Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Fuel
journal homepage: www.elsevier.com/locate/fuel
h i g h l i g h t s
Coking tendency and aromatic structures of bio-oil change during hydrotreatment.
Repolymerisation surpasses the hydrogenation of bio-oil at mild conditions.
Coking tendency is reduced under severe hydrotreating conditions.
Combined esterication and hydrotreatment can produce more stable biofuel.
a r t i c l e
i n f o
Article history:
Received 24 December 2012
Received in revised form 10 August 2013
Accepted 15 August 2013
Available online 5 September 2013
Keywords:
Bio-oil
Upgrading
Hydrotreatment
Esterication
Coke
a b s t r a c t
This study has investigated the hydrotreatment of bio-oil (derived from the fast pyrolysis of mallee
woody biomass) in a batch reactor under 10 MPa pressure with Pd/C catalyst at temperatures between
150 C and 300 C. Our results indicate that the chemical fractions, coking tendency as well as the aromatic structures are highly inuenced by the hydrotreating conditions such as temperature and time.
The repolymerisation surpasses the hydrogenation of bio-oil at the low hydrotreating temperatures
(e.g. 150200 C) and short hydrotreating durations (e.g. <3 h). On the contrary, high hydrotreating temperatures (e.g. 250300 C) and long reaction durations (e.g. 612 h) can effectively convert the heavier
fractions into lighter fractions, and thus further reduce the coking tendency of the hydrotreated products.
However, these harsh operational conditions cannot decrease the number of large aromatic ring systems.
Most importantly, it is found that the combination of esterication and hydrotreatment can produce
more stable bio-oil with lower coking tendency and less large aromatic ring systems than the direct
hydrotreatment of bio-oil.
2013 Elsevier Ltd. All rights reserved.
1. Introduction
The fast pyrolysis of biomass is one of the most promising biofuel technologies to produce liquid bio-oil and solid bio-char.
While the bio-char is returned to the eld as a soil conditioner
and for carbon bio-sequestration, bio-oil can be converted to green
transport biofuels or feedstocks for gasiers/boilers [1]. However,
bio-oil is a complex mixture of hundreds of chemicals. It not only
has high acidity and water content, but also shows high thermal
instability and polymerisation tendency [2]. Therefore, bio-oil
must be upgraded signicantly to improve its physical and chemical properties before it can be used as a liquid fuel [3].
Corresponding author. Tel.: +61 8 9266 1131; fax: +61 8 9266 1138.
E-mail address: chun-zhu.li@curtin.edu.au (C.-Z. Li).
0016-2361/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2013.08.046
Various severe bio-oil upgrading processes have been investigated including hydrodeoxygenation, hydrocracking and high
pressure thermal treatment (HPTT) [310]. However, the major
problem in these upgrading processes is the deactivation of catalysts due to formation of heavy tar and coke from the bio-oil. A
two-stage hydrotreatment process using conventional petroleum
HDS catalysts (such as sulphided NiMo/Al2O3 and CoMo/Al2O3) in
continuous process has been proposed by Elliott et al. [3,5,11],
which appeared to be the most effective process so far to avoid
excessive coking. However, extremely long reaction times and
excessive hydrogen consumption were always required to reach
high deoxygenation levels, indicating the low activity of the
petroleum hydrotreating catalysts. Therefore, some noble-metal
catalysts (such as Ru, Pt and Pd) on various supports (such as alumina, carbon and titanium) were explored for the hydrotreatment
of bio-oil and model compounds [6]. It was found that the Ru/C and
Pd/C catalysts presented much higher oil yields and the deoxygenation levels compared with other noble-metal catalysts. Unfortunately, various quantities of coke/solid were unavoidably formed
during the hydrotreatment of bio-oil with the noble-metal catalysts, though this was highly dependent on the operational
conditions.
