international journal of hydrogen energy xxx (xxxx) xxx

Available online at www.sciencedirect.com

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Co-production of upgraded bio-oils and H2-rich gas

from microalgae via chemical looping pyrolysis

Yongzhuo Liu a,*, Jingjing Liu a, Tao Wang a, Xintao Zhang a,

Lingyun Wang a,**, Xiude Hu b, Qingjie Guo a,b
a
Key Laboratory of Clean Chemical Engineering in Universities of Shandong, College of Chemical Engineering,
Qingdao University of Science & Technology, Qingdao 266042, People's Republic of China
b
State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, Ningxia University,
Yinchuan 750021, People's Republic of China

highlights graphical abstract

A novel pyrolysis (CLPy) based on

the chemical looping concept was
proposed.

The heating value of bio-oil
increased from 20.5 MJ/kg to
36 MJ/kg.

The content of H2 in the pyrolytic
gas increased to 50%.

CO-rich or H2-rich syngas was
generated in the gasification stage
of pyrolytic char.

article info abstract

Article history: In order to produce high-quality bio-oils and syngas from biomass, a novel pyrolysis
Received 29 January 2021 approach based on the chemical looping concept, namely chemical looping pyrolysis
Received in revised form (CLPy), was proposed. In the current work, thermodynamic feasibility study and experi-
6 May 2021 mental investigations of the proposed CLPy with calcium-ferrite oxygen carriers and
Accepted 7 May 2021 Nannochloropsis sp. microalgal biomass were conducted. The results suggested that the
Available online xxx reduced calcium-ferrite oxygen carrier facilitated the denitrification, ketonization, and
hydrodeoxygenation (HDO) of bio-oils during the pyrolysis stage. Since large amounts of
Keywords: oxygen in bio-oils were transferred to the reduced oxygen carrier, the heating value of bio-
Chemical looping pyrolysis oils was remarkably increased up to 34.2 MJ/kg and 36.0 MJ/kg by employing the reduced
Reduced oxygen carrier CaFe2O4 and Ca2Fe2O5 oxygen carrier, respectively. In addition, a high H2 content of 50% in
Microalgae the pyrolysis gas was observed at the optimal pyrolysis temperature. In the gasification
Ketonization stage, the production of high-quality syngas was achieved. The content of H2 accounted for
Hydrodeoxygenation up to 70% of the gasification products when taking steam as gasifying agent, while that of
CO was composed of 66% without the use of a gasifying agent. Moreover, the oxygen carrier
was reduced to its reduction state, available for the next loop. In summary, CLPy proposed

* Corresponding author.
** Corresponding author.
E-mail addresses: yzliu@qust.edu.cn (Y. Liu), wangly412@qust.edu.cn (L. Wang).
https://doi.org/10.1016/j.ijhydene.2021.05.047
0360-3199/© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article as: Liu Y et al., Co-production of upgraded bio-oils and H2-rich gas from microalgae via chemical looping py-
rolysis, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.05.047
2 international journal of hydrogen energy xxx (xxxx) xxx

in this work involves the continuous transference of the oxygen from bio-oils to syngas by
an oxygen carrier and provides a brand-new approach for the comprehensive utilization of
biomass.
© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

carriers can not only catalyse the pyrolysis of biomass but

Introduction also serve as oxygen receptors from oxygenated pyrolysis
products. In the gasification reactor (GR), oxygen carriers from
With the increasing demand for fossil fuels and growing PR act as oxygen donors for the gasification of pyrolysis semi-
concerns about climate change, the exploitation of renewable char, resulting in the regeneration of reduced oxygen carriers
and environmentally friendly energy resources is of urgency and the production of high-quality syngas. Consequently, the
and significance. Biomass is regarded as one of the most regeneration or separation of catalysts from semi-char seen
important renewable energy sources due to its abundance, in the traditional catalytic pyrolysis is avoided. Moreover, two
renewability, and potential carbon neutrality [1,2]. The kinds of products, i.e., upgraded bio-oils and high-quality
biomass investigated currently includes wood, residues from syngas are obtained from PR and GR, respectively. Alterna-
agriculture or forestry, the organic component of municipal tively, another oxidation reactor (AR) can be added to provide
and industrial waste and oil-rich algae such as microalgae. heat for GR. The generalized reactions occurring in three re-
Due to the advantages of fast growth rate, high efficiency in actors are expressed as R1-R3, where biomass, bio-oils, semi-
CO2 capture, and non-competitiveness with land for food char and oxygen carrier are simplified as CxHyOz, Cx-bHy-cOz-a,
crops, microalgal biomass has been considered as a promising C, and MeO, respectively.
biofuel source, and the valorization of microalgae has attrac-
ted growing attention in recent years [3e5].
PR: CxHyOz þ aMe ¼ Cx-bHy-cOz-a þ aMeO þ bC þ 0.5cH2
Among potential approaches, pyrolysis of microalgal
DH<0 (1)
biomass is regarded as one of the most efficient routes for
generating renewable hydrocarbon fuels or commodity
GR: bMeO þ bC þ H2O ¼ bMe þ H2 þ bCO DH>0 (2)
chemicals, due to the advantages of simplicity, short conver-
sion time, high productivity, and compatibility [6]. Generally,
AR: (b-a)Me þ 0.5(b-a)O2 ¼ (b-a)MeO DH<0 (3)
the complex composition of biomass gives the bio-oils ob-
tained from direct pyrolysis undesirable properties, such as As a novel thermochemical conversion method, chemical
high oxygen content, elevated acidity, and high nitrogen looping technology provides a brand new route for converting
content. Several measures have been examined for upgrading biomass with high efficiency and low pollution level [16,17].
the quality of microalgae-derived bio-oils, such as ex-situ The reported studies on biomass chemical looping process
catalytic hydrogenation of the obtained bio-oils [7], co- mainly focus on chemical looping combustion (CLC) and
pyrolysis with coal or H-rich waste [8e10], and in-situ cata- chemical looping gasification (CLG). However, it is necessary
lytic pyrolysis [11e14]. to reconsider the distinct composition and structure charac-
Catalytic pyrolysis can convert biomass to high quality teristics of biomass. First, as a result of the abundant
biofuels or valuable chemicals [15]. The reported catalysts for hydrogen and long-chain structure of biomass, the catalytic
biomass pyrolysis included zeolites-based catalysts and metal pyrolysis method is superior to the two-step process of first
oxides such as TiO2, ZrO2, Al2O3, CeO2, MnO2, Fe2O3, and CaO gasification and then F-T synthesis in terms of the generation
[6]. However, the strong deactivation of most catalysts limited of high-quality liquid fuels. Meanwhile, due to the high vola-
their regeneration and continuous utilization [7]. For ex-situ tiles of biomass, the liquid products tar, as a contamination
catalytic pyrolysis, the strong polymerization of pyrolysis bio-
oils could lead to the carbon deposition on catalysts, while the
direct contact of the catalysts and biomass would make it
difficult to separate catalysts from bio-char for in-situ catalytic
pyrolysis. To the best of our knowledge, the regeneration or
separation of catalysts from bio-char has not been fully
addressed thus far.
To simultaneously meet the requirements for the upgrade
of pyrolysis bio-oils and the regeneration of catalysts, a novel
pyrolysis approach based on the chemical looping concept,
chemical looping pyrolysis (CLPy), was proposed in this work.
As illustrated in Fig. 1, the proposed CLPy consists of two
stages run in two separated reactors, viz. the pyrolysis of
biomass at 400e650  C and the gasification of pyrolysis char at Fig. 1 e Schematic diagram of chemical looping pyrolysis
800e900  C. In the pyrolysis reactor (PR), reduced oxygen (CLPy).

