Available online at www.sciencedirect.

com

ScienceDirect
Energy Procedia 105 (2017) 82 – 87

The 8th International Conference on Applied Energy – ICAE2016

Direct conversion of bio-syngas to gasoline fuels over a

Fe3O4@C Fischer-Tropsch synthesis catalyst
Junling Tua, Mingyue Ding*b,c, Tiejun Wang *b, Longlong Ma b, Yongjun Xua,
Shimin Kanga, Gang Zhanga
a
Key Laboratory of Distributed Energy Systems of Guangdong Province, Department of Energy and Chemical Engineering,
Dongguan University of Technology, Dongguan 523808, China.
b
CAS Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences,
Guangzhou, 510640, P. R. China.
c
Wuhan University, Wuhan, 430072, P. R. China.

Abstract

Fischer-Tropsch synthesis (FTS), as an alternative process for producing liquid fuels from bio-syngas, is receiving
renewed interest for both industrial and academic applications. A novel carbon-encapsulated Fe3O4 nanocatalyst is
designed to optimize the product distribution of hydrocarbons. Several techniques such as XRD, H 2-TPR, BET, XPS,
LRS, SEM and TEM are used to characterize the catalyst samples. The characterization results indicated that
combination of glucose and iron species led to the formation of carbon-encapsulated Fe3O4 nanoparticles (Fe3O4@C),
and the increasing glucose content in the catalysts resulted in the decrease of Fe3O4@C nanoparticle sizes. Fe3O4@C
with smaller particle sizes provided more surface amounts of iron species, which facilitated the reduction of iron
oxides and formation of active iron sites. However, the excess addition of glucose resulted easily in the formation of
more carbon deposition on the surface of Fe3O4@C. Compared to the traditional Fe2O3 catalyst, the Fe3O4@C
catalyst showed excellent catalytic activity and higher selectivity of gasoline products. Especially, decreasing
nanoparticle sizes for the carbon-encapsulated Fe3O4 catalysts improved obviously the catalytic activity and increased
the selectivity of C2-4 hydrocarbons.

Keywords: Bio-syngas; Liquid fuels; Fischer-Tropsch synthesis; Fe3O4@C

1. Introduction

Fischer-Tropsch synthesis (FTS), as an important technology in the production of liquid fuels and
chemicals from syngas derived from coal, natural gas, and biomass materials, is receiving a renewed
interest for both industrial and academic applications because of the emergency of transportation fuel
shortage in the whole world [1]. Compared to other FTS catalysts (including Co, Ru, Ni), the iron-based

* Corresponding author. Tel.: +0-20-87057790; fax: +0-20-87057789.

E-mail address: dingmy@ms.giec.ac.cn, wangtj@ms.giec.ac.cn.

1876-6102 © 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the scientific committee of the 8th International Conference on Applied Energy.
doi:10.1016/j.egypro.2017.03.283
 Junling Tu et al. / Energy Procedia 105 (2017) 82 – 87 83

catalyst is more attractive for FTS with lower H2/CO ratio syngas derived from coal or biomass due to its
higher water-gas shift activity, lower cost, flexible product distribution and favorable engineering
characteristics [2].
During Fischer-Tropsch synthesis there is the formation of widely C1-C50 hydrocarbons, which brings
us the difficulty to adjust hydrocarbons distribution within the designed range. Some chemical promoters
such as basic and transition metals (K, Cu, Mn and so on) , as well as structure promoters (including Al,
Si, Zn et al.) are added into the Fe catalysts to improve FTS performances. Recently, design and
application of core-shell materials have attracted more and more attention because of space confinement
and synergistic function for restraining the agglomeration of nanoparticles. The spatial and chemical
characteristics of core-shell materials provide us an excellent way to optimize the FTS performances.
However, controlled synthesis of iron-based core-shell materials and particle size effects on Fischer-
Tropsch synthesis are rarely reported.
Acted as a structure sensitive reaction for Fischer-Tropsch synthesis, the catalytic activity and
selectivity are believed to depend on the particle size [3]. It has been reported that turnover frequency
(TOF) is in relationship with cobalt particle sizes in smaller size (<8 nm), whereas independent of particle
sizes in bigger size (>8 nm).
Herein, we investigate the controlled preparation of carbon-encapsulated Fe3O4 catalysts with
different particle sizes via an improved one-step solvothermal method, and particle size effects on FTS
performances. Because of complex micro-structures of Fe3O4@C, several methods including X-ray
diffraction (XRD), N2 adsorption-desorption, scanning and transmission electron microscopy (SEM and
TEM, respectively), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy (LRS) and
temperature programmed reduction with hydrogen (H2-TPR) were combined together to characterize the
samples.

