. The ash content was determined by
the resulting bio-crude oil, even though the underlying synergistic
combusting feedstocks at 575 C for 3 h, according to ASTM E1755-
effects from blending these biomasses are not well understood.
01 (ASTM, 2007). The elemental compositions were determined by
From an economic perspective, co-liquefaction has additional
using an Elemental Analyzer (vario EL cube Elementar). The holo-
benefit, significant reduction in the logistics costs associated with
cellulose content was determined using the modified Chlorination
collection and haulage to a center processing plant. Biomass is bulky,
method (ASTM, 1978) and the protein content was calculated
has a low energy density and may vary by season. It may be difficult
based on the nitrogen composition from elemental analysis using
to collect sufficient quantity of one type biomass in a region to make
the nitrogen factor of 6.25 (Lpez et al., 2010). Extractives content
the overall production economically viable (Overend, 1982).
was determined by using Soxhlet extraction according to the
Spent coffee grounds (SCG) are solid residue from the coffee
method of Chemical Analysis and Testing Task Laboratory Analyt-
brewing process. They are generally underutilized, in many
ical Procedure (Ehrman, 1994). The lignin (Klason) content was
instances disposed in landfills (Kondamudi et al., 2008). In our pre-
determined through sulfuric acid hydrolysis according to the
vious study (Yang et al., 2016a,b), SCG was identified as a promis-
method of Chemical Analysis and Testing Task Laboratory Analyt-
ing feedstock for bio-crude oil production via HTL. The yield of the
ical Procedure (Templeton and Ehrman, 1995).
bio-crude oil from SCG was higher than those of bio-crude oils
derived from lignocellulosic biomass and the HHVs were compara-
ble. The particle size of SCG was in the range of 200300 mm, suit- 2.2. Co-liquefaction and product separation Procedure
able for direct liquefaction without pre-grinding process. However,
the coffee stores are widely distributed, and thus may not be eco- Co-liquefaction experiments were carried out using a 100 cm3
nomically feasible to collect over longer distances. Mixing SCG stainless-steel autoclave (Parr 5513 Micro Bench top reactor) with
110 L. Yang et al. / Bioresource Technology 237 (2017) 108121

Fig. 1. Yields of bio-crude oil, solid residue, gas and WSP from co-liquefaction of SCG with PF, CS and WPB at various reaction temperature.

Table 1
Characterization of SCG, PF, CS and WPB.

SCG PF CS WPB
a
Proximate analysis
Volatile matterb 75.2 79.4 68.9 70.5
Ashc 1.1 0.5 2.4 1.1
Elemental compositiond
Carbon 51.4 50.1 44.4 42.7
Hydrogen 7.7 6.2 6.3 6.8
Nitrogen 2.1 0.2 0.5 0
Oxygenee 38.8 43.5 48.9 50.5
Chemical composition
Holocellulosef 61.4 91.5 67.9 44.1
Proteing 13.0 1.2 3.1 -
Extractivesh 10.5 7.3 1.3 5.1
Lignini 27.7 0.7 18.6 49.7
a
On dry mass basis; in mass fraction.
b
Determined by thermogravimetric analysis (TGA) in N2 at 10 C min1 to 800 C.
c
Determined by biomass combustion at 575 C for 3 h, according to ASTM E1755 [37].
d
Determined by elemental analyzer; on dry and ash free basis.
e
By difference.
f
Determined according to the modified Chlorination method (ASTM D1104) [38].
g
Calculated based on nitrogen composition from elemental analysis using the nitrogen factor of 6.25 [39].
h
Determined according to the method of Chemical Analysis and Testing Task Laboratory Analytical Procedure (LAP-010) [40].
i
Determined according to the method of Chemical Analysis and Testing Task Laboratory Analytical Procedure (LAP-003) [41].

a maximum working temperature and pressure of 500 C and range of 510 MPa depending on reaction temperature. After
5000 psi, respectively. In a typical run, SCG and different lignocel- 10 min, the liquefaction reaction was stopped by quenching the
lulosic biomass (PF, CS or WPB) were mixed with distilled water to reactor using a water/ice bath. After the system was cooled down
make a feedstock slurry with water/feedstock mass ratio of 5:1. A to the room temperature, the gaseous product in the reactor was
total of 60 g feedstock slurry containing 10 g solids and 50 g dis- collected in a gas bag for GC-TCD (Agilent Micro-GC 3000) analysis,
tilled water was loaded in the reactor. The reactor was subse- and 120 cm3 of air was injected into the gas bag as an internal stan-
quently sealed and purged with high purity nitrogen to remove dard for each test. The reactor was opened and rinsed with acetone
the residual air, and then was pressurized with nitrogen (initial for several times and the contents were transferred into a beaker.
pressure of 0.5 MPa), stirred at 4.8 Hz, heated up to the pre-set The slurry and rinsing acetone was vacuum-filtered with a Buchner
temperature (varied from 225 C to 325 C) at a heating rate of funnel and the solid residue was washed with acetone several
10 C/min, and held for 10 min, and the final pressure was in the times until the filtrate became colorless. The collected filtrate
L. Yang et al. / Bioresource Technology 237 (2017) 108121 111