Please cite this article as: Liu Y et al., Co-production of upgraded bio-oils and H2-rich gas from microalgae via chemical looping py-
rolysis, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.05.047
 international journal of hydrogen energy xxx (xxxx) xxx 3

for syngas or products of incomplete combustion, is inevitably First, analytically pure Ca(NO3)2∙4H2O and Fe(NO3)3∙9H2O
generated during the reported chemical looping process for with the desired molar ratio of Ca/Fe were dissolved in
biomass. To avoid the occurrence of tar pollution, biofuels or deionized water. Then, an appropriate amount of urea fuel
chemicals can be produced from biomass by a pyrolysis pro- was added, and the solution was stirred at 90  C until a viscous
cess prior to CLC and CLG. Therefore, in comparison with sol-gel was formed. The obtained sol-gel was combusted at
biomass CLC and CLG, the CLPy proposed in the work can 300  C for 1 h, and then calcined at 900  C for 5 h in a muffle
simultaneously gain high quality bio-oils and clean syngas by furnace. After being cooled to room temperature, the calcined
isolating biomass pyrolysis from bio-char gasification. To materials were crushed, and sieved for use using 80 mesh and
date, few studies have demonstrated that iron-based oxygen 100 mesh standard sieves. Here, CaFe2O4 and Ca2Fe2O5, with
carriers are potential catalysts for the pyrolysis of biomass Ca/Fe molar ratio 1:2 and 1:1 were named as CF2 and CF,
[18,19]. Moreover, the pyrolysis behaviour of biomass in the respectively. The corresponding reduced oxygen carriers, pre-
presence of an oxygen carrier is unclear, especially at the reduced by CH4 at 850  C for 30 min, were named as Re-CF2
traditional pyrolysis temperatures 400e650  C. and Re-CF, respectively. In the reference test, the oxygen
Calcium ferrites, which exhibited the selective oxidation of carrier was substituted by quartz sand. The average particle
carbonaceous fuel to syngas (i.e., H2 and CO) rather than CO2 size of the two calcium-ferrite oxygen carrier was 150 mm, as
and H2O, were verified to be promising oxygen carriers for CLG determined by a laser particle size analyser.
of coal and biomass [20e22]. Hence, calcium ferrites (CaFe2O4 Nannochloropsis sp. was obtained from Yantai Hairong
and Ca2Fe2O5) were selected as oxygen carriers for the CLPy Biotechnology Company, China. Before use, the sample was
proposed in this work. Recently, an investigation into CLG of dried at 105  C for 24 h, sequentially ground and sieved to a
microalgae with calcium ferrites as oxygen carrier was carried size smaller than 100 mm. The proximate analysis, ultimate
out [23,24]. The results indicated that the employment of analysis, and chemical components are tabulated in Table 1. It
Ca2Fe2O5 enhanced microalgae gasification with efficiency of is clearly observed that the proportion of volatile content of
92.49% for syngas production at 850  C, and the calcium ferrite Nannochloropsis sp. is extremely high, and mainly derived from
oxygen carrier was reduced to CaO, Fe, and FeO under gasifi- three chemical components, i.e., proteins, lipids, and poly-
cation conditions. Among the reduced products, CaO and Fe saccharides. Additionally, oxygen accounts for 35.44% of the
have been proven to be effective catalysts for the pyrolysis of mass, which may lead to undesirable bio-oil characteristics of
biomass. Huang et al. [25] and Zhang et al. [26] found that an high oxygen content and elevated acidity [29].
Fe/CaO catalyst upgraded biomass fast pyrolysis vapors by Crystalline structures of the oxygen carriers prepared and
reducing the percentage of oxygenated compounds. In addi- used were analysed using X-ray diffraction (XRD, Rigaku D/
tion, many studies have demonstrated that CaO could promote max-Rb, Japan). All X-ray diffraction patterns were analysed
the formation of hydrocarbons, eliminate acids, and increase by means of Jade 7.5 from Material Data, Inc. (MDI). The sur-
ketone selectivity [27,28]. The presence of Fe in biomass py- face morphology and microstructure of fresh and used oxygen
rolysis led to the increase of gaseous products and solid char carriers were determined by a scanning electron microscope
yield on the one hand, and to the decrease of the bio-oil yield (SEM, JEOL JSM-6700F, Japan).
on the other hand [29]. Moreover, the yield of ketones and acids
were promoted up to 67.51% at 700e800  C by the introduction Experimental setup and procedure
of Fe. Collard et al. [30] concluded that the impregnation of Fe
on biomass decreased the yield of oxygenated compounds and To investigate the reactivity of oxygen carriers with micro-
increased the yield of H2. The excellent catalytic property of algae, tubular reactor experiments were carried out, as illus-
CaO or Fe on biomass pyrolysis and the outstanding redox trated in Fig. 2. In each test, mixtures composed of 2 g oxygen
performance for CLG makes the calcium-ferrite oxygen carrier carrier or quartz sand and 2 g microalgae were filled into
a promising candidate for the proposed CLPy. a ceramic boat, placed in the left end of the quartz tube,
In the current work, the feasibility of the proposed CLPy and kept out of the heating zone. After the pipelines were
process of Nannochloropsis sp. microalgae with calcium fer- connected without gas leakage, the reactor was purged with
rites (CaFe2O4 and Ca2Fe2O5) as oxygen carriers was exam- argon at a flow rate of 200 mL/min for 30 min to guarantee an
ined. The effect of temperature on the pyrolysis of microalgal inert atmosphere inside the reactor. When the reactor was
biomass run with reduced oxygen carriers was probed heated to the desired temperature by an electric heating
experimentally. In addition, the gasification of pyrolysis char furnace (OTF-1200X), ceramic boat filled with samples was
was investigated with and without steam as the gasifying pushed into the constant temperature zone of the reactor.
agent. Furthermore, probable reaction paths for microalgae At the same time, two connected absorption bottles filled
pyrolysis in the presence of the reduced oxygen carrier were with quantitative isopropanol and immersed in an ice-water
discussed preliminarily. mixture were used to collect the liquid products, while the
non-condensable gas was collected by Tedlar bags every
2 min. When pyrolysis experiments finished, the temperature
Materials and methods was elevated to 850  C to conduct the gasification of the py-
rolysis char. The generated syngas was collected by Tedlar
Preparation and characterization of materials bags every 2 min. The pyrolysis and gasification experiments
were carried out for 30 min and 40 min, respectively. In the
As described in the literature [31], two calcium-ferrite oxygen presence of gasification agent, 2 g/min deionized water was
carriers were prepared by the sol-gel combustion method. vaporized to produce a steam atmosphere. All pyrolysis and