To date insufcient study has been carried out on the mechanism of coke formation on catalyst during the hydrotreatment of
bio-oil [12,13]. Especially, little is known about the relationship between the coking tendency and the transformation of aromatic
compounds as well as the high molecular weight species in the
bio-oil, which are believed to be the most important precursors
of coke formation. UV-uorescence spectroscopy has been successfully used to analyse the concentration and relative size of aromatic ring structures in bio-oil. Thermogravimetric analysis
(TGA) has been widely employed as a good indicator of the distribution of chemical fractions in bio-oil based on their different volatility [1420]. The combination of these two instrumental
techniques is believed to be greatly benecial in understanding
the formation of coke on catalysts by elucidating the formation
of aromatic structures and the fate of high molecular weight species in the bio-oil.
According to our recent study, the polymerisation of lignin-derived oligomers during the pyrolysis of bio-oil can be greatly enhanced by the cellulose/hemicelluloses-derived species in the
bio-oil [18]. Interestingly, we also found that highly reactive species in bio-oil such as carboxylic acids, aldehydes and even simple
sugars (which are typical cellulose/hemicelluloses-derived species)
can be easily stabilised by catalytic esterication under mild conditions [20,21]. In order words, the esterication can effectively reduce the number of reactive species in the bio-oil and thus should
decrease coke formation on catalyst during the further hydrotreatment of esteried bio-oil. To our best knowledge, no one has conducted such two-step upgrading of bio-oil (including initial
esterication and nal hydrotreatment) to investigate the changes
in chemical fractions, aromatic structures as well as coking tendency during the upgrading process.
The objective of this study is to investigate the changes in cokeforming propensity and aromatic structures during the catalytic
hydrotreatment of fast pyrolysis bio-oil under various upgrading
temperatures and durations. Especially, the esteried bio-oil was
hydrotreated under the same conditions as the raw bio-oil for
exploring more effective upgrading technology to minimise the
coking problem. We have chosen the Pd/C catalyst that has shown
good activities for the hydrotreatment of bio-oil [6]. Screening the
performance of various catalysts is beyond the scope of this study.
While the different chemical fractions and coking tendency of
hydrotreated bio-oil were characterised with TGA, UV-uorescence spectroscopy was employed to trace the overall changes in
aromatic ring systems in the hydrotreated products.
643
644
that the catalyst was active even at very low temperature (e.g.
150 C). In particular, the catalyst must have been able to activate
hydrogen to produce active hydrogen at these low temperatures.
The active hydrogen could then react with the bio-oil molecules
(or fragments) adsorbed on the catalyst to cause their hydrogenation, including hydrodehydrogenation.
It was found that the overall liquid mass balance closure was
more than 80 wt%, and the difference between the liquid products
and the raw bio-oil was mainly due to the formation of gases, solids/cokes and unavoidable losses during the collection of products.
It was clearly shown that the liquid phase distribution remained
relatively stable with increasing hydrotreating temperature and
time [see Fig. 1ac]. However, the amounts of oil and aqueous
phases gradually declined with increasing esterication temperature from 90 C to 170 C as shown in Fig. 1d. This is possibly
caused by the loss of bio-oil fraction during esterication and distillation process. According to our previous study, some medium or
heavy fractions in bio-oil can be converted into lighter fractions
during esterication, which were subsequently removed during
vacuum distillation [20]. Although the direct gas yield was not
measured during the experiment, it may indirectly be deduced that
the gas yield increased gradually with increasing hydrotreating
temperature and time, since the difference between the total liquid
product yields and the raw bio-oil present a similar increasing
trend. A possible explanation is the occurrence of catalytic decarboxylation/decarbonylation to produce gaseous components (such
as CO2, CO and CH4) at higher temperatures and longer reaction
times, as reported previously [3,6]. The direct coke formation
Fig. 1. Phase distribution of liquid products after the hydrotreatment of bio-oil as a function of (a) temperature, (b) time at 250 C, (c) time at 300 C and (d) effects of
esterication.
645
during hydrotreatment was only determined for duplicated experiments at 250 C and 300 C, which are 1.20 wt% and 1.22 wt%,
respectively. This is in good agreement with literature reporting
that a Pd/C catalyst gave a low coke yield during the hydrotreatment of bio-oil [6].