was transferred to a pre-weighed Erlenmeyer flask and was rotary relative molecular mass Mn (number average), Mw (weight aver-
evaporated at 90 C under reducing pressure to remove acetone age) and polydispersity index (PDI = Mw: Mn) of the resulting
and water. Finally, the bio-crude oil product was obtained and bio-crude oils were analyzed using Waters Breeze gel permeation
weighed. The acetone insoluble fraction was oven-dried at 105 C chromatography (GPC) instrument (1525 Binary HPLC, UV detector
for 24 h, giving the solid residue product (SR). The yields of each set at 270 nm, Water Styrange HR1 column set at 40 C).
product were calculated as a mass percentage on a dry basis and Tetrahydrofuran (THF) was used as a mobile phase at a flow rate
defined as follows: of 1 cm3min1. Linear polystyrene standards were used for cali-
moil bration. The viscosity of the resulting oil products were measured
Y oil %  100 1 by Brookfield CAP 2000 + Viscometer and the measurements were
mfeedstock
recorded at 80 C.
mSR
Y SR %  100 2
mfeedstock
3. Results and discussions
Y gasWSP % 1  Y oil  Y SR 3
3.1. Effect of temperature on product distribution
Y conv ersion % 1  Y SR 4
During a HTL process, reaction temperature was found to be the
where Yoil, YSR, and Ygas+WSP denote the yields of crude bio-oil, solid most influential parameter on the distribution of product streams
residue, and combined gas /water soluble product, respectively, in (gas, liquid and solid) (Akhtar and Amin, 2011). The impact of tem-
mass percentage, on a dry basis; moil, mfeedstock, mSR, mgas+WSP repre- perature on the co-liquefaction of SCG with PF, CS and WPB was
sent the mass of bio-crude oil, feedstock loaded to the reactor, solid first examined, varying the reaction temperature from 225 C to
residue, and gas and water soluble product, respectively, on a dry 325 C. Fig. 1 shows the effect of reaction temperature on distribu-
basis; Yconversion denotes the feedstock conversion rate of the lique- tion between three product streams in the reaction time of 10 min,
faction process. water/feedstock mass ratio of 5:1 and feedstock combination mass
The co-liquefaction experiments were repeated in triplicate and ratio of 50% SCG with 50% PF, CS and WPB respectively. As the gas
the typical variance in the data within 5%. The mean of product yields were relatively low (less than 1%) for all experiments, they
yield and their standard deviations were shown in all figures. were added to water soluble product (WSP) and presented as com-
The synergetic effect (SE) of various feedstock combinations in a bined gas and WSP yield.
co-liquefaction process is defined as the difference between the In general, an increment of reaction temperature from 225 C to
actual oil yield obtained from the co-liquefaction experiment and 325 C, the yields of different product streams obtained from co-
the theoretical value calculated based on the actual oil yield liquefaction process presented different trends. As shown in
obtained from single feedstock with the mass percentage of indi- Fig. 1, when the temperature increased from 225 C to 250 C,
vidual biomass component in the feedstock. The SE (%) is evaluated the yield of bio-crude oil increased from 13.8%, 10.2% and 15.5%
as follows: to 18.3%, 21.6% and 15.6% for the co-liquefaction of SCG with PF,
CS and WPB, respectively. However, a further increase of tempera-
SE% Y actual  Y theo =Y theo ture (reached 325 C) led to a slight decrease in oil yield to 15.2%,
Y actual  xSCG  Y oilSCG 1  xSCG  Y oilother =Y theo 5 16.7%, and 15.4%, for three feedstock combinations respectively. It
is well established that biomass degrades through hydrolysis,
where Yactual and Ytheo denote the actual yield of bio-crude oil from dehydration, condensation, decarboxylation and decarbonylation
co-liquefaction and the theoretical value of bio-crude oil yield, etc., all of which occur in sequence and/or in parallel. Generally,
respectively; Yoil-SCG and Yoil-other represent the bio-crude oil yields biomass decomposition was accelerated by increasing tempera-
obtained from the liquefaction of pure SCG and pure PF, CS or WPB, ture. Lignin is a rigid component and a high temperature promotes
individually, under the same operation conditions; xSCG denotes the its complete decomposition. However, too high temperature might
mass fraction of SCG in the mixed feedstock. further decompose the oil compounds/intermediates to form water
soluble short carbon chain compounds, which reduces the oil yield.
2.3. Bio-crude oil characterization Optimization of temperature has potential to favor reactions for
bio-crude oil formation. In this study, a relatively low temperature
The elemental composition (C, H and N) of the feedstock and the was favorable to obtain more bio-crude oil from SCG, while a high
resulting bio-crude oil was analyzed using an Elemental Analyzer temperature benefited formation of bio-crude oil from lignin rich
(vario EL cube Elementar) with the oxygen content (O) determined feedstock. The highest oil yields for the co-liquefaction of these
by difference. The higher heating values (HHV) of the feedstock, three feedstock combinations were obtained at 250 C. When a
and the bio-crude oils were calculated using the Dulong formula higher temperature was applied (>250 C), the yield of oil product
based on the elemental compositions (Xu and Lad, 2008): decreased and the yield of gas and WSP increased from 32.6%,
1 38.8% and 32.6% to 55.8%, 56.6% and 51.3%, due to the secondary
HHVMJ  kg 0:3383C 1:442H  O=8 6
decomposition of oil fragments. The optimized temperature
where C, H and O are the mass percentages of carbon, hydrogen and resulted from comprising the relative contents of carbohydrate
oxygen in the bio-crude oil, respectively, obtained from the elemen- and lignin in two feedstocks. In terms of solid residue products,
tal analysis. their yields decreased gradually from 53.6%, 51.0% and 52.0% to
The volatile components of the resulting bio-crude oils were 28.0%, 26.8% and 32.3% with increasing temperature. This is due
analyzed using GCMS (Agilent Technologies, 5977A MSD) with a to a high temperature favored the decomposition of rigid con-
SHRXI -5MS column (30 m  250 mm  0.25 mm). The initial col- stituent in biomass, particularly, lignin. Therefore, high tempera-
umn temperature was set at 60 C and held for 2 min, then ture led to a higher biomass conversion rate and overall
increased to 280 C at a heating rate of 20 Cmin1 and held for liquefaction efficiency. These results are consistent with other
5 min. The compounds in the oil product were identified by com- research on impact of temperature on liquefaction of biomass
paring the spectra of the chromatogram peaks with the mass spec- reported in the literature (Gai et al., 2015; Jin et al., 2013;
tra from the NIST Mass Spectra Database library (NIST11). The Pedersen et al., 2015; Xiu et al., 2011; Zhang et al., 2011). For
112 L. Yang et al. / Bioresource Technology 237 (2017) 108121

example, Gai and coworkers co-liquefied microalgae and lignocel- oil yields of pure SGC and CS were 19.6% and 20.8% respectively,
lulose biomass from 200 C to 350 C when the feedstock combina- and thus the bio-crude oil yield of the mixed feedstock (50% and
tion mass ratio was 1:1. Their results showed that the yield of 50%) in theory was 20.2%, while the actual value of bio-crude oil
resulting bio-crude oil increased from 15.5% at 200 C to 37.6% at yield resulted from co-liquefaction was 21.4%. Adding 5% NaOH