Please cite this article as: Liu Y et al., Co-production of upgraded bio-oils and H2-rich gas from microalgae via chemical looping py-
rolysis, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.05.047
4 international journal of hydrogen energy xxx (xxxx) xxx

Table 1 e Characterization of biomass Nannochloropsis sp.

Proximate analysis wt. %, ad Ultimate analysis wt. %, daf Chemical component wt. %
M V A FC C H N Oa protein lipid polysaccharide Othersa
3.90 82.91 6.07 7.12 50.67 7.35 6.54 35.44 44 30 21 5
a
Calculated by difference.

Fig. 2 e Diagram of the experimental system of the tubular reactor.

gasification experiments were carried out in triplicate, and the the short pre-reduction time (30 min), Ca2Fe2O5 was not
obtained values were averaged. thoroughly reduced to CaO and Fe. In addition, a minor
The collected non-condensable gas was analysed by gas amount of Fe3C (JCPDS PDF#85e1317) was observed in the Re-
chromatography (GC, PE CLARUS 500, USA) with a TX-01 col- CF2 oxygen carrier, but not in the Re-CF oxygen carrier. The
umn using a thermal conductivity detector. After being formation of Fe3C was probably related to the relatively high
dehydrated with CaO and filtered by a syringe filter, the bio- Fe content in the Re-CF2 oxygen carrier.
oils were analysed by means of the gas chromatography-
mass spectrometry (GC-MS, 7890A-5975C, Agilent, USA) with Thermodynamic feasibility of CLPy process
an HP-5MS capillary column (60 m  0.25 mm  0.25 mm). The
major peaks in the chromatogram were identified by the mass Standard Gibbs free energy (DG) data for potential reactions
spectral data library of National Institute of Standards and between C/CO2/H2O and oxidized or reduced oxygen car-
Technology (NIST). The peaks were also integrated using the riers at different temperatures are shown in Fig. 4. Potential
GC-MS program to determine the relative peak areas.

Results and discussions

Characterization of the prepared oxygen carrier

The XRD patterns of the fresh oxygen carrier are illustrated in

Fig. 3. It was observed that two desired calcium ferrites
(CaFe2O4 and Ca2Fe2O5) were successfully prepared. CaFe2O4
(JCPDS PDF#72e1199) generated with a brownmillerite-type
structure in the Ca/Fe mole ratio of 1:2, while Ca2Fe2O5
(JCPDS PDF#71e2108) with a spinel structure formed when the
Ca/Fe mole ratio is equal to 1:1.
After reduction by CH4, it was observed that both calcium-
ferrite oxygen carriers were mainly converted to their reduced
state. It was acknowledged that CaFe2O4 was first reduced to
Ca2Fe2O5 and FeO, and then Ca2Fe2O5 was reduced to CaO and
Fe directly [20,21]. The Re-CF2 oxygen carrier was composed of
Fe (JCPDS PDF#87e0721), CaO (JCPDS PDF#77e2010) and Fig. 3 e XRD patterns of fresh oxygen carrier and reduced
Ca2Fe2O5, which was in accordance with the literature. Due to oxygen carrier.

Please cite this article as: Liu Y et al., Co-production of upgraded bio-oils and H2-rich gas from microalgae via chemical looping py-
rolysis, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.05.047
 international journal of hydrogen energy xxx (xxxx) xxx 5

FeO at a lower temperature, while the reduction of Ca2Fe2O5

requires a higher temperature. Carbon was oxidized to CO2
thermodynamically when temperature exceeds 860  C. In
addition, the iron-steam reaction R11 can increase the yield of
hydrogen, while the carbonation reaction of CaO R12 can
improve the concentration of hydrogen in the pyrolysis gas. In
the pyrolysis stage, the reactions between the reduced cal-
cium ferrite and the generated H2O/CO2 can not only produce
a great deal of H2 for upgrading of pyrolysis bio-oils, but also
achieve the oxygen transference from bio-oils to oxygen car-
riers. When the temperature is higher than 700  C, i.e. in the
gasification stage, reactions R7-R10 between oxygen carrier
and carbon will realize the gasification of pyrolysis char as
well as the regeneration of the reduced oxygen carrier. The
Fig. 4 e Gibbs free energies of potential reactions at generated oxygen carrier is then available for the next loop. In
different temperatures. terms of the thermodynamics, the proposed CLPy process is
practicable.

Effect of temperature on the pyrolysis stage

reactions between the oxygen carrier and biomass can be
divided into two types: reactions R4-R6 between the reduced Temperature is an important factor in determining the yield
oxygen carrier and CO2/H2O, and reactions R7-R10 between of gas-liquid-solid products as well as the compositions of gas
the oxidized oxygen carrier and carbon. In addition, the iron- and liquid products. In the pyrolysis stage, the pyrolysis
steam reaction R11 and the carbonation of CaO R12 are also behaviour of Nannochloropsis sp. with and without the reduced
considered. calcium-ferrite oxygen carrier was investigated at five tem-
peratures, 450  C, 500  C, 550  C, 600  C, and 650  C. The
2CaO þ 2Fe þ 3H2O ¼ Ca2Fe2O5 þ 3H2 (R4) collected bio-oils were characterized by GC-MS and element
analysis, while the major non-condensable gases in the py-
2CaO þ 2Fe þ 3CO2 ¼ Ca2Fe2O5 þ 3CO (R5) rolysis gas were analysed by GC.