(a)
(b)
(c)
(d)
Fig. 2. Effects of hydrotreating temperature on (a) the DTG curves of aqueous phase, (b) the DTG curves of oil phase, (c) the DTG curves of sums of all phases and (d) the
potential coke yield of the bio-oil after hydrotreatment for 3 h.
646
instability and polymerisation tendency, which is in good agreement with other reports [6,22]. For the bio-oils hydrotreated at
200 C and 250 C, a signicant increase in light fractions with boiling points around 100 C is observed, implying large amounts of
water and volatiles were produced via hydrodeoxygenation of oxygen-containing compounds. The medium fractions in these two
hydrotreated samples, however, decreased in TGA temperature
range of 150300 C and then increased rapidly in the temperature
range of 320420 C. Moreover, their heavy fractions and total potential coke yields [56 wt% in Fig. 2d] both reduced to a similar level, which implies that the hydrotreatment of bio-oil at mild
temperature (between 200 C and 250 C) would only marginally
reduce the polymerisation tendency and improve the thermal stability. Although the DTG curve of bio-oil hydrotreated at 300 C is
similar to the lower hydrotreating temperature samples, the higher
magnitude of light fractions and medium fraction (with TGA temperature below 250 C) were observed in this sample. Surprisingly,
the total potential coke yield decreased to 2 wt%, which suggests
that a higher hydrotreating temperature (such as 300 C) would
effectively convert the heavy fractions into lighter ones through
hydrodeoxygenation and/or hydro-cracking and thus reduce the
coking tendency in the hydrotreated product.
Due to the negligible uorescence intensity in the aqueous
phase of hydrotreated bio-oil, Fig. 3 only compares the synchronous spectra of oil phase products at various hydrotreating temperatures. The raw bio-oil clearly shows three broad peaks
centred at 270280 nm, 320330 nm and 350360 nm in the synchronous spectra. Especially, the peak at 350360 nm is always
more intense than the other two peaks, implying the presence of
abundant large aromatic ring systems (e.g. two or more fused benzene rings) in the raw bio-oil which are normally originated from
lignin-derived oligomers [14,17,18]. The synchronous spectra for
the hydrotreated bio-oil samples, however, mainly present two
peaks centred around 270280 nm and 320330 nm. With increasing hydrotreatment temperature from 150 C to 300 C, the rst
peak (around 270280 nm) showed negligible change at temperature lower than 250 C, but it increased signicantly to a large value at a hydrotreating temperature of 300 C. In contrast, the
second peak (around 320330 nm) tended to increase monotonically with hydrotreating temperature. It is also interesting to see
that hydrotreated samples between 150 C and 200 C presented
relatively low uorescence intensity compared with the spectrum
of raw bio-oil, possibly due to the polymerisation of small ring systems into extremely large ring systems and/or cokes which are beyond the detection limit of the current synchronous spectral
method. However, the hydrotreated samples at 300 C not only
showed almost double the uorescence intensity of raw bio-oil,
Fig. 4. Effects of hydrotreating time on (a) the DTG curves of aqueous phase, (b) the
DTG curves of oil phase and (c) the potential coke yield of bio-oil after
hydrotreatment at 250 C.
It is necessary to point out that around 40 wt% of the total hydrotreated products has been transferred into aqueous phase [see
Fig. 1b] due to the polarity change after hydrotreatment. Based
on the DTG curves in Fig. 4a, it is believed that most of the aqueous
phase products are light and medium fractions. Therefore, it is
understandable that the oil phase products in Fig. 4b might contain
much smaller amounts of light and medium fractions in comparison to the raw bio-oil. With increasing reaction time, only a
slightly increasing trend was displayed in the aqueous phase samples, as shown in Fig. 4a. In the oil phase [see Fig. 4b], however, the
amount of light fractions gradually increased while the medium
and heavy fractions reduced comparably with the reaction time.
As expected, the potential coke yields greatly declined with
increasing reaction time, as shown in Fig. 4c, which conrms that
a longer reaction time would effectively reduce the heavy fractions
and coking tendency of hydrotreated product. However, the potential coking yields for the rst 3 h are fairly constant at around
5 wt%, which was almost three times higher than the samples in
the period 612 h (about 1.5 wt%). A closer examination of the
DTG curves of the samples after the rst 3 h also reveals that the
medium and heavy fractions (with TGA temperature higher than
300 C) rose to a higher level compared against other samples, possibly due to the formation of intermediate components (e.g. low
molecular oligomer) via the breakdown of heavy fractions (e.g.
high molecular oligomer).