2. Experimental

Synthesis of carbon-encapsulated Fe3O4 nanoparticles: nano-Fe3O4@C catalysts (NFCs) were

fabricated by an improved solvothermal reaction of FeCl 3, Glucose and urea in ethylene glycol (EG)
solvent.
Textural properties of the catalysts were measured by N2 physisorption at -196 oC using a
Micromeritics ASAP 2010 instruments. Powder X-ray diffraction patterns (XRD) of the catalyst samples
were measured on a D/max-RA X-ray diffractometer (Rigaku, Japan). Temperature program reduction of
hydrogen (H2-TPR) was carried out in a U-tube quartz reactor with a hydrogen-argon mixture (containing
5 vol % of hydrogen) as the reductive gas. The morphology and microstructure were observed with
scanning electron microscopy (SEM) on a HITACHI S-4800 electron microscope operating at 2 kV.
High-resolution TEM (HRTEM) photographs were taken on a JEOL-2010 Model (Japan) transmission
electron microscope. The Fischer-Tropsch synthesis tests were conducted in a fixed-bed, stainless flow
micro-reactor.

3. Results and discussion

3.1 Structure properties of the catalysts

The SEM and TEM images of iron-based materials with adding different glucose amounts are shown
in Fig. 1. For the Fe3O4 catalyst without adding of glucose (shown in Fig. 1a), the sample consists of a
hollow iron-based sphere, which has the particle size of about 300 nm. With gradual addition of glucose
(shown in Fig. 1b-1e), the catalyst presents a spherical shape with different particle sizes. The TEM
84 Junling Tu et al. / Energy Procedia 105 (2017) 82 – 87

images (shown in Fig. 1f) present that the spherical nanoparticle has a core-shell structure with a Fe3O4
core and carbon shell, indicating that the Fe3O4@C catalyst may be synthesized by improved one-step
solvothermal method. As the adding glucose concentration is low (0.1 g) in Fe3O4@C, the nanoparticle
size is about 33 nm. Accompanied with gradual increasing of glucose concentration, the particle size of
Fe3O4@C presents a decreasing trend, suggesting that changing glucose amount in Fe3O4@C may adjust
efficiently the particle size of core-shell structure. The crystallite sizes calculated from XRD (shown in
Table 1) display that the nanoparticle size of Fe3O4@C decreases gradually from 32 nm to 7 nm with the
increasing of glucose concentration from 0.1 g to 0.4 g, which is consistent with the SEM results.
In addition, both the BET surface area and pore volume present an increasing trend with the
increasing glucose content in Fe3O4@C, indicating that the increase of glucose content results in the
decrease of nanoparticle sizes and dispersion of iron species, promoting the increase of BET surface area.
As the glucose content increases to 0.4 g (NFC4), both the BET surface area and pore volume begin to
decrease, which imply that the excess addition of glucose in Fe3O4@C leads probably to the formation of
more carbon deposition on the catalyst surface, restraining the pore structures and decreasing the BET
surface area of Fe3O4@C.

Figure 1 SEM and TEM images of Fe3O4@C with different particle sizes prepared under various initial
amounts of glucose: a 0 g, b 0.1 g, c 0.2 g, d 0.3 g, e 0.4 g. (a-e, SEM images of NFC0, NFC1, NFC2,
NFC3, NFC4, respectively; f, TEM image of NFC2)
Table 1 Properties of Fe3O4@C with different particle sizes
BET surface Pore Average pore
Glucose Crystallite size; Particle size;
Samples area; volume; size;
(g) XRD (nm) SEM (nm)
(m2/g) (cm3/g) (nm)
NFC0 0 60.6 300 8.82 0.048 21.95
NFC1 0.1 32.2 33 60.02 0.286 19.03
NFC2 0.2 17.7 21 98.94 0.286 11.56
NFC3 0.3 14.4 18 117.34 0.288 9.82
NFC4 0.4 7.1 10 106.88 0.181 6.75

3.2 Phase compositions of the catalysts

Phase compositions of carbon-encapsulated iron catalysts are characterized by XRD and RLS. As
shown in Fig. 2a, all of the catalysts present mainly the diffraction peaks at 2θ of (30.08 o, 35.46 o, 43.01 o,
 Junling Tu et al. / Energy Procedia 105 (2017) 82 – 87 85