0.5Ca2Fe2O5 þ FeO þ 0.5H2O ¼ CaFe2O4 þ 0.5H2 (R6) Effect of temperature on the distribution of gas-liquid-solid
products
CaFe2O4 þ 0.5C ¼ 0.5Ca2Fe2O5 þ FeO þ 0.5CO (R7) To investigate the distribution of gas-liquid-solid products,
the weight of solid-phase and liquid-phase were obtained by
Ca2Fe2O5 þ 3C ¼ 2CaO þ 2Fe þ 3CO (R8) calculating the weight difference before and after pyrolysis,
from the ceramic boat filled with the samples and absorption
Ca2Fe2O5 þ 1.5C ¼ 2CaO þ 2Fe þ 1.5CO2 (R9) bottles respectively. And the weight of the gaseous phase was
determined by mass balance. The distribution of gas-liquid-
FeO þ C ¼ Fe þ CO (R10) solid products of Nannochloropsis sp. pyrolysis is depicted in
Fig. 5. In the absence of oxygen carrier, the yield of gaseous
Fe þ H2O ¼ FeO þ H2 (R11)

CaO þ CO2 ¼ CaCO3 (R12)

From the DG values of R4-R6, we know that the Re-CF ox-

ygen carrier, composed of CaO and Fe, can be oxidized by CO2/
H2O over the whole temperature range 400e1000  C. CO/H2
and the oxidized oxygen carrier Ca2Fe2O5 are thereby gener-
ated. However, the Re-CF2 oxygen carrier, composed of
Ca2Fe2O5 and FeO, is hardly oxidized by CO2/H2O when the
temperature is higher than 400  C. Since plentiful H2O and CO2
are generated during the pyrolysis process of biomass, large
amounts of CO and H2 will be produced by reaction R4 and R5
in the pyrolysis stage. The generated H2 provides a potential
hydrogen source for the in-situ upgrade of pyrolysis bio-oils at
a lower temperature. As shown in Fig. 4, reactions R7-R10
indicate that the oxidized oxygen carrier can be reduced
thermodynamically at temperatures higher than 580  C for R7, Fig. 5 e Distribution of gas-liquid-solid three-phase yield of
718  C for R10, 775  C for R8, and 860  C for R9, respectively. It pyrolysis products (a) gaseous phase; (b) liquid phase; (c)
suggests that CaFe2O4 can be easily converted to Ca2Fe2O5 and solid phase.

Please cite this article as: Liu Y et al., Co-production of upgraded bio-oils and H2-rich gas from microalgae via chemical looping py-
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6 international journal of hydrogen energy xxx (xxxx) xxx

phase increased obviously with a temperature rise from 450  C left the insufficient oxygen for char gasification. Considering
to 550  C, while both the solid phase and liquid phase yield the oxygen-receptor role of oxygen carriers from bio-oils in
decreased. With increasing temperature, more volatile matter the pyrolysis stage, 600  C may be an optimal final tempera-
tended to be released from biomass, while the large molecules ture. Furthermore, the carbon balance of gas-liquid-solid
in the liquid phase leant to break into small molecules in the phase at 600  C was calculated based on the carbon percent-
form of gaseous phase. When the temperature was elevated age in each phase (Table S1). It was clear that the contents of
from 550  C to 650  C, the yield of three phases changed carbon in both pyrolysis gas and bio-oils were increased by the
slightly with increasing temperature. It appears that the py- introduction of reduced oxygen carriers, despite the yield of
rolysis of microalgae is minimal below a temperature of both pyrolysis gas and bio-oils was decreased.
550  C.
Compared with the case without oxygen carrier at the Effect of temperature on the composition of bio-oils
same temperature lower than 600  C, both the reduced Due to the complexity of generated products and the lack
calcium-ferrite oxygen carriers could significantly increase of commercially available standards, the GC-MS technique
the yield of solid-phase, consequently decrease the yield of could not be used for quantitative analysis of the compounds.
the liquid phase and gaseous phase. Two aspects related to However, the chromatographic peak area percentage of a
the reduced calcium-ferrite oxygen carriers accounted for this compound is linearly to its relative content in bio-oils. Thus,
variation. First, the reduced calcium-ferrite oxygen carrier peak area percentages were used to indicate the relative
was thermodynamically susceptible to oxidization by steam, content of compounds in bio-oils formed under different
CO2, and other oxygenated chemicals. The oxygen transferred conditions. The total ion chromatograms of bio-oils formed
from pyrolysis products to oxygen carrier could countervail with and without oxygen carriers at different temperatures
part of the decreased weight of microalgae, and thus resulting are listed in Figs. S1-S3 (Supplementary Data). To depict the
in the increase of solid phase yield. Second, the reduced effects of oxygen carriers on functional group reactions, the
calcium-ferrite oxygen carrier could improve the quality of identified compounds were divided into five groups: hydro-
the liquid phase by catalysing the decarboxylation and/or carbons (aromatic hydrocarbons, alkanes, and olefins), phe-
decarbonylation of bio-oils, which would lower the yield of nols, oxygenated compounds (alcohols, carboxylic acids,
the liquid phase. The effect of oxygen carriers on the quality ketones, and esters), N-containing compounds (nitriles) and
of bio-oils will be discussed in detail below. Unlike the Re- other complex compounds.
CF oxygen carrier, Re-CF2 oxygen carrier generated more Fig. 6 shows the relative content of each compound in bio-
gaseous phase at the expense of the solid phase. XRD patterns oils formed as a function of the temperature in the absence
below demonstrated that the principal reason was the pres- of oxygen carriers. Contents of N-containing compounds
ence of more Fe phase in the Re-CF2 oxygen carrier. decreased with increasing temperature, while those of hy-
When temperature was elevated from 600  C to 650  C, the drocarbons increased. The relative content of N-containing
yield of liquid phase decreased remarkably in the presence of compounds (mostly nitriles) was as high as 45%, and its
oxygen carrier, resulting in the increase of gaseous phase. A minimum value was still higher than 30% at 650  C. N-con-
higher temperature of 650  C not only accelerated the taining compounds were originated from the proteins in
destruction of liquid phase, but also produced a bio-oil with a microalgae primarily, with the proportion as high as 44% in
much more complicated composition. The composition of the the investigated microalgae. High contents of N-containing
liquid phase will be discussed in the following section. In compounds could lead to poor quality bio-oils formed
addition, the reaction between oxygen carrier and solid char from the direct pyrolysis of microalgae. As illustrated in
was enhanced, but consumed oxygen from oxygen carrier and Fig. 6b, the increases in hydrocarbons content with increasing

Fig. 6 e Relative content of (a) five groups; (b) hydrocarbons; (c) oxygenated compounds in bio-oils as a function of
temperature without oxygen carriers.