In Fig. 5, the synchronous spectra for hydrotreated bio-oil samples (oil phase only) at 250 C are shown as a function of reaction
time with an energy difference of 2800 cm 1. The major peaks of
hydrotreated samples are centred around 270280 nm and 320
330 nm, and the latter shows much higher intensity than the former. Compared with the raw bio-oil, the hydrotreated samples
show slightly higher intensity at both peaks. However, the peak
centred around 350360 nm in the raw bio-oil is scarcely present
in the hydrotreated samples, except for the sample obtained after
a reaction time of 3 h. This trend coincides with the changes in
the shape of DTG curves after rst 3 h as shown in Fig. 4b, indicating some intermediate aromatic ring systems could be derived
from the cracking/hydrogenation of large ring systems at the initial
stage (e.g. rst 3 h) of hydrotreatment at 250 C. With increasing
reaction time between 6 h and 12 h, both peaks in hydrotreated
samples gradually increased to an identical (maximum) intensity.
This result is also consistent with the coke tendency data in
Fig. 4c, where the potential coke yield of oil phase was stable
around 1 wt% at hydrotreating period from 6 to 12 h.
647
The DTG curves and coking tendency of the bio-oils hydrotreated at 300 C are shown as a function of reaction time in Fig. 6. Since
the aqueous phase showed almost identical DTG curves in Fig. 6a
and the similar potential coke yields in Fig. 6c for each other, only
the oil phase products will be compared in details in this section.
Similar to the bio-oil hydrotreated at 250 C in Fig. 4, the amount
of light fraction in oil phase slightly increased along with reaction
time, while the medium and heavy fractions gradually decreased.
Fig. 6. Effects of hydrotreating time on (a) the DTG curves of aqueous phase, (b) the
DTG curves of oil phase and (c) the potential coke yield of bio-oil after
hydrotreatment at 300 C.
648
(a)
Fig. 7. Effects of hydrotreating time on the synchronous spectra (with a constant
energy of 2800 cm 1) of bio-oil after hydrotreatment at 300 C.
(b)
(c)
Fig. 8. Effects of esterication on (a) the DTG curves of aqueous phase, (b) the DTG
curves of oil phase and (c) the potential coke yield of bio-oil after hydrotreatment at
300 C for 3 h.
649
tendency and less large aromatic ring systems than the directly
hydrotreated bio-oil.
Acknowledgments
Australian Government funding through the Second Generation
Biofuels Research and Development Grant Program supports this
project. The study also received support from the Government of
Western Australia via the Centre for Research into Energy for Sustainable Transport (CREST).
References
[1] Mohan D, Pittman Jr CU, Steele PH. Pyrolysis of wood/biomass for bio-oil: a
critical review. Energy Fuels 2006;20:84889.
[2] Huber GW, Iborra S, Corma A. Synthesis of transportation fuels from biomass:
chemistry, catalysts, and engineering. Chem Rev 2006;106:404498.
[3] Elliott DC. Historical developments in hydroprocessing bio-oils. Energy Fuels
2007;21:1792815.
[4] Oasmaa A, Kuoppala E, Ardiyanti A, Venderbosch RH, Heeres HJ.
Characterization of hydrotreated fast pyrolysis liquids. Energy Fuels
2010;24:526472.
[5] Elliott DC, Hart TR, Neuenschwander GG, Rotness LJ, Zacher AH. Catalytic
hydroprocessing of biomass fast pyrolysis bio-oil to produce hydrocarbon
products. Environ Progr Sustain Energy 2009;28:4419.
[6] Wildschut J, Mahfud FH, Venderbosch RH, Heeres HJ. Hydrotreatment of fast
pyrolysis oil using heterogeneous noble-metal catalysts. Ind Eng Chem Res
2009;48:1032434.