300 C, then decreased to 33.1% when the temperature further as a catalyst resulted in significant synergistic effect. The actual
increased to 350 C. The yield of solid residue decreased from bio-crude oil yield from liquefying 50% SCG and 50% CS was
34.9% to 10.8% as the temperature increased, while the WSP and 29.5%, much higher than the theoretical yield value of 24.4%, the
gas product showed an opposite trend (Gai et al., 2015). synergistic effect was determined to be 20.9%.
Fig. 1 showed the performance of various feedstock combina- As for the combination of spent coffee grounds and white pine
tions in the co-liquefaction process. SCG and CS was found to be bark in Fig. 2c, it showed opposite trend to SCG + PF and SCG + CS.
the most suitable feedstock combination in the co-liquefaction Without a catalyst, the yield of bio-crude oil obtained from co-
process, giving the highest yield of bio-crude oil while the lowest liquefaction was 15.9%, higher than that of the calculated theoret-
yield of SR within the range of reaction temperature tested. For ical value of 13.2%. In contrast, adding catalyst gave the bio-crude
instance, the oil yield obtained from SCG and CS combination oil yield of 17.4%, lower than the theoretical value of 21.3% calcu-
was 21.6%, 20.1%, and 17.5% at 250 C, 275 C and 300 C, respec- lated from those of liquefaction of SCG and WPB individually, a
tively, which were all higher than those obtained from the other negative synergistic effect was observed.
two feedstock combinations. While for SR, the yield was 36.8%, The synergetic effects (SE) of the three feedstock combinations
30.3% and 26.6% under such temperatures, which were all lower on bio-crude oil yield are summarized in Table 2. Based on obser-
than those of the other two feedstock combinations. The SR yield vations in this study, it is concluded that mixing different feed-
from co-liquefaction of SCG with WPB was the highest and the stocks does lead to synergistic effects on the yield of bio-crude
yield of gas and WSP were the lowest among three feedstock com- oil. However, this kind of effect could be positive (SCG + PF and
binations. This is due to a higher lignin content in WPB (50%), SCG + CS with catalyst addition, SCG + WPB without catalyst), neg-
which is the most difficult component to be decomposed in sub- ative (SCG + WPB with catalyst addition), or non-significant (SCG
critical water compared to other biomass components (Akhtar + PF and SCG + CS without catalyst).
and Amin, 2011; Nigam and Singh, 2011; Sakaki et al., 1996). The It was interestingly found that in the absence of catalyst, the
higher proportion of incomplete de-polymerization consequently significance of SE among three feedstock combinations ranked
resulted in a higher yield of SR. In addition, WPB had the lowest as: 20.4% (SCG + WPB) > 5.9% (SCG + CS) > 0.5% (SCG + PF), which
holocellulose content of 44.1%, which led to a lower yield of WSP coincided with the order of lignin content in the feedstock:
(Karagz et al., 2005). 49.7% (WPB) > 18.6% (CS) > 0.7% (PF). Therefore, we speculated
According to the experimental results, 250 C was the most that the SE in the co-liquefaction process might be associated
suitable reaction temperature to obtain the highest bio-crude oil with the possible interactions between lignocellulose content in
yield, 18.3%, 21.4% and 15.9% for the co-liquefaction of SCG with the feedstock and other chemical components, particularly lipids
PF, CS and WPB, respectively. Therefore, the reaction temperature in spent coffee grounds. The organic acids were formed in the
of 250 C was used in the following work to investigate the effect early stage of hydrolysis of lipid and thus the free fatty acids in
of catalyst on the co-liquefaction process. the SCG may enhance the degradation of lignin in acidic environ-
ment, resulting in a higher oil yield (Chen et al., 2014; Jin et al.,
3.2. Effect of catalyst on bio-crude oil yield 2013). The free fatty acids in SCG may also react with lignin via
acid catalyzed reaction (mainly dehydration and esterification)
An addition of alkali catalysts such as NaOH, Na2CO3 and KOH, to form more esters which contributes to oil compounds (Ye
has been widely reported to have a positive effect on bio-crude oil et al., 2012).
production, and is able to enhance biomass conversion rate Alkaline catalysts, e.g., KOH, NaOH, Na2CO3, were widely
(Minowa et al., 1998a, 1998b; Yang et al., 2009; Zhu et al., employed in the liquefaction of lignocellulose biomass (especially
2015a,b). In this study, NaOH (5% mass fraction of feedstock) was woody biomass), which was demonstrated to favor the lignin
added as a catalyst in the co-liquefaction process to examine the decomposition and enhance oil formation (Zhang et al., 2011). In
potential synergistic effect of the blended feedstocks on the bio- this study, for individual feedstock such as spend coffee grounds
crude oil yields. The choice of the type of catalyst and concentra- and white pine bark, an addition of catalyst increased the oil yield
tion is based on our previous research (Yang et al., 2016a), prelim- significantly. For corn stalk, the yield of bio-crude oil stayed indif-
inary experiments and reported studies (Akhtar and Amin, 2011; ferent with or without catalyst. However, addition of catalyst
Peterson et al., 2008). Fig. 2ac presented the bio-crude oil yields decreased the oil yield of paper filter when liquefied alone. This
obtained from co-liquefaction of SCG with PF, CS and WPB, respec- might be due to a high holocellulose content in paper filter which
tively, at 250 C with and without catalysts. could be degraded to water soluble compounds in a basic environ-
For the feedstock combination of spent coffee grounds and ment, leading to a low yield of bio-crude oil. When alkali catalysts
paper filter, without a catalyst, there was no significant synergistic were added in the mixed feedstock, a strong positive synergistic
effect observed. As shown in Fig. 2a, the bio-crude oil yields of pure effect was observed in the co-liquefaction of spent coffee grounds
SGC and PF were 19.6% and 16.8% respectively, and the bio-crude and corn stalk, and a moderate one in co-liquefaction of spent cof-
oil yield of the mixed feedstock (50% and 50%) in theory was fee grounds and paper filter. This was understandable that SGG, CS
18.2% presented in the blue bar. The bio-crude oil yield from a and PF has low content of lignin, and thus was not very sensitive to
co-liquefaction of SCG and PF was 18.3% shown in the brown bar, the change in alkalinity of reaction medium. In the presence of
very close to the theoretical value. However, with an addition of alkali catalysts, at the early stage of HTL, the base environment
5% NaOH catalyst, the actual bio-crude oil yield from the co- promoted the decomposition of cellulose, hemicellulose and lipid
liquefaction of SCG and PF was 22.5% in the brown bar, higher than through weakening glucoside bond and base-catalyzed hydrolysis
the theoretical value of 20.3% presented in the blue bar by 10.8% of lipid. Following that, with formation of organic acids, an envi-
increment. ronment with a lower pH value was still be able to decompose
Fig. 2b shows the bio-crude oil yields in the HTL processes of holocellulose, favor oil phase formation and offer hydrogenating
spent coffee grounds, corn stalk CS and their mixture. Without a agents to suppress the secondary-decomposition of oil fragments.
catalyst, a slight synergistic effect was observed. The bio-crude (Xiu et al., 2010, 2011; Teri et al., 2014)
L. Yang et al. / Bioresource Technology 237 (2017) 108121 113