Please cite this article as: Liu Y et al., Co-production of upgraded bio-oils and H2-rich gas from microalgae via chemical looping py-
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 international journal of hydrogen energy xxx (xxxx) xxx 7

temperature were due to the conversion of long-chain com- and ketones were in the majority. Predictably, the acidity of
pounds into short olefins, as well as into aromatic hydrocar- the obtained bio-oils was significantly reduced. Considering
bons. The relative content of oxygenated compounds that the oxygen content of 1-mol of mono-alcohol or mono-
accounted for approximately 30% of the bio-oils, but changed ketones is half that of 1-mol of mono-carboxylic acid, the ef-
slightly with increasing temperature. From Fig. 6c, we could fect of the reduced oxygen carrier on the removal of oxygen in
know that more than 60% oxygenated compounds were car- bio-oils was noticeable. Alcohols are highly desirable for fuel
boxylic acids. The generated carboxylic acids elevated the production, while ketones are building blocks that can un-
acidity of the generated bio-oils and led to difficulties in sub- dergo further aldol condensation to increase the carbon
sequent processing. In addition, the phenol content first number of molecules [33]. Therefore, the generation of both
increased and then decreased with increasing temperature, alcohols and ketones was beneficial to the further processing
and its minimum level of production appeared at 550  C. of bio-oils. Ketones were probably derived from the ketoni-
Fig. 7 shows the relative content of each compound with zation of carboxylic acids, which involved in the reaction of
increasing temperature in the presence of the Re-CF2 oxygen two carboxylic acids with a-H atoms [34,35]. The generalized
carrier. In comparison with the cases run without an oxygen ketonization of carboxylic acid is shown in reaction R13,
carrier (Fig. 6), it was observed that the relative content of N- which involves in the reaction of two carboxylic acid mole-
containing compounds decreased dramatically, while that of cules to form a molecule of ketone, CO2 and H2O. Furthermore,
hydrocarbons increased greatly at all investigated tempera- the variation in both the content and carbon-chain length
tures. Taking 550  C as an example, the addition of Re-CF2 of ketones corresponded with those of carboxylic acids.
oxygen carrier resulted in the fact that the relative content For instance, as shown in Figs. S2e3, the increase in 2-
of N-containing compounds decreased from 47.8% without an heptadecanone (17-carbon ketone) content was accompa-
oxygen carrier to 4%, while the relative content of hydrocar- nied by the disappearance of n-hexadecanoic acid (16-carbon
bons was enhanced from 20.7% to 48.3%. The variations in acid) and acetic acid. 2-heptadecanone was probably pro-
both N-containing compounds and hydrocarbons involved duced by the reaction of n-heptadecanoic acid with acetic
the thermal cracking of long-chain nitriles to generate large acid. The relative content of 2-heptadecanone was higher
amounts of short-chain hydrocarbons. Yi et al. [32] reported than 10% at the investigated temperature. Its maximum value
that mixed Fe/Ca additives could effectively affect nitrogen was as high as 19% at 450  C. In addition, the relative content
transformation by forming intermediates FeNx and CaCNx of oxygenated compounds decreased sharply when the tem-
during proteins and amino acids pyrolysis process. And these perature was elevated to 650  C from 600  C. This tendency
intermediates would further convert into N2 in the presence of may be ascribed to the HDO reaction and the cracking reaction
Ca2Fe2O5. In this work, the main component of microalgae of ketones.
were proteins and the reduced oxygen carrier was a mixture of
CaO, Fe and Ca2Fe2O5. Hence, it could be predicted that ni- RCOOH þ RʹCH2COOH ¼ RCOCH2Rʹ þ CO2 þ H2O (R13)
trogen in the microalgae underwent an analogical trans-
formation route. Nevertheless, this hypothesis needs further Contrary to the variation of oxygenated compounds con-
investigation, since unstable intermediates such as FeNx and tent, the relative content of hydrocarbons increased with
CaCNx were not observed yet in the current work. increasing temperature. This result indicated that the higher
For oxygenated compounds, its relative content increased, temperature facilitated the upgrade of bio-oils. On the other
while the composition changed remarkably. As shown in hand, when the temperature was elevated from 550  C to
Fig. 7c, carboxylic acids almost disappeared, while alcohols 650  C, contents of N-containing compounds and other

Fig. 7 e Relative content of (a) five groups; (b) hydrocarbons; (c) oxygenated compounds in bio-oils as a function of
temperature with the Re-CF2 oxygen carrier.

Please cite this article as: Liu Y et al., Co-production of upgraded bio-oils and H2-rich gas from microalgae via chemical looping py-
rolysis, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.05.047
8 international journal of hydrogen energy xxx (xxxx) xxx