[7] Venderbosch RH, Ardiyanti AR, Wildschut J, Oasmaa A, Heeres HJ. Stabilization
of biomass-derived pyrolysis oils. J Chem Technol Biotechnol 2010;85:67486.
[8] de Miguel Mercader F, Groeneveld MJ, Kersten SRA, Venderbosch RH,
Hogendoorn JA. Pyrolysis oil upgrading by high pressure thermal treatment.
Fuel 2010;89:282937.
[9] Ardiyanti AR, Gutierrez A, Honkela ML, Krause AOI, Heeres HJ. Hydrotreatment
of wood-based pyrolysis oil using zirconia-supported mono- and bimetallic
(Pt, Pd, Rh) catalysts. Appl Catal A: Gen 2011;407:5666.
[10] Samolada MC, Baldauf W, Vasalos IA. Production of a bio-gasoline by
upgrading biomass ash pyrolysis liquids via hydrogen processing and
catalytic cracking. Fuel 1998;77:166775.
[11] Elliott DC, Neuenschwander GG. Liquid fuels by low-severity hydrotreating of
biocrude. In: Bridgwater AV, Boocock DGB, editors. Developments in
thermochemical biomass conversion, vol. 1. London: Blackie Academic &
Professional; 1996. p. 61121.
[12] Laurent E, Centeno A, Delmon B, Delmon B, Froment GF. Coke formation during
the hydrotreating of biomass pyrolysis oils: inuence of guaiacol type
compounds. In studies in surface science and catalysis, vol. 88. Elsevier;
1994. p. 5738.
[13] Wildschut J, Arentz J, Rasrendra CB, Venderbosch RH, Heeres HJ. Catalytic
hydrotreatment of fast pyrolysis oil: model studies on reaction pathways for
the carbohydrate fraction. Environ Progr Sustain Energy 2009;28:45060.
[14] Min Z, Asadullah M, Yimsiri P, Zhang S, Wu H, Li CZ. Catalytic reforming of tar
during gasication. Part I. Steam reforming of biomass tar using ilmenite as a
catalyst. Fuel 2011;90:184754.
[15] Min Z, Yimsiri P, Asadullah M, Zhang S, Li CZ. Catalytic reforming of tar during
gasication. Part II. Char as a catalyst or as a catalyst support for tar reforming.
Fuel 2011;90:254552.
[16] Garcia-Perez M, Wang S, Shen J, Rhodes M, Lee WJ, Li C-Z. Effects of
temperature on the formation of lignin-derived oligomers during the fast
pyrolysis of mallee woody biomass. Energy Fuels 2008;22:202232.
[17] Garcia-Perez M, Wang XS, Shen J, Rhodes MJ, Tian F, Lee W-J, et al. Fast
pyrolysis of oil malee woody biomass: effect of temperature on the yield and
quality of pyrolysis products. Ind Eng Chem Res 2008;47:184654.
[18] Wang Y, Li X, Mourant D, Gunawan R, Zhang S, Li C-Z. Formation of aromatic
structures during the pyrolysis of bio-oil. Energy Fuels 2012;26:2417.
[19] Garcia-Perez M, Chaala A, Pakdel H, Kretschmer D, Roy C. Characterization of
bio-oils in chemical families. Biomass Bioenergy 2007;31:22242.
[20] Li X, Gunawan R, Lievens C, Wang Y, Mourant D, Wang S, et al. Simultaneous
catalytic esterication of carboxylic acids and acetalisation of aldehydes in a
fast pyrolysis bio-oil from mallee biomass. Fuel 2011;90:25307.
[21] Gunawan R, Li X, Larcher A, Hu X, Mourant D, Chaiwat W, et al. Hydrolysis and
glycosidation of sugars during the esterication of fast pyrolysis bio-oil. Fuel
2012;95:14651.
[22] Ardiyanti AR, Venderbosch RH, Heeres HJ. In process-product studies on
pyrolysis oil upgrading by hydrotreatment with Ru/C catalysts. In: Conference
proceedings 2009 AIChE spring national meeting and 5th global congress on
process safety, 2009.