Fig. 2. Bio-crude oil yields from co-liquefaction at 250 C with/without adding 5% NaOH. (a) SCG and PF (b) SCG and CS (c) SCG and WPB.

Table 2
The synergetic effects (SE) of mixing feedstock on bio-crude oil yield.

Feedstock combination Without catalyst With catalyst


Theo. yield Actual yield SE Theo. yield Actual yield SE
% % % % % %
SCG + PF 18.2 18.3 0.5 20.3 22.5 10.8
SCG + CS 20.2 21.4 5.9 24.4 29.5 20.9
SCG + WPB 13.2 15.9 20.4 21.3 17.4 18.3

As for the co-liquefaction of spend coffee grounds and white ingly produced organic acids would decrease the concentration of
pine bark, a negative effect was observed that the experimental alkali catalyst, and thus majority of lignin could not be decom-
biocrude yield of spend coffee grounds and white pine bark posed, leading to less phenolic compounds formation and a low
decreased by 18.3% compared to the mass average yield calculated biocrude yield. This is our speculation and we cannot provide evi-
from individual feedstock. This was most likely due to the increas- dence as the impact of catalyst concentration on co-liquefaction
114 L. Yang et al. / Bioresource Technology 237 (2017) 108121

was beyond the scope of this study. There might be other interac- yield of 30.7% and 50.9% respectively. Obviously, the oil yield of
tions among individual components and formed intermediates single feedstock WPB was much lower than that of SCG. The possi-
impacting the co-liquefaction process. At the current stage of the ble reason for such varied potential for producing oil was due to
research, a full explanation of the underlying mechanism is not their various proportion of chemical components. For example, a
available. higher content of holocellulose/lipid (71.9% in SCG vs. 49.1% in
WPB) made the decomposition of biomass in subcritical water
3.3. Effect of feedstock combination mass ratios on the product much easier WPS, and resulted in a greater amount of oil formed.
distribution However, a higher content of lignin in biomass materials (49.7%
in WPB vs. 27.7% in SCG) led to a higher yield of SR. Fig. 4c also
The observed synergistic effect in the co-liquefaction of the shows that the resulting oil yield decreased constantly from
mixed feedstocks on the bio-oil yield led to a further study on 26.7% to 16.0% as the mass ratio of WPB increased from 0% to
the influence of feedstock combination mass ratios. Fig. 3ac pre- 100%. The yield of gas/WSP also reduced from 42.6% to 33.2%,
sent the effect of various feedstock combination mass ratios on and the SR yield rose steadily from 30.7% to 50.9% as the proportion
the product distribution in the co-liquefaction of SCG with PF, CS of WPB increased. Unexpectedly, mixing SCG and WPB demon-
and WSP, respectively, at 250 C with an addition of 5% NaOH as strated a negative synergetic effect, lowering the bio-crude oil
a catalyst. yield. This implies that the high lignin content in WPB might hin-
The product distribution from a co-liquefaction of spent coffee der the bio-crude oil formation from decomposing high lipid and
grounds and paper filter is depicted in Fig. 3a. As the mass ratio holocellulose content in SCG, or accelerate the decomposition of
of PF increased, the bio-crude oil yield decreased from 26.7% at the formed esters via acidly-catalysis to acid phases (in WSP).
the combination of 0% PF with 100% SCG to 13.8% at the combina-
tion of 100% PF with 0% SCG. This is understandable as the bio-
crude oil yield of HTL of pure SCG was higher than that of pure 3.4. Characterization of the resulting bio-crude oil
PF, therefore, a higher proportion of SCG in the mixed feedstock
led to a higher yield of bio-crude oil. Interestingly, it was observed 3.4.1. Elemental composition
that the bio-crude oil yield at the mass ratio of SCG and PF of 1:1, To investigate the synergistic effect on the oil quality in the co-
was slightly higher than those of other feedstock combinations liquefaction of SCG with PF, CS and WPB, elemental analysis were
(mass ratio of 7:3 or 3:7). The SR yield obtained from the co- conducted for both feedstocks and the resulting oil products
liquefaction process remained constant at 31% as the mass ratio obtained at 250 C with/without adding 5% NaOH in various feed-
of PF increased from 0% to 50%. When the mass ratio of PF was fur- stock combination mass ratios. The results for the feedstock com-
ther increased to 100%, the SR yield increased from 31% to 39.7% bination of SCG with PF, CS, and WPB are presented in Table 3a
then decreased to 16.1%. In contrast, the yield of gas and WSP c respectively.
increased significantly from 44.3% to 70.1% with an increase of PF Table 3a displays the elemental compositions of SCG, PF, and
proportion from 70% to 100%, which could result from the decom- the resulting bio-crude oils derived from the co-liquefaction of
position of the high holocellulose content in PF to water soluble SCG and PF. The result shows that the two individual raw materials
compounds. These trends suggest that a synergistic interaction had similar content of carbon and hydrogen, while SCG contained a
between SCG and PF did exist during the co-liquefaction process, lower amount of oxygen, resulting in a slightly higher HHV of
which altered the product distribution. 21.5 MJkg1, compared with PF of 18.1 MJkg1. In the absence
Fig. 3b presents the effect of corn stalk proportion on the pro- of a catalyst, the resulting oil obtained from HTL of SCG had a
duct distribution in a co-liquefaction of SCG with CS. As the mass higher content of carbon and hydrogen and a reduced content of
ratio of CS increased, the yield of bio-crude oil gradually increased oxygen, leading to a significant increase in HHV (40.4 MJkg1).
from 26.7% at the feedstock combination of 0% CS with 100% SCG to However, the HHV of the oil obtained from HTL of PF was not
29.7% at the combination of 50% CS with 50% SCG, then decreased remarkably improved. As for the co-liquefaction of SCG with PF,
to 23.0% as the CS proportion further increased. Fig. 4b shows that the HHV of the oil obtained at a combination of 50% SCG and
these two feedstocks had a similar potential in bio-crude oil pro- 50% PF was 25.6 MJkg1, which was lower than the theoretical
duction, and the bio-crude oil yield were 26.7% and 22.0%, respec- HHV value (30.7 MJkg1). This result indicates that a negative syn-
tively when liquefied independently. This is most likely due to ergistic effect of co-liquefying SCG and PF on the HHV value when
similar chemical compositions in the two biomass materials. When no catalyst was added. By adding a catalyst, 5% NaOH, the yield of
the two feedstocks were mixed at a ratio of 1:1, the highest bio- bio-crude oil derived from SCG was increased significantly from
crude oil yield of 29.7% was obtained. The SR yield shows a concave 19.6% to 26.7% as presented in section 3.2, however, resulted in a
trend as the mass ratio of CS increased from 0% to 100% and the lower HHV of 31.9 MJkg1, compared to that of bio-crude oil from
lowest SR formation of 25.4% was obtained at a combination of a HTL process without a catalyst (40.4 MJkg1). This result sug-
50% SCG with 50% CS, corresponding to the highest bio-crude oil gests that 5% NaOH had a negative impact on HHV value and pos-
yield obtained at this point. In contrast, the yield of gas/WSP shows itive effect on the oil yield. For the other feedstock, PF, a different
a protruding curve with a maximum yield of 47.8% obtained at the trend was observed. An addition of 5% NaOH showed a slightly pos-
combination of 70% SCG with 30% CS. With a particular interest of itive impact on the HHV value (22.1 MJkg-1) of bio-crude oil,
maximizing the yield of oil product, the best performance was higher than that (18.1 MJkg1) of oil obtained from a HTL process
obtained for the feedstock mixture of 50% SCG and 50% CS, at without adding catalyst. As for the co-liquefaction of SCG and PF,
which the oil yield reached the highest value of 29.7% under the the HHVs of the oils obtained at the combinations of 70% SCG with
experimental scope in this study, demonstrating an enhancement 30% PF, 50% SCG with 50% PF, and 30% SCG with 70% PF were
in bio-crude oil formation. The results strongly indicate the exis- 32.1 MJkg1, 27.3 MJkg1, and 28.9 MJkg1, respectively, which
tence of a significantly positive synergistic effect between SCG were all higher than the theoretical values of 29.0 MJkg1,
and CS in the co-liquefaction process. 27.0 MJkg1, and 25.0 MJkg1. From above results, it was found
The product distribution from a co-liquefaction of SCG with that in the presence of alkali catalyst, co-liquefaction of spend cof-
WPB in various feedstock combination mass ratios is illustrated fee grounds and paper filter was favorable. The biocrude yield was
in Fig. 4c. The results show that the yield of bio-crude oil obtained enhanced by 10.8% as shown in Table 2 and the HHV was improved
from HTL of pure SCG and WPB was 26.7% and 16.0%, with a SR slightly.
L. Yang et al. / Bioresource Technology 237 (2017) 108121 115

Fig. 3. Yields of bio-crude oil, solid residue, gas and WSP from co-liquefaction at 250 C with adding 5% NaOH in various feedstock combination mass ratios. (a) SCG and PF (b)
SCG and CS (c) SCG and WPB.
116 L. Yang et al. / Bioresource Technology 237 (2017) 108121

Fig. 4. Effect of catalyst and feedstock combination ratios on the composition of bio-crude oil derived from co-liquefaction. (a) SCG and PF (b) SCG and CS (c) SCG and WPB.

Table 3b presents the elemental analysis of SCG, CS and the bio- Without adding a catalyst, the liquefaction processes significantly
crude oils obtained from the co-liquefaction of SCG and CS. SCG increased the HHVs of the resulting bio-crude oils, 40.4 MJkg1
had a higher HHV (21.5 MJkg1) than that of CS (15.2 MJkg1). for SCG bio-crude oil and 27.9 MJkg1 for CS bio-crude oil, which
L. Yang et al. / Bioresource Technology 237 (2017) 108121 117

Table 3
Elemental analysis of bio-crude oils at 250 C with/without 5% NaOH in various feedstock combination mass ratios.

Sample Elemental compositions, % HHVb HHVctheo


a (MJkg1) (MJkg1)
C H N O
(a) Co-liquefaction SCG and PF
Feedstockd SCG 51.4 7.7 2.1 38.8 21.5
PF 50.1 6.2 0.2 43.5 18.1
Without catalyst Oil from SCG 73.9 12.3 0.8 13.0 40.4 40.4
Oil from SCG:PF (5:5) 60.4 7.4 1.7 30.5 25.6 30.7
Oil from PF 56.4 6.0 0 37.6 20.9 20.9
With 5% NaOH Oil from SCG 66.6 9.2 2.3 21.9 31.9 31.9
Oil from SCG:PF (7:3) 67.6 9.0 2.3 21.1 32.1 29.0
Oil from SCG:PF (5:5) 62.3 7.8 1.6 28.2 27.3 27.0
Oil from SCG:PF (3:7) 65.3 7.8 2.0 24.9 28.9 25.0
Oil from PF 56.5 6.7 0.1 36.8 22.1 22.1
(b) Co-liquefaction SCG and CS
Feedstockd SCG 51.4 7.7 2.1 38.8 21.5
CS 44.4 6.3 0.5 48.9 15.2
Without catalyst Oil from SCG 73.9 12.3 0.8 13.0 40.4 40.4
Oil from SCG:CS (5:5) 71.7 8.5 1.9 17.9 33.3 34.2
Oil from CS 67.3 6.7 0.9 25.1 27.9 27.9
With 5% NaOH Oil from SCG 66.6 9.2 2.3 21.9 31.9 31.9
Oil from SCG:CS (7:3) 65.0 8.8 2.0 24.1 30.4 30.4
Oil from SCG:CS (5:5) 65.0 8.1 1.7 25.2 29.1 29.5
Oil from SCG:CS (3:7) 68.5 7.9 1.7 21.8 30.7 28.5
Oil from CS 64.7 6.9 1.0 27.3 27.0 27.0
(c) Co-liquefaction SCG and WPB
Feedstockd SCG 51.4 7.7 2.1 38.8 21.5
WPB 42.7 6.8 0 50.5 15.1
Without catalyst Oil from SCG 73.9 12.3 0.8 13.0 40.4 40.4
Oil from SCG:WPB (5:5) 61.9 7.3 2.0 28.8 26.2 33.0
Oil from WPB 61.9 7.1 0.3 30.7 25.6 25.6
With 5% NaOH Oil from SCG 66.6 9.2 2.3 21.9 31.9 31.9
Oil from SCG:WPB (7:3) 62.9 8.7 2.0 26.4 29.0 30.2
Oil from SCG:WPB (5:5) 66.3 9.3 1.0 23.4 31.6 29.0
Oil from SCG:WPB (3:7) 61.9 8.9 0.8 28.4 28.6 27.8
Oil from WPB 64.0 6.7 0.2 29.0 26.1 26.1

a
By mass difference;
b
Higher heating value calculated by the Dulong formula: HHV (MJkg1) = 0.3383C + 1.442 (H  (O/8));
c
Theoretical higher heating value calculated by: HHVtheo = HHVoil-SCG  xSCG + HHVoil-WPB  (1  xSCG);
d
On a dry basis.