complex compounds began to increase. As shown in Fig. 7b, chains of biodiesel and jet fuel range between C14eC20, and
the relative content of aromatics in hydrocarbons was C11-15, respectively. The distribution of the carbon chain
increased remarkably at temperatures higher than 550  C, and lengths of the alkanes and olefins obtained at the optimal
further enhanced the formation of tar. Therefore, there was temperature, i.e., 600  C, is presented in Fig. 9. Almost all the
an optimal pyrolysis temperature for upgrading the quality of alkanes generated with or without the reduced oxygen carrier
bio-oils. Considering the reactivity of the oxygen carrier and exhibited chain lengths in the range C11eC16, which falls
the quality of the bio-oils, 600  C was supposed to be the within the range of jet fuel. However, the carbon chain lengths
optimal temperature for microalgae pyrolysis with the Re-CF2 of olefins were different from each other. For the Re-CF oxygen
oxygen carrier. carrier, the carbon chain lengths of all the generated olefins
Fig. 8 shows the relative content of each compound in bio- were higher than 11. In comparison, the carbon chain length
oils as a function of the temperature in the presence of the Re- of nearly half of the olefins generated with the Re-CF2 oxygen
CF oxygen carrier. Re-CF oxygen carrier also could upgrade the carrier were lower than 11. From this standpoint, the Re-CF
quality of bio-oils by decreasing the relative content of N- oxygen carrier was more suitable for the generation of jet fuel.
containing compounds and increasing the relative content of Furthermore, the elemental composition of bio-oils made
hydrocarbons. The four groups with both reduced oxygen from pyrolysis at 600  C was analysed. As tabulated in Table 2,
carriers shared the same trend with increasing temperature. the contents of C and H in the bio-oils increased remarkably in
In comparison with the case without an oxygen carrier, the the presence of the reduced oxygen carriers, while the content
change in the relative content of each compound in bio-oils of O was notably reduced. The decrease in O content in the
with the Re-CF oxygen carrier was smaller than that with bio-oils was attributed to the conversion of carboxylic acids to
the Re-CF2 oxygen carrier, due to the different compositions alcohols or ketones, which was in accordance with the pre-
of the reduced oxygen carrier. In the pre-reduction process, vious discussion. According to elemental analyses [37], the
CaFe2O4 was reduced to FeO and Ca2Fe2O5 at first and then to predicted heating values were increased from 20.5 MJ/kg for
CaO and Fe. Thus, more Fe in the Re-CF2 oxygen carrier
abstracted more oxygen from pyrolysis products and gener-
ated more H2 by the iron-steam process to provide for in-situ
upgrading of bio-oils.
The relative content of straight-chain hydrocarbons is
significant for the use of bio-oils as an alternative fuel. As
mentioned above, both generated alkanes and olefins were
mainly straight-chain hydrocarbons, which improved the
quality of bio-oils as an alternative fuel. Straight-chain hy-
drocarbons in bio-oils probably resulted from catalytic
cracking of both long-chain nitriles by denitrification and
carboxylic acids by decarboxylation. A possible route for long
carbon chain hydrocarbons involved the dehydration or HDO
of alcohols, which originated from HDO of ketones [36].
Dehydration of alcohols generated olefins, while HDO of al-
cohols produced alkanes.
Fig. 9 e Distribution of carbon chain length of alkanes and
The length of the carbon chain is another important indi-
olefins.
cator for bio-oil fuels. Generally, the lengths of the carbon

Fig. 8 e Relative content of the composition in bio-oils as a function of temperature with the Re-CF oxygen carrier (a) five
groups; (b) hydrocarbons; (c) oxygenated compounds.

Please cite this article as: Liu Y et al., Co-production of upgraded bio-oils and H2-rich gas from microalgae via chemical looping py-
rolysis, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.05.047
 international journal of hydrogen energy xxx (xxxx) xxx 9

evidence has been provided on the contributions of these

Table 2 e Elemental composition and heating value of
specific reactions to the observed yield. Except for the further
bio-oils.
pyrolysis reaction of microalgae, reactions R4 and R11 be-
C, wt. % H, wt. % O, wt. % N, wt. % HHV, MJ/kg [37]
tween steam and the reduced oxygen carrier resulted in the
MA 48.62 7.50 37.64 6.53 20.5 generation of a great deal of H2, while the ketonization reac-
Re-CF2 69.84 8.64 14.41 7.11 34.2 tion R13 was responsible for the generation of CO2 and H2O.
Re-CF 71.89 8.95 12.74 6.42 36.0
Furthermore, the H2O generated in R13 provided an in-situ
hydrogen source for reactions R1, R4 and R9. Although the
carbonation of CaO R12 and reaction R5 between CO2 and the
bio-oils produced without oxygen carrier up to 34.2 MJ/kg and
reduced oxygen carrier potentially lowered the amount of CO2
36.0 MJ/kg for bio-oils generated with the Re-CF2 and Re-CF
present, the facile ketonization reaction and water-gas shift
oxygen carriers, respectively. The high heating value of the
reaction led to a decrease in CO2 amount.
generated bio-oils made it a promising alternative fuel (e.g.
It was also observed that the yields of both CO2 and H2 with
biodiesel with a heating value of 33e41 MJ/kg or jet fuel with a
Re-CF2 oxygen carrier were higher than those observed using
heating value of 42.5 MJ/kg). Certainly, a further upgrade is
Re-CF oxygen carrier. The lower molar ratio of CaO to Fe in the
required for the prepared bio-oils before it can meet the
Re-CF2 oxygen carrier was responsible for this phenomenon.
standard of an alternative fuel.
As the molar ratio of CaO to Fe decreased, the carbonation
reaction of CaO would be hindered, while the iron-steam
Effect of oxygen carrier on the composition of pyrolysis gas
process was enhanced. In summary, H2-rich pyrolysis gas
was produced in the presence of both reduced calcium-ferrite
To obtain a complete picture of the microalgae conversion, the
oxygen carriers in the pyrolysis stage.
major non-condensable gases in the pyrolysis stage were
analysed. The gas yield of each component (H2, CO, CH4, and
Gasification behaviour of pyrolysis char
CO2) in pyrolysis gas obtained at 600  C is illustrated in Fig. 10.
In the absence of an oxygen carrier, the total yield of pyrolysis
In the pyrolysis stage, the reduced oxygen carrier was con-
gas was only 63.8 mL/g microalgae, and the main component
verted to its oxidized state by the oxygen in microalgae.
was CO2 at 18.8 mL/g microalgae. Pyrolysis gas made without
Consequently, high-quality biofuel with low oxygen content
oxygen carriers primarily resulted from direct pyrolysis of
and H2-rich pyrolysis gas was obtained. The left solid residue
volatiles. It was found that the introduction of reduced oxygen
remaining after pyrolysis was a mixture of oxidized oxygen
carriers efficiently facilitated the generation of pyrolysis gas.
carrier and bio-char. In comparison with the direct CLG of
The total yield of pyrolysis gas was as high as 173.1 mL/g
microalgae, the pyrolysis stage of CLPy eliminated the vola-
microalgae and 151.6 mL/g microalgae by using the Re-CF2
tiles in microalgae at a lower temperature in the pyrolysis
and Re-CF oxygen carriers, respectively. This result seemed
stage, and further reduced the amount of tar generated at
to contrast with the distribution of gas-liquid-solid products.
the gasification temperature. In the gasification stage, the
According to the abovementioned yield, the weight yield of
remaining solid consisted of the oxidized oxygen carrier and
the gaseous phase varied little upon addition of the reduced
bio-char, and they reacted with each other as shown in the
oxygen carrier. However, among the four components, the
earlier thermodynamic analysis. When the temperature was
volume yield of H2 generated in the presence of both reduced
higher than 700  C, the reactions between the oxidized oxygen
oxygen carriers accounted for more than 50% of the total. The
carrier and bio-char occurred, i.e., bio-char CLG proceeded. In
increasing volume yield of pyrolysis gas was compatible with
light of the reported bio-char CLG, the temperature for the
its weight yield.
gasification of bio-char was set at 850  C in the current work.
Observations were used to support the hypothesis that
To probe the effect of steam on bio-char CLG, the experiments
certain reactions were dominant, because no experimental
with and without the gasifying agent, namely steam in this
case, were carried out.
The accumulated gas yield of each component of syngas
with and without the gasifying agent is depicted in Fig. 11. It
was observed that the gaseous products in the gasification
stage of each oxygen carrier mainly consisted of CO without a
gasifying agent, while the dominant component with the
gasifying agent was H2. Without the gasifying agent, reaction
R8 between the oxidized oxygen carrier and char occurred,
producing a considerable amount of CO. The accumulated
yield of CO was as high as 131 and 234 mL/g microalgae for CF2
and CF oxygen carrier, respectively. The generation of H2
without steam resulted from the further pyrolysis of char,
while CH4 was hardly generated under the four sets of con-
ditions. Together with reactions R4 and R11 occurring be-
tween the reduced oxygen carrier and steam, reaction R14
Fig. 10 e Gas yield of pyrolysis gas formed with and involving steam and char also took place in the presence of
without a reduced oxygen carrier. steam. The accumulated yields of H2 were as high as 693 and