56.92 o, 62.52 o), which are attributed to Fe3O4 (JCPDS card No. 75-1069). From the XRD results it is
obvious that the peak intensity of Fe3O4 presents a decreasing trend with the increase of glucose content,
indicating that increasing glucose content in the catalyst reduces the nanoparticle size. This is consistent
with the SEM results. The diffraction peaks of NFC4 are very shallow and poorly resolved, and impure
FeCO3 phases are observed in the same patterns. As we known, decomposition of glucose may produce
some acids (acetic acid) and CO2, excess of which has a significant effect on the process of synthesis. The
crystallite size calculated using Scherer’s equation taking diffraction peak at 2 Theta = 43.5° is estimated
to be between 7 and 60 nm (Table 1).
Carbon species on the surface layers are analyzed by Raman spectrum. From Fig. 2b it can be found
that the diffraction peaks of Fe3O4 are observed for all of the catalysts. As glucose is added into the Fe 3O4
catalyst, two main peaks centered at 1357 cm−1 (D-band) and 1566 cm−1 (G-band) are appeared, which
are attributed to amorphous carbon. The peak intensity of surface amorphous carbon increases gradually
with the increasing glucose content. As the glucose content increases to 0.4 g, large amounts of
amorphous carbon are formed on the surface layers.
Peak G
i ͧaͨ
iFe3O4 i Fe3O4 Peak D
(b)
’FeCO3

i NFC4
i i
i
i i ii i
i
NFC0
Intensity (a.u.)

Intensity (a.u.)

NFC1 NFC3

NFC2
NFC2
NFC3
’ ’
NFC4 ’ NFC1

i NFC0
Fe3O4 JCPDS 75-1609 i i

200 400 600 800 1000 1200 1400 1600 1800

10 20 30 40 50 60 70 80
2 Theta (deg.) Raman Shift (cm-1)

Figure 2 X-Ray diffraction patterns and Raman spectrums of fresh NFC nanocatalysts with different
particle size (a, XRD patterns; b, Raman spectrums)
The analysis of NFC nanocatalysts prepared by the solvothermal method demonstrates that different
Fe3O4 particle sizes are obtained with various initial amounts of glucose added. In our system, glucose,
FeCl3 and urea are initially dissolved in deionized water and resulted in a homogeneous solution. The
Fe3O4 nanoparticles are formed via reduction of Fe3+ by EG under alkaline conditions obtained by the
decomposition of urea. When these small magnetic particles form in solution, they expose a reactive
surface outside, catalyze following the carbonization of glucose, and lead to in situ deposition of
carbonaceous products around the Fe3O4 particle surface for forming a carbonaceous shell. Large number
of Fe3O4 nanoparticles with higher surface energy aggregate rapidly. The amorphous carbon adsorbs on
the surface of Fe3O4 nanocrystal due to the carbonization of glucose, and presents the further aggregation.
The results show that glucose plays an essential role in preparation of NFC. Firstly, glucose supplies the
carbon source. Secondly, the adsorption of carbon onto the surface of Fe 3O4 nanocrystals prevents their
further aggregation, leading to monodisperse nanoparticles. Thirdly, the glucose can also decrease the
interfacial tension between the crystallizing phase and surrounding solution, and provide a high
nucleation frequency of the Fe3O4 product, leading to a small grain size.

3.3 Reduction and carburization behaviors

Reduction behaviour of NFC nanocatalysts is characterized by H2-TPR. The TPR patterns of NFC
catalysts exhibit two peaks at about 640-760 K and 700-1050 K, corresponding to the reduction of carbon
86 Junling Tu et al. / Energy Procedia 105 (2017) 82 – 87

shell and Fe3O4 → FeO + Fe, respectively. The first peak should not be considered as the reduction stage
of Fe2O3 to Fe3O4, and no reduction peak of carbon shell is observed for the NFC0 catalyst. As the
particle size of NFC catalyst increases, the second reduction peak moves to higher temperature. The
increased intensity of second peak suggests easy and more favored reduction for the smaller nanoparticles.
Phase transformation from the surface to bulk regions over the reduced catalysts is investigated
by X-Ray diffraction and Raman spectra (Figure 4). XRD patterns of the reduced samples are also
shown in Fig. 4a. A broad peak located at about 43º is attributed to iron carbides (especially χ-Fe5C2),
indicating that high concentration of iron carbides are formed after reduction. The peak intensity of iron
carbides presents a slightly increasing trend with the decreasing nanoparticle size, indicating that the
Fe3O4@C catalyst with smaller particle sizes is more favorable to the formation of iron carbides, which
are considered widely as active sites for FTS. From Fig. 4b it is seen that the amounts of amorphous
carbon present an increasing trend with the gradual addition of glucose.

(a)
ͧbͨ Peak G
Peak D
NFC4
NFC4

NFC4
NFC3
H2 Consumption (a.u.)

NFC3
Intensity (a.u.)