were both higher than those of the raw materials. As for the co- rized in Table 3c. SCG had a higher HHV (21.5 MJkg1) than that
liquefaction process, the HHV of the resulting oil (34.2 MJkg1) of WPB (15.1 MJkg1). The resulting oil product obtained from
was close to the theoretical value (33.3 MJkg1), indicating no sig- HTL of SCG (40.4 MJkg1) was higher than that from HTL of WPB
nificantly synergistic effect observed in the absence of a catalyst. (25.6 MJkg1). As for their co-liquefaction, the HHV of the result-
Table 3b also shows that an addition of 5% NaOH had no apparent ing oil product was 26.2 MJkg1, which was lower than the theo-
impact on the HHV of bio-crude oil derived from CS as the HHV retical value of 33.0 MJkg1. Therefore, a negative synergistic
was 27.0 kJkg1, similar to that (27.9 MJkg1) of the bio-crude effect on the HHV of the bio-crude oil was observed in the absence
oil obtained from a HTL process in the absence of a catalyst. Addi- of a catalyst. Similarly to the HTL of CS, an addition of catalyst
tionally, the interaction effect on the oils HHVs in their co- showed no impact on the HTL of WPB. The HHV of the oil product
liquefaction process was also insignificant. For instance, when resulting from a process with an addition of 5% NaOH was
the feedstock combination was 70% SCG with 30% CS, 50% SCG with 26.1 MJkg1, which was close to that (25.6 MJkg1) of bio-crude
50% CS, and 30% SCG with 70% CS, the HHVs of the resulting oil oil derived from a process without a catalyst. Also, the HHVs of
products were 30.4 MJkg1, 29.1 MJkg1, and 30.7 MJkg1, the oil products obtained from co-liquefaction of SCG and WPB
respectively, all of which were close to the theoretical values of in various feedstock combination mass ratio were 29.0 MJkg1,
30.4 MJkg1, 29.5 MJkg1 and 28.5 MJkg1. This result indicates 31.6 MJkg1, and 28.6 MJkg1, which were all similar to the theo-
that with or without catalyst, no significant positive impact on retical values of 30.2 MJkg1, 29.0 MJkg1, and 27.8 MJkg1. This
the HHVs of biocrude derived from the co-liquefaction processes results reveals that no synergistic effect was observed on the oils
although a strong synergetic effect on the yield of biocrude (SE of HHVs in this co-liquefaction process when 5% NaOH was applied.
20.9%) was observed. To examine the synergistic effect of the co-liquefaction pro-
Table 3b. Elemental analysis of SCG, CS and bio-crude oils from cesses on the chemical compositions of the resulting bio-crude oils,
their co-liquefaction at 250 C with/without adding 5% NaOH in GCMS analysis was conducted to identify the major compounds
various feedstock combination mass ratios. existing in the oil products. As shown in Fig. 4ac, the major com-
The elemental analysis of SCG, WPB and the resulting oil prod- pounds were categorized into five classes based on the functional
ucts obtained from co-liquefaction of SCG and WPB are summa- groups, including (1) long-chain carboxylic acids, (2) hydrocarbons
118 L. Yang et al. / Bioresource Technology 237 (2017) 108121