Please cite this article as: Liu Y et al., Co-production of upgraded bio-oils and H2-rich gas from microalgae via chemical looping py-
rolysis, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.05.047
10 international journal of hydrogen energy xxx (xxxx) xxx

PDF#72e1650), leaving part of the Fe phase in the mixed solid

residues. According to literature [35], CaO served as a catalyst
for the ketonization of carboxylic acids, by forming carbox-
ylate salts (RCOO)2Ca, and further generating ketones and
CaCO3. On the other hand, (RCOO)2Ca could be directly
cracked into hydrocarbons and CaCO3. The appearance of FeO
in the CaFe2O4 oxygen carrier after the pyrolysis stage resulted
from the reaction of Fe with H2O. In addition, the relatively
weak peak intensity for the Ca2Fe2O5 oxygen carrier in the
mixed solid residue after the pyrolysis stage was probably
attributed to the coverage of unreacted pyrolysis char, due to
insufficient oxygen in Ca2Fe2O5. This phenomenon agreed
with the yield of the solid phase in the pyrolysis stage and
carbonaceous gas in the gasification stage. In sum, re-oxidized
Ca2Fe2O5 obtained in the pyrolysis stage was able to supply
oxygen for the gasification of pyrolysis char in the gasification
stage.
XRD patterns of the mixed solid residue remaining after
the gasification stage with/without steam as the gasifying
agent are depicted in Fig. 12cef. In the absence of steam, the
Fig. 11 e Accumulated yield of each component of syngas overwhelming majority of both CF2 and CF oxygen carriers
with and without gasifying agent. (a) CF2 oxygen carrier were reduced to CaO and Fe, with minimal production of
without steam; (b) CF2 oxygen carrier with steam; (c) CF Fe3C. The formation of Fe3C was related to the carburization
oxygen carrier without steam; (d) CF oxygen carrier with on the surface of the oxygen carrier. The reduced calcium-
steam. ferrite oxygen carrier was available for the next pyrolysis-
gasification loop. It should be noted that the impact of ash
on the reactivity of the oxygen carrier in CLPy process was also
417 mL/g microalgae for CF2 and CF oxygen carrier, significant, just as it was in the other chemical-looping pro-
respectively. cesses led by solid fuels. In the presence of a gasifying agent,
the calcium-ferrite oxygen carrier was re-oxidized by the
C þ H2O ¼ CO þ H2 (R14) excess steam, affecting the realization of the next pyrolysis-
gasification loop. Two approaches, controlling the ratio of
Due to the higher Fe content present in the Re-CF2 oxygen
carrier (relative to Re-CF), more microalgae was pyrolysed,
resulting in a lower yield of solid phase in the pyrolysis stage
and a higher yield of H2 in the gasification stage. The higher
yield of the solid phase with the Re-CF oxygen carrier led to a
higher yield of carbonaceous gas. Because of the lower oxi-
dizability of Ca2Fe2O5, the main product of the reaction be-
tween the calcium-ferrite oxygen carrier and char was CO
rather than CO2. In addition, it should be pointed out that the
oxygen carrier reduced by char could be re-oxidized in-situ by
the excess steam, which would further decrease the amount
of oxygen carrier available for the next pyrolysis stage. The
proportion of steam used should be investigated in the future.

Characterization of the used oxygen carrier

To reveal the effect of the calcium-ferrite oxygen carrier at

both the pyrolysis stage and gasification stages, the mixed
solid residue remaining after pyrolysis and gasification was
analysed by using XRD and SEM.
XRD patterns of the mixed solid residue after pyrolysis are
illustrated in Fig. 12a and Fig. 12b. It is clear that most of the
reduced oxygen carriers were oxidized to Ca2Fe2O5 after the
pyrolysis stage. This involves reactions R4-R7 of the reduced Fig. 12 e XRD patterns of mixed solid residues after
oxygen carrier. Meanwhile, a great deal of hydrogen or CO was pyrolysis with (a) CF2 oxygen carrier; (b) CF oxygen carrier
produced, which is in accord with the composition of the and after gasification stage: (c) CF2 oxygen carrier without
pyrolysis gas. In addition, some of the CaO in the reduced steam; (d) CF2 oxygen carrier with steam; (e) CF oxygen
oxygen carrier appeared as a new phase CaCO3 (JCPDS carrier without steam; (f) CF oxygen carrier with steam.

