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Article history: The gas phase hydrodeoxygenation (HDO) of guaiacol, as a model compound for pyrolysis oil, was tested
Received 26 March 2010 on a series of novel hydroprocessing catalysts transition metal phosphides which included Ni2 P/SiO2 ,
Received in revised form 14 July 2010 Fe2 P/SiO2 , MoP/SiO2 , Co2 P/SiO2 and WP/SiO2 . The turnover frequency based on active sites titrated by
Accepted 21 July 2010
the chemisorption of CO followed the order: Ni2 P > Co2 P > Fe2 P, WP, MoP. The major products from
Available online 30 July 2010
hydrodeoxygenation of guaiacol for the most active phosphides were benzene and phenol, with a small
amount of methoxybenzene formed. Kinetic studies revealed the formation of reaction intermediates
Keywords:
such as catechol and cresol at short contact times. A commercial catalyst 5% Pd/Al2 O3 was more active
Hydrodeoxygenation
Guaiacol
than the metal phosphides at lower contact time but produced only catechol. A commercial CoMoS/Al2 O3
Biooil deactivated quickly and showed little activity for the HDO of guaiacol at these conditions. Thus, transition
Transition metal phosphides metal phosphides are promising materials for catalytic HDO of biofuels.
Ni2 P 2010 Elsevier B.V. All rights reserved.
CoMoS
0926-860X/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2010.07.039
306 H.Y. Zhao et al. / Applied Catalysis A: General 391 (2011) 305310
activated carbon, and the catalyst showed good stability and poten- silica by the incipient wetness method. The obtained samples were
tial for catalytic hydrotreating system [21]. Noble metal Pt as an dried and calcined at 500 C for 6 h, then ground with a mortar
active component was added to a conventional CoMoS catalyst and and pestle, pelletized with a press (Carver, Model C), and sieved to
showed no signicant improvement [17]. According to this study, particles of 6501180 m diameter (16/20 mesh). Second, the solid
monometallic and bimetallic noble metal catalysts supported on phosphates were reduced to phosphides at 2 C min1 in owing
zirconia have lower coke formation than a CoMoS/Al2 O3 catalyst H2 [1000 cm3 (NTP) min1 g1 ]. Reduction temperatures were
and in particular Rh-containing catalysts demonstrate potential in 568 C for Ni2 P/SiO2 , 680 C for Fe2 P/SiO2 , 680 C for Co2 P/SiO2 ,
biofuel upgrading. Given the propensity of biofuels to thermally 494 C for MoP/SiO2, and 527 C for WP/SiO2 . The samples were
decompose to form coke and coke-like matter, catalysts with sup- kept at the reduction temperature for 2 h, followed by cooling to RT
ports that are less active for coke formation or more hydrogenating under He ow [100 cm3 (NTP) min1 ], and then were passivated
catalysts permitting a rapid transformation of dioxygenated reac- at RT in a 0.5% O2 /He for 4 h. The Ni, Fe, Mo, Co, W molar loading
tants (guaiacol, catechol) into less coke-forming products (phenol) were all 1.6 mmol g1 (mmol per g of support), corresponding to
would be highly desirable. a weight loading of Ni2 P of 8.6% with an initial Ni/P ratio of 1/2,
Hydrodeoxygenation of actual biooils has been studied with Fe2 P of 8.3% with an initial Fe/P ratio of 1/2, MoP 12.8% with initial
two stages because of the thermal instability of the oil [22]. In Mo/P ratio of 1, Co2 P of 8.6% with initial Co/P ratio 1, WP 19.9%
a rst stage, a stabilization process was carried out at low tem- with initial W/P ratio 1.
perature to eliminate reactive compositions like ketones. In a
second stage, deoxygenation of the phenolic-type molecules was 2.3. Characterization
carried at higher temperatures. Using diluted model oxygenated
compound solutions for hydrodeoxygenation study will give more Irreversible CO uptake measurements were used to titrate the
precise chemical information and avoid thermal polymerization surface metal atoms and to provide an estimate of the active sites
reactions [23]. In the present study, guaiacol (methoxyphenol) on the catalysts for the noble metals and the transition metal phos-
is chosen as model compound for hydrodeoxygenation because phides. Usually, 0.3 g of a passivated sample was loaded into a
guaiacol and substituted guaiacols constitute a relatively high con- quartz reactor. Noble metal catalysts were reduced in H2 at 325 C
centration of the lignin-derived fraction (up to 0.5 wt%) and these for 2 h while passivated transition metal phosphides were reduced
have a high tendency to coke. Guaiacols contains two different at 450 C for 2 h with H2 at 300 ml (NTP) min1 . After cooling in He,
oxygenated functions (phenolic and methoxy groups), so are chal- pulses of CO in a He carrier at 43 mol s1 [65 cm3 (NTP) min1 ]
lenging molecules to completely deoxygenate. Transition metal were injected at RT through a sampling valve, and the mass 28
phosphides supported on neutral silica are a promising class of new (CO) signal was monitored with a mass spectrometer. CO uptake
hydroprocessing catalysts [24,25], and it was of interest to investi- was calculated by measuring the decrease in the peak areas caused
gate them for guaiacol catalytic hydrodeoxygenation in comparison by adsorption in comparison with the area of a calibrated vol-
to commercial catalysts such as CoMoS/Al2 O3 and 5% Pd/Al2 O3 . ume (19.5 mol). Low temperature O2 chemisorption was used for
CoMo/Al2 O3 applying the same technique. Prior to the measure-
ment the sample was sulded in a ow of 10% H2 S/H2 at 400 C.