(e.g., alkanes, alkenes and their derivatives), (3) N & O-heterocyclic formed. Alkali catalysts also promoted the decomposition of lipids
compounds, (4) esters, ketones, alcohols and aldehydes, and (5) to form more carboxylic compounds and the degradation of lignin
cyclic oxygenates (e.g., phenols and their derivatives). It should to generate more phenolic compounds as shown in Fig 4b blue and
be noted that the compounds containing more than one functional yellow bar respectively. When the mass ratio of CS increased from
group were categorized into only one class. The major compounds 0% to 100%, the amount of carboxylic acids in the oil product
of the resulting oil products with the relative total peak area lower decreased from 100% to 64.1%. This might be attributed to a
than 1% were not included in the body text, however are available reduced proportion of SCG in the feedstock, which led to a lower
in Supplementary data. content of lipids, and consequently reduced the formation of car-
Fig. 4a illustrates the chemical components of the oil products boxylic acids. A higher amount of aldehydes and phenols was
obtained from the co-liquefaction of spent coffee grounds and detected with increasing CS proportion, which was clearly due to
paper filter. In the absence of a catalyst, the main volatile com- the higher content of holocellulose in the CS and the enhancement
pounds in the oil obtained from HTL of SCG were long-chain car- of alkaline catalyst on the lignin decomposition.
boxylic acids (98.98%), mainly including n-hexadecanoic acid Fig. 4c presents the chemical compositions of the resulting bio-
(46.23%) and 9,12-octadecadienoic acid (Z,Z)- (50.83), which were crude oils obtained from a co-liquefaction of spent coffee grounds
most likely derived from lipids/proteins in the SCG. As for the HTL and white pine bark. In the absence of a catalyst, the major compo-
of PF, almost 100% of the detected compounds were 5-HMF (alde- nents in the WPB oil were long-chain carboxylic acids (64.34%), 5-
hydes) and no phenolic compounds in the resulting oil product, HMF (31.89%) and hydrocarbons (3.76%, methyl 9, 12-
which were derived from the high content of holocellulose heptadecadienoate). Interestingly, no phenols or its derivations
(91.5% shown in Table 1) in the raw material following the dehy- were detected even the lignin content in WPB was pretty high
dration pathway proposed by Pedersen et al. (2016). Interestingly, (50%). This is obviously due to insufficient decomposition/de-po
the major compounds in the oils derived from the co-liquefaction lymerization of lignin content in the WPB at such a low reaction
process were similar to the SCG oil, containing mainly long-chain temperature (at 250 C in this study) and without alkali catalysts.
carboxylic acids (94.64%), namely n-Hexadecanoic acid (45.40%) Similarly to the co-liquefaction of SCG with PF and SCG with CS,
and octadecadienoic acid (Z,Z)- (46.82%) and a small amount of a large amount of carboxylic acids were detected in the oil product
ester/aldehydes contributed by paper filter. This result indicates from co-liquefaction of SCG and WPB, which were mainly derived
that the volatile compounds in the oil obtained from co- from the lipids in the SCG, while the contribution of WPB to the
liquefaction of SCG and PF were primarily derived from the decom volatile compound formation was negligible. With an addition of
position/de-polymerization of lipid content in the SCG when no 5% NaOH, the amount of aldehyde, hydrocarbon and phenolic com-
catalyst was added. The experimental biocrude yield of mixture pounds in the oil product derived from WPB alone were greatly
was equivalent to the mass average yield of SCG and PF. By adding increased from 31.89%, 3.76% and 0% to 40.79%, 24.01% and
5% NaOH as a catalyst, the yield of bio-crude derived from SCG 5.97%, respectively. This result revealed that the decomposition
alone increased significantly (Fig. 2) and the biocrude contained of lignin was very sensitive to the alkalinity of reaction medium
98.83% of carboxylic acids, similar to that obtained from SCG with- and alkali catalysts could effectively accelerate degradation of lig-
out a catalyst. However for PF alone, in the presence of catalyst, no nin, generating more aldehyde, hydrocarbon and phenolic com-
volatile compounds were detected, accompanying with a decrease pounds, which has been well established in the reported studies
in oil product yield (Fig. 2) These results implied that an addition of (Peterson, 2008, Pedersen et al., 2015). In the co-liquefaction of
alkali catalyst generated a severe reaction condition, in which SCG and PF, the various feedstock combination mass ratios had
holocellulose most likely took retro-Aldol reaction pathway pro- no effect on the chemical compositions of oil, majority of which
moted by high alkalinity to produce short chain compounds sol- were carboxylic acids.
uble in water phase, non-detectable by GCMS. The chemical Different from most studied lignocellulose biomass, spent cof-
composition in the resulting oil products from mixed feedstock fee grounds have a certain amount of protein, it is therefore impor-
showed no significant difference among these feedstock combina- tant to trace nitrogen in co-liquefaction processes. Generally,
tions with various mass ratios, all of which contained carboxylic nitrogen containing compounds in the resulting biocrude is unde-
acids as their major compounds. sirable due to either nitrogen oxides (NOx) emissions upon oil
Fig. 4b provides the chemical compositions of the resulting bio- combustion or additional efforts required in downstream refining.
crude oils derived from the co-liquefaction of spent coffee grounds From GCMS analysis, there were little amount of N & O hetero-
and corn stalk. It can be seen from Fig. 4b that the major com- cyclic compounds (i.e., 2.84% of 5-methyl-3-(piperidin-1-ylme
pounds in the oil product derived from CS without adding catalyst thyl)-1, 2, 4-oxadiazole) were detected. Elemental analysis also
were aldehydes (30.38%) (i.e., 5-HMF, and Vanillin), long-chain car- demonstrated that the nitrogen content in the biocrude was in
boxylic acids (32.6%) (i.e., n-hexadecanoic acid and octadeca- the range of 1.62.3%. There might be some N-compounds exiting
dienoic acid (Z,Z)-), and cyclic oxygenates (25.74%) (i.e., phenol, in water soluble phase or/and ammonia in the gaseous stream
4-ethyl- and phenol, 2,6-dimethoxy-), not surprisingly correspond- (Biller et al., 2011). Unfortunately, quantification is not available
ing to the chemical composition of corn stalk stock (67.9% holocel- as the aqueous and gas phases were discarded in our experiments.
lulose, 18.6% lignin and 4.4% lipid/protein). The aldehydes and
carboxylic acids were most likely derived from holocellulose in 3.4.2. GPC
the CS, and the cyclic oxygenates, mainly containing phenols and The relative molecular mass of bio-crude oil was reported to
its derivations, were derived from the lignin content in this feed- have significant impact on the properties of oil product such as vis-
stock. As for the co-liquefaction, the major compounds in the oil cosity and HHV (Cheng et al., 2010). The relative molecular mass
product detectable by GC was carboxylic acids, similar to the co- and its distribution of the resulting bio-crude oils from the co-
liquefaction of SCG and PF. With an addition of 5% NaOH, the liquefaction of three feedstock combinations were measured using
resulting bio-crude oil obtained from pure CS contained a higher GPC and summarized in Table 4ac.
amount of carboxylic acids (64.1%) while a relatively low amount Table 4a presents the average molecular mass (Mw and Mn) of
of aldehydes (8.9%), compared to the process without a catalyst. the bio-crude oils derived from the co-liquefaction of spent coffee
This result suggested that an increased alkalinity in reaction med- grounds and paper filter at 250 C with/without a catalyst at vari-
ium could route holocellulose to take retro-Aldol reaction pathway ous feedstock combination mass ratios. The results show that the
rather than dehydration pathway, therefore less furfural/5-HMF relative molecular mass and distribution of the oil products
L. Yang et al. / Bioresource Technology 237 (2017) 108121 119

obtained under all reaction conditions were similar, where the Mn, grounds and corn stalk, namely increased 20.9% as shown in
Mw and PDI were in the range of 200 g/mol to 310 g/mol, Table 2. Liquefaction of such a mixture also reduced the molecular
390 g/mol790 g/mol, and 1.622.63, respectively. In the absence mass of the bio-crude products, which is desirable for its down-
of a catalyst, the Mw of bio-crude oil obtained from the HTL of stream applications.
SCG alone was 790 g/mol, much higher than Mw of 390 g/mol of Table 4c shows that the Mw of the bio-crude oils obtained from
PF oil; and the PDI of SCG biocrude (2.63) was also higher than that white pine bark was 360 g/mol without catalyst and 620 g/mol
of PF (1.95). This might be attributed to that the long carbon chain with a catalyst. Without a catalyst, most lignin in WPB could not
of triglyceride in SCG was still kept after being hydrolyzed into be decomposed, and thus only compounds such as aldehydes,
fatty acids while holocellulose in paper filter was decomposed into acetic acids, alcohol and esters were derived from dehydration of
small fragments such as aldehydes, alcohols and acetic acids etc. In holocellulose, leading to the lowest molecular mass of 380 g/mol
the presence of catalyst, Mw and PDI of SCG dropped slightly. Sur- among all bio-crude oils obtained in this study. This speculation
prisingly, the molecular mass of the oil products obtained from can be supported by the evidence of a very low biocrude yield
their co-liquefaction was 480 g/mol with a catalyst and (6.9%) obtained in HTL of WPB alone without a catalyst. The Mw
470 g/mol without catalysts respectively. This result indicates that of the bio-crude oils from the co-liquefaction of SCG and WPB
a positive effect resulted from the co-liquefaction of SCG and PF, was in the range of 510 g/mol580 g/mol, which was slightly lower
leading to a reduced relative molecular mass which is one of the than those of SCG oil and the WPB oil.
favorable fuel properties. Despite no explicit explanation to inter-
actions between two feedstocks under investigated liquefaction 3.4.3. Viscosity
conditions, we speculate that individual component such as holo- Viscosity is another important measure for the evaluation of the
cellulose, lignin, protein and lipid do not necessarily follow their oil quality. It represents the fluidity of liquid fuels. A low viscosity
reaction pathways independently as identified in HTL of each com- results in a higher fluidity. The viscosity of the resulting bio-crude
ponent alone. Mixing feedstock is not a liner addition of fractions oils obtained from co-liquefaction of SCG with PF, CS and WPB at
of each individual component, and it might reroute the reaction 250 C were also measured and summarized in Table 5. The viscos-
pathway and also shift the dynamics of intermediate reactions. ity of the SCG oil resulting from in a process without a catalyst was
Table 4b illustrates the average molecular mass of the oils 409 cP, much lower than those of PF oil (2989 cP), CS oil (3251 cP)
obtained from the co-liquefaction of spent coffee grounds and corn and WPB oil (11374 cP). This result suggests that the oils obtained
stalk at various feedstock combination ratios. The molecular mass from the HTL of SCG were better than the others in terms of the oil
(Mw) of SCG oil and CS oil were 790 g/mol and 610 g/mol, respec- viscosity and fluidity. As for the co-liquefaction of SCG with PF, CS
tively, more close to each other compared to SCG and PF, originat- and WPB, the viscosity of the resulting oils was greatly reduced to
ing their similar chemical compositions in the two raw materials. the values of 169 cP, 1420 cP, and 480 cP, respectively, indicating a
By adding 5% NaOH catalyst, the Mw of the oils obtained from positive effect of co-liquefaction on the bio-crude oils viscosity.
the co-liquefaction at various combination ratios was in the range However, adding catalyst had a negative impact on the viscosity
of 500 g/mol560 g/mol, which was lower than that of oils of PF oil and CS oil as seen in Table 5, the viscosity increased from
obtained from the both of two feedstocks. The result is extremely 2989 cP and 3251 cP, to 8044 cP and 11,926 cP, respectively. In
promising as a strong positive synergistic effect on the yield of contrast, such an impact on the SCG oil and WPB oil was less
bio-crude oil was observed in co-liquefaction of spent coffee significant. With the increase in SCG proportion in the mixed

Table 4
Average molecular mass of bio-crude oils obtained from co-liquefaction at 250 C with/without catalyst addition in various feedstock combination mass ratios.