Intensity (a.u.)
NFC2 NFC3
NFC2

NFC1 NFC2
NFC1

NFC0
NFC1

Fe5C2
NFC0
JCPDS 200508 NFC0
400 500 600 700 800 900 1000 1100 1200 10 20 30 40 50 60 70 80
200 400 600 800 1000 1200 1400 1600 1800
Temperature (K) 2 Theta (deg.)
Raman Shift (cm-1)

Fig. 3 H2-TPR profiles Figure 4 X-Ray diffraction patterns and Raman spectrums of reduced
catalysts (a, XRD patterns; b, Raman spectrums)

3.4 FTS performances

The NFC nanocatalysts are tested in a fixed bed reactor at 553 K, 2.0 MPa under H 2/CO = 1 and
GHSV= 3000 ml/(gcat.h). The catalytic activities are expressed as moles of CO converted to
hydrocarbons per gram of iron per second (FTY) (shown in Figure 5). It is apparent that the Fe3O4
catalyst without adding glucose presents the lowest catalytic activity, and decreases gradually in activity
with time on stream. Compared to the Fe3O4 catalyst, the Fe3O4@C catalysts show higher activity and
excellent stability. Especially, the catalytic activity increases gradually with the addition of glucose in the
Fe3O4@C catalysts. As the content of glucose increases to 0.3 g, the catalytic activity of NFC3 reaches
the maximum value. However, as the adding content of glucose is excess, the catalytic activity (NFC4)
decreases obviously and deactivates quickly with time on stream, indicating that the excess adding of
glucose results in the formation of more carbon deposition on the surface of Fe 3O4@C, restraining the
catalytic activity.
The product distribution of hydrocarbons for NFC nanocatalysts is shown in Figure 6. The Fe3O4
catalyst (NFC0) presents the lowest CH4 selectivity and highest C5+ hydrocarbons selectivity. In contrast,
the Fe3O4@C catalysts facilitate the product distribution shifting towards light hydrocarbons.
Accompanied with the gradual increase of glucose content in the Fe 3O4@C catalysts, the selectivity of C2-
4 hydrocarbons presents an increasing trend.
 Junling Tu et al. / Energy Procedia 105 (2017) 82 – 87 87

55
3.5
50
3.0

Product selectivity (%)

45 methane
FTY (10-4molco/gFe s)

C2-4
2.5 40 C5+
35
2.0
30
1.5
25
NFC0
NFC1
1.0 NFC2 20
NFC3
NFC4 15
0.5
0 10 20 30 40 50 0 10 20 30 40 50 60 70
TOS (h)
Particle size (nm)

Fig. 5 Iron time yield with time on stream Fig. 6 Product selectivity of the catalysts

4. Conclusions

Size controllable Fe3O4 nanoparticles with carbon shell (NFCs) were prepared by the solvothermal
method. Specially, glucose was used to adjust the particle size in this work. An appropriate initial amount
of glucose (0.1-0.3 g) produces spherical nanoparticles with uniform size, however, excess of glucose
leads to non-uniform and aggregation of nanoparticles with high coverages of carbon on the active
surface. Furthermore, hollow Fe3O4 spheres with big size of 300 nm is obtained in the absence of glucose.
Bigger particles suppress the dispersion of active sites and smaller particle size accelerates the reduction
of active metal oxides, but smallest particles with high coverages of carbon on surface lead to loss of
active sites. Hence, optimal particles size is promising for FTS. The catalytic activity of Fe3O4@C
increases gradually with the addition of glucose, and reaches the maximum value as the adding content of
glucose increases to 0.3 g. In addition, the Fe3O4@C catalyst with higher glucose content facilitates the
product distribution shifting towards light hydrocarbons.

Acknowledgements

The authors gratefully acknowledge the financial support from the Natural Science Foundation of
China (U1362109, 51561145010), National Key Basic Research Program of China (No. 2013CB228105)
and the Science and Technology projects of Guangdong Province (2013B010405012, 2015A010106011).

References

[1] Kieffer M, Brown T, Brown RC. Flex fuel polygeneration: Integrating renewable natural gas into Fischer-Tropsch synthesis.
Appl Energ. 2016;170:208-18.
[2] Davis BH, Occelli ML. Fischer-Tropsch synthesis, catalysts and catalysis. Amsterdam: Elsevier; 2006.
[3] Dong HH, Xie MJ, Xu J, Li MF, Peng LM, Guo XF, et al. Iron oxide and alumina nanocomposites applied to Fischer-
Tropsch synthesis. Chemical Communications. 2011;47:4019-21.

Biography
Dr. Mingyue Ding, Professor, Doctor Tutor, engaged in the study on the key technology of
clean liquid fuels synthesis, system integration and engineering demonstration for biomass
conversion into higher alcohols, eher and hydrocarbons.