Please cite this article as: Liu Y et al., Co-production of upgraded bio-oils and H2-rich gas from microalgae via chemical looping py-
rolysis, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.05.047
 international journal of hydrogen energy xxx (xxxx) xxx 11

char to steam or adding another reduction stage involving molecule gases (e.g. NH3) were resulted from the direct py-
pyrolysis gas or syngas, could be adopted in the future. In rolysis of proteins, while the majority of oxygenated products,
addition, in the presence of steam, other phases were gener- especially long-chain carboxylic acids originated from the
ated, such as Fe3O4 (JCPDS PDF#88e0866), and CaFe3O5 (JCPDS direct pyrolysis of lipids and polysaccharides. With the addi-
PDF#72e0890), which would affect the properties of multiple tion of reduced oxygen carrier, reactions such as catalytic
redox cycles of oxygen carrier. cracking, denitrification, decarboxylation, HDO, and ketoni-
Fig. 13 shows the morphological characterization of the zation occurred. Based on the results discussed above, the
freshly reduced oxygen carrier and the mixture after pyrolysis possible pyrolysis paths for microalgae reacting in the pres-
is illustrated in. As illustrated in Fig. 13a and b, it can be seen ence of reduced oxygen carriers are demonstrated in Fig. 14.
that both the Re-CF2 and Re-CF oxygen carrier possessed Denitrification involves the breakage of long-chain nitriles
smooth surfaces and well-developed pore structures after into olefins, alkanes and small N-containing gases. A probable
they were reduced by CH4. After the pyrolysis stage, the sur- route was the generation of N2 in the presence of Ca2Fe2O5
faces of the two oxygen carriers were partly covered by the originated from the intermediates FeNx and CaCNx [32].
pyrolysis char, and some pore structures on the surface of the Certainly, this hypothesis requires the further verification.
oxygen carrier were blocked (Fig. 13c and d). Nevertheless, the Ketonization of carboxylic acids in the presence of a reduced
char covered on the surface of oxygen carrier could facilitate oxygen carrier occurred via two pathways [34e36]: bulk
the solid-solid reaction between oxygen carrier and pyrolysis ketonization of CaO, which occurred via decomposition of
char in the gasification stage. The porous pyrolysis char on the the corresponding carboxylate salts (RCOO)2Ca, and surface
oxygen carrier surface could also benefit the subsequent ketonization of metal oxides, which was catalysed by solid
gasification reaction at high temperature. surfaces. As with the metal oxide (e. g. CeO2) reported for
ketonization reaction [33,34], the Ca2Fe2O5 oxygen carrier
Reaction paths of the CLPy process underwent fast multistep reduction/oxidation cycles. It
was first reduced by an a-hydrogen abstracted from the
In contrast to lignocellulosic biomass, the microalgal biomass oxygenated pyrolysis products and then re-oxidized through
is composed of proteins, lipids, and polysaccharides. The the combination of the proton and a hydroxyl group from the
pyrolysis behaviour of individual components is respon- acid to form water and CO2, i.e., reaction R13. HDO could give
sible for the paths for overall pyrolysis of microalgae. Pyrol- rise to the formation of alcohols from ketones, thereby further
ysis involves a series of bond breaking reactions, and free generating alkanes and olefins. It has been verified that the
radical reactions, as well as oligomerization and cyclization. oxidation reaction of the reduced oxygen carrier could provide
Nitrogen-containing components such as nitriles and small a sufficient hydrogen source for HDO. Two reactions are

Fig. 13 e SEM of (a) fresh Re-CF2 oxygen carrier; (b) fresh Re-CF oxygen carrier; and of the mixed solid residue after pyrolysis
stage of (c) CF2 oxygen carrier; (d) CF oxygen carrier.

Please cite this article as: Liu Y et al., Co-production of upgraded bio-oils and H2-rich gas from microalgae via chemical looping py-
rolysis, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.05.047
12 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 14 e Possible pyrolysis paths for microalgae in the presence of a reduced oxygen carrier.

responsible for hydrogen production. One reaction is the iron- microalgae can be divided into three aspects, i. e., denitrifi-
steam process R9, resulting from the oxophilicity of Fe and the cation, ketonization, and HDO. Ketonization involved both
ubiquity of H2O in biomass conversion [38]. The other reaction bulk ketonization with CaO and surface ketonization with
R4 between reduced oxygen carrier and H2O has been proven Ca2Fe2O5, while two hydrogen-generating reactions were
to be thermodynamically and experimentally favourable. In responsible for HDO. Certainly, more investigations including
addition, carboxylic acids or other compounds also acted as multiple reaction cycles will be required in the further to
internal hydrogen donors, resulting in the simultaneous assess its potential applications.
ketonization and HDO.

Declaration of competing interest

Conclusions
The authors declare that they have no known competing
In seeking to upgrade the quality of pyrolysis bio-oils and
financial interests or personal relationships that could have
convert the pyrolysis char to H2/CO-rich syngas, a novel py-
appeared to influence the work reported in this paper.
rolysis process, chemical looping pyrolysis (CLPy), was pro-
posed, and its feasibility was testified thermodynamically and
experimentally. The following conclusions can be drawn: 1)
Both the reduced calcium-ferrite oxygen carriers could up- Acknowledgements
grade the quality of bio-oils by decreasing the oxygen and
nitrogen content, and produce H2-rich pyrolysis gas and H2- The authors gratefully acknowledge the financial support
rich or CO-rich pyrolysis gas. 2) The quality of pyrolysis from the National Natural Science Foundation of China
products were significantly affected by the pyrolysis temper- (51506105, 21706141), the Qingdao Application Foundation
ature and the type of oxygen carrier. At the optimal pyrolysis Research Project (17-1-1-37-jch), the State Key Laboratory of
temperature of 600  C, the heating value of bio-oils was High-efficiency Utilization of Coal and Green Chemical Engi-
dramatically increased up to 34.2 MJ/kg and 36.0 MJ/kg by neering (2019-KF-03), and the Talent Fund of Shandong
employing the Re-CF2 and Re-CF oxygen carrier, respectively, Collaborative Innovation Center of Eco-Chemical Engineering
while H2 content in the pyrolysis gas was as high as 50%. 3) (XTCXQN06).
The oxygen derived from the pyrolysis bio-oils in reduced
oxygen carrier can easily gasify the pyrolysis char, whether or
not a gasifying agent was used. H2 accounted for 70% of syngas Appendix A. Supplementary data
when steam was used as the gasifying agent, while CO
comprised up to 66% without gasifying agent. 4) The effects of Supplementary data to this article can be found online at
the reduced oxygen carrier on the upgrading of bio-oils from https://doi.org/10.1016/j.ijhydene.2021.05.047.

Please cite this article as: Liu Y et al., Co-production of upgraded bio-oils and H2-rich gas from microalgae via chemical looping py-
rolysis, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.05.047
 international journal of hydrogen energy xxx (xxxx) xxx 13

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Please cite this article as: Liu Y et al., Co-production of upgraded bio-oils and H2-rich gas from microalgae via chemical looping py-
rolysis, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2021.05.047