Sample Mn Mw PDI
(a) Spent coffee grounds and paper filter
Without catalyst Oil from SCG 300 790 2.63
Oil from SCG:PF (5:5) 240 480 2
Oil from PF 200 390 1.95
With 5% NaOH Oil from SCG 310 710 2.29
Oil from SCG:PF (7:3) 280 470 1.68
Oil from SCG:PF (5:5) 280 470 1.68
Oil SCG:PF (3:7) 280 460 1.64
Oil from PF 290 470 1.62
Sample Mn Mw PDI
(b) Spent coffee grounds and corn stalk
Without catalyst Oil from SCG 300 790 2.63
Oil from SCG:CS (5:5) 290 520 1.79
Oil from CS 310 610 1.97
With 5% NaOH Oil from SCG 310 710 2.29
Oil from SCG:CS (7:3) 290 510 1.76
Oil from SCG:CS (5:5) 310 560 1.81
Oil from SCG:CS (3:7) 310 500 1.61
Oil from CS 350 710 2.03
Sample Mn Mw PDI
(c) Spent coffee grounds and white pine bark
Without catalyst Oil from SCG 300 790 2.63
Oil from SCG:WPB (5:5) 260 540 2.08
Oil from WPB 210 380 1.81
With 5% NaOH Oil from SCG 310 710 2.29
Oil from SCG:WPB (7:3) 300 570 1.9
Oil from SCG:WPB (5:5) 290 580 2
Oil from SCG:WPB (3:7) 300 510 1.7
Oil from WPB 360 620 1.72
120 L. Yang et al. / Bioresource Technology 237 (2017) 108121

Table 5
Viscosity of bio-crude oils obtained from co-liquefaction of SCG with PF, CS and WPB at 250 C with/without adding 5% NaOH in various feedstock combination mass ratios.

Feedstock Without catalyst With adding 5% NaOH


SCG SCG:PF PF SCG SCG:PF SCG:PF SCG:PF PF
(5:5) (7:3) (5:5) (3:7)
Viscosity 80 C (cP) 409 169 2989 375 2592 1845 6599 8044
Feedstock SCG SCG:CS CS SCG SCG:CS SCG:CS (5:5) SCG:CS (3:7) CS
(5:5) (7:3)
Viscosity 80 C (cP) 409 1420 3251 375 6531 964 9120 11926
Feedstock SCG SCG:WPB WPB SCG SCG:WPB SCG:WPB SCG:WPB WPB
(5:5) (7:3) (5:5) (3:7)
Viscosity 80 C (cP) 409 480 11374 375 7118 375 2681 10821

feedstock, the viscosity of the oils obtained from co-liquefaction of Biller, P., Riley, R., Ross, A.B., 2011. Catalytic hydrothermal processing of microalgae:
decomposition and upgrading of lipids. Bioresour. Technol. 102, 48414848.
SCG with PF and CS was both reduced. For instance, the oil prod-
Chen, W.T., Zhang, U.H., Zhang, J.X., Schideman, L., Yu, G., Zhang, P., Minarick, M.,
ucts obtained at a combination of 70% SCG with 30% PF and 70% 2014. Co-liquefaction of swine manure and mixed-culture algal biomass from a
SCG with 30% CS, had a viscosity of 2592 cP and 6531 cP, respec- wastewater treatment system to produce bio-crude oil. Appl. Energy. 128, 209
tively, both of which were lower than that those of bio-crude oils 216.
Cheng, S.N., Dcruz, I., Wang, M.C., Leitch, M., Xu, C.C., 2010. Highly efficient
obtained with the combinations of 30 SCG with 70% PF and 30% liquefaction of woody biomass in hot-compressed alcohol-water co-solvents.
SCG with 70% CS. Regarding the co-liquefaction of SCG with Energy Fuels 24, 46594667.
WPB, an increase in SCG proportion led to a higher oil viscosity. Ehrman, T., 1994. Standard method for the determination of extractives in biomass.
Chemical Analysis and Testing Task Laboratory Analytical Procedures (LAP -
Interestingly, in the co-liquefaction of SCG with PF, SCG with CS 010), NREL Ethanol Project.
and SCG with WPB at a 50% and 50 mixing ratio, appeared to be Elliott, D.C., Biller, P., Ross, A.B., Schmidt, A.J., Jones, S.B., 2015. Hydrothermal
the most suitable feedstock combination ratio, in which the lowest liquefaction of biomass: developments from batch to continuous process.
Bioresour. Technol. 178, 147156.
oil viscosity of 1845 cP, 964 cP and 375 cP was obtained Feng, S.H., Yuan, Z.S., Leitch, M., Xu, C.B., 2014. Hydrothermal liquefaction of barks
respectively. into bio-crude effects of species and ash content/composition. Fuel 116, 214
Overall, it was found that the co-liquefaction process had a pos- 220.
Gai, C., Li, Y., Peng, N.N., Fan, A.N., Liu, Z.G., 2015. Co-liquefaction of microalgae and
itive effect on the viscosity of bio-crude oil, adding another benefit lignocellulosic biomass in subcritical water. Bioresour. Technol. 185, 240245.
of co-liquefaction of biomass. Similar results were also reported in Huang, H.J., Yuan, X.Z., 2015. Recent progress in the direct liquefaction of typical
Xius research on the co-liquefaction of swine manure and free biomass. Prog. Energy Combust. Sci. 49, 5980.
Huang, H.J., Yuan, X.Z., Li, B.T., Xiao, Y.D., Zeng, Z.M., 2014. Thermochemical
fatty acids (Xiu et al., 2010).
liquefaction characteristics of sewage sludge indifferent organic solvents. J.
Anal. Appl. Pyrolysis 109, 176184.
Jin, B.B., Duan, P.G., Xu, Y.P., Wang, F., Fan, Y.C., 2013. Co-liquefaction of micro- and
4. Conclusion
macroalgae in subcritical water. Bioresour. Technol. 149, 103110.
Karagz, S., Bhaskar, T., Muto, A., Sakata, Y., Oshiki, T., Kishimoto, T., 2005. Low-
Co-liquefaction of spent coffee grounds with lignocellulosic bio- temperature catalytic hydrothermal treatment of wood biomass: analysis of
liquid products. Chem. Eng. J. 108, 127137.
mass were conducted to explore the impact of mixing feedstock on
Kondamudi, N., Mohapatra, S.K., Misra, M., 2008. Spent coffee grounds as a versatile
the yield and quality of bio-crude oil. The best feedstock combina- source of green energy. J. Agric. Food Chem. 56, 1175711760.
tion is spent coffee ground and corn stalk. The biocrude yield from Liu, H.M., Li, M.F., Sun, R.C., 2013. Hydrothermal liquefaction of cornstalk: 7-Lump
the mixture exceeded the mass averaged yield of individual feed- distribution and characterization of products. Bioresour. Technol. 128, 5864.
Lpez, C.V.G., Garca, M.D.C.C., Fernndez, F.G.A., Bustos, C.S., Chisti, Y., Sevilla, J.M.F.,
stock by 20.9%. The quality of the resulting oil product was 2010. Protein measurements of microalgal and cyanobacterial biomass.
improved in terms of viscosity and average molecular mass. A sig- Bioresour. Technol. 101, 75877591.
nificant positive synergetic effect observed in such a co- Minowa, T., Kondo, T., Sudirjo, S.T., 1998a. Thermochemical liquefaction of
Indonesia biomass residues. Biomass Bioenergy 14, 517524.
liquefaction process demonstrated potential to improve the yield Minowa, T., Zhen, F., Ogi, T., 1998b. Cellulose decomposition in hot-compressed
and/or optimize the properties of oil product according to its water with alkali or nickel catalyst. J. Supercrit. Fluid. 13, 253259.
downstream applications. Nigam, P.S., Singh, A., 2011. Production in liquid biofuels from renewable resources.
Prog. Energy Combust. Sci. 37, 5268.
Overend, R.P., 1982. The average haul distance and transportation work factors for
Acknowledgement biomass delivered to a central plant. Biomass Bioenergy 2, 7579.
Pavlovic, I., Knez, Z., kerget, M., 2013. Hydrothermal reactions of agricultural and
food processing wastes in sub- and supercritical water: a review of
The authors would like to acknowledge the NSERC Discovery, fundamentals, mechanisms, and state of research. J. Agric. Food Chem. 61,
grant number RGPIN 04211 and BioFuelNet, grant number BFN 80038025.
67-Xu. One of the authors (L.Y.) is grateful for the facilities and sup- Pedersen, T.H., Rosendahl, L.A., 2015. Production of fuel range oxygenates by
supercritical hydrothermal liquefaction of lignocellulosic model systems.
port offered by Institute for Chemicals and Fuels from Alternative Biomass Bioenergy 85, 206215.
Resources (ICFAR) during her visiting studies at Western Pedersen, T.H., Jasiunas, L., Casamassima, L., Singh, S., Jensen, T., Rosendahl, L.A.,
University. 2015. Synergetic hydrothermal co-liquefaction of crude glycerol and aspen
wood. Energy Convers. Manage. 106, 886891.
Pedersen, T.H., Grigoras, I.F., Hoffmann, J., Toor, S.S., Daraban, I.M., Jensen, C.U.,
References Iversen, S.B., Madsen, R.B., Glasius, M., Arturi, K.R., Nielsen, R.P., S/gaard, E.G.,
Rosendahl, L.A., 2016. Continuous hydrothermal co-liquefaction of aspen wood
Akhtar, J., Amin, N.A.S., 2011. A review on process conditions for optimum bio-oil and glycerol with water phase recirculation. Appl. Energy 162, 10341041.
yield in hydrothermal liquefaction of biomass. Renewable Sustainable Energy Pei, X.K., Yuan, X.Z., Zeng, G.M., Huang, H.J., Wang, J.Y., Li, H., Zhu, H.N., 2012. Co-
Rev. 15, 16151624. liquefaction of microalgae and synthetic polymer mixture in sub- and
ASTM, 1978. Method of Test for Holocellulose in Wood. ASTM International, West supercritical ethanol. Fuel Process. Technol. 93, 3544.
Conshocken, PA, pp. D1104D1156. Peterson, A.A., Vogel, F., Lachance, R.P., Frling, M., Antal, M.J., Tester, J.W., 2008.
ASTM, 2007. Standard Test Method for Ash in Biomass. ASTM International, West Thermochemical biofuel production in hydrothermal media: a review of sub-
Conshocken, PA. E1755 01. and supercritical water technologies. Energy Environ. Sci. 1, 3265.
Biller, P., Ross, A.B., 2011. Potential yields and properties of oil from the Sakaki, T., Shibata, M., Miki, T., Hirosue, H., Hayashi, N., 1996. Reaction model of
hydrothermal liquefaction of microalgae with different biochemical content. cellulose decomposition in near-critical water and fermentation of products.
Bioresour. Technol. 102, 215225. Bioresour. Technol. 58, 197202.
L. Yang et al. / Bioresource Technology 237 (2017) 108121 121

Singh, R., Balagurumurthy, B., Bhaskar, T., 2015. Hydrothermal liquefaction of macro Yang, L.X., Nazari, L., Yuan, Z.S., Corscadden, K., Xu, C.B., He, Q., 2016b. Hydrothermal
algae: effect of feedstock composition. Fuel 104, 6974. liquefaction of spent coffee grounds in water medium for bio-oil production.
Singh, R., Krishna, B.B., Mishra, G., Kumar, J., Bhaskar, T., 2016. Strategies for Biomass Bioenergy 86, 191198.
selection of thermo-chemical processes for the valorisation of biomass. Ye, Z.Y., Xiu, S.N., Shahbazi, A., Zhu, S.M., 2012. Co-liquefaction of swine manure and
Renewable Energy 98, 226237. crude glycerol to bio-oil: model compound studies and reaction pathways.
Templeton, D., Ehrman, T., 1995. Determination of acid-insoluble lignin in biomass. Bioresour. Technol. 104, 783787.
Chemical Analysis and Testing Task Laboratory Analytical Procedures (LAP- Yuan, X.Z., Cao, H.T., Li, H., Zeng, G.M., Tong, J.Y., Wang, L.H., 2009. Quantitative and
003). qualitative analysis of products formed during co-liquefaction of biomass and
Teri, G., Luo, L.G., Savage, P.E., 2014. Hydrothermal treatment of protein, synthetic polymer mixtures in sub- and supercritical water. Fuel Proc. Technol.
polysaccharide, and lipids alone and in mixtures. Energy Fuels 28, 75017509. 90, 428434.
Theegala, C.S., Midgett, J.S., 2012. Hydrothermal liquefaction of separate dairy Zhai, Y.B., Chen, Z., Chen, H.M., Xu, B.B., Li, P., Qing, R.P., Li, C.T., Zeng, G.M., 2015. Co-
manure for production of bio-oils with simultaneous waste treatment. liquefaction of sewage sludge and oil-teacake supercritical methanol: yield of
Bioresour. Technol. 107, 456463. bio-oil, immobilization and risk assessment of heavy metals. Environ. Technol.
Toor, S.S., Rosendahl, L., Rudolf, A., 2011. Hydrothermal liquefaction of biomass: a 36, 27702777.
review of subcritical water technologies. Energy 36, 23282342. Zhang, L.H., Champagne, P., Xu, C.B., 2011. Bio-crude production from secondary
Xiu, S.N., Shahbazi, A., Shirley, V., Mims, M.R., Wallace, C.W., 2010. Effectiveness and pulp/paper-mill sludge and waste newspaper via co-liquefaction in hot-
mechanisms of crude glycerol on the biofuel production from swine manure compressed water. Energy 36, 21422150.
through hydrothermal pyrolysis. J. Anal. Appl. Pyrolysis 87, 194198. Zhu, Y.H., Biddy, M.J., Jones, S.B., Elliott, D.C., Schmidt, A.J., 2014. Techno-economic
Xiu, S.N., Shahbazi, A., Wallace, C.W., Wang, L.J., Cheng, D., 2011. Enhanced bio-oil analysis of liquid fuel production from woody biomass via hydrothermal
production from swine manure co-liquefaction with crude glycerol. Energy liquefaction (HTL) and upgrading. Appl. Energy 129, 348394.
Convers. Manage. 52, 10041009. Zhu, Z., Rosendahl, L., Toor, S.S., Yu, D.H., Chen, G.Y., 2015a. Hydrothermal
Xu, C.B., Lad, N., 2008. Production of heavy oils with high caloric values by direct liquefaction of barley straw to bio-crude oil: effects of reaction temperature
liquefaction of woody biomass in sub/near-critical water. Energy Fuels 22, 635 and aqueous phase recirculation. Appl. Energy 137, 183192.
642. Zhu, Z., Toor, S.S., Rosendahl, L., Yu, D.H., Chen, G.Y., 2015b. Influence of alkali
Yang, Y., Gilbert, A., Xu, C.B., 2009. Production of bio-crude from forestry waste by catalyst on product yield and properties via hydrothermal liquefaction of barley
hydro-liquefaction in sub-/super-critical methanol. AlChE 55, 807819. straw. Energy 80, 284292.
Yang, L.X., Mahmood, N., Corscadden, K., Xu, C.B., He, Q., 2016a. Production of crude
bio-oil via direct liquefaction of spent K-cups. Biomass Bioenergy 95, 354363.