2. Experimental
Surface areas of the samples were obtained using the BET
method based on adsorption isotherms at liquid nitrogen temper-
2.1. Materials
ature, and using a value of 0.162 nm2 for the cross-sectional area of
a N2 molecule. The measurements were performed in a volumetric
The 5% Pd/Al2 O3 commercial catalyst was provided by BASF
adsorption unit (Micromeritics ASAP 2000). X-ray diffraction (XRD)
Catalysts, In. and the CoMo/Al2 O3 hydrotreating catalyst was pro-
patterns of the samples were obtained with PANalytical Xpert Pro
vided by Haldor Topse. Transition metal phosphides Ni2 P/SiO2 ,
powder diffractometer operated at 45 kV and 40 mA, using Cu K
Fe2 P/SiO2 , MoP/SiO2 , Co2 P/SiO2 and WP/SiO2 were synthesized as
monochromatized radiation ( = 0.154178 nm).
will be described below, using a fumed silica EH-5 support provided
by Cabot Corp. The chemicals used in the synthesis of the cata-
2.4. Reactivity studies
lysts were Ni(NO3 )2 6H2 O (Alfa Aesar, 99%), Fe(NO3 )3 9H2 O (Alfa
Aesar, 99%), (NH4 )6 Mo7 O24 4H2 O (Alfa Aesar, 99%), Co(NO3 )2 6H2 O
Hydrodeoxygenation activity was measured in a packed bed
(Alfa Aesar, 99%), (NH4 )6 W12 O39 xH2 O (Aldrich, 99%), (NH4 )2 HPO4
reactor at atmospheric pressure. Guaiacol was introduced by means
(Aldrich, 99%). The chemicals used for the reactivity tests were
of a saturator at 25 C with a concentration of 0.024 mol%. The
guaiacol (Alfa Aesar, 98%). The gases employed were H2 (Airco,
dimensions of the reactors were 1.5 cm i.d. 25.5 cm long, and were
Grade 5, 99.99%), He (Airco, Grade 5, 99.99%), CO (Linde Research
loaded with 30 mol active sites. To start a reaction, catalysts were
Grade, 99.97%), 0.5% O2 /He (Airco, UHP Grade, 99.99%), O2 (Airco,
placed in the catalytic reactor and pretreated at the same condi-
UHP Grade, 99.99%), N2 (Airco, Grade 5, 99.99%). Chemical stan-
tions as used for chemisorption. After pretreatment, a ow mixture
dards for GC and mass spectrometry were benzene, phenol, toluene,
of hydrogen and nitrogen at a ratio of 4 to 1 saturated with guaiacol
methoxybenzene (Alfa Aesar, 98%), cyclohexane (Alfa Aesar, 99%).
was introduced at 150 cm3 (NTP) min1 . The hydrogen to guaiacol
molar ratio was 33. The catalysts were stabilized for 6 h after the
2.2. Metal phosphides synthesis feed was introduced. Then samples were taken every 23 h until the
conversion of guaiacol reached steady-state. Reactivity testing was
Ni2 P/SiO2 [2628], Fe2 P/SiO2 [27], MoP/SiO2 [29,30], Co2 P/SiO2 performed as a function of temperature, starting at the highest tem-
[27] and WP/SiO2 [31] were prepared by temperature-programmed perature of 300 C and was varied downwards and upwards with
reduction (TPR), following procedures reported previously the initial temperature repeated at the end. Generally it took about
[32,33]. Briey, the synthesis of the catalysts involved two 100 h of on-stream time to collect the rate data at several different
stages. First, solutions of the corresponding metal phos- temperatures. The reaction products were analyzed using an online
phate precursors were prepared by dissolving appropriate gas chromatograph (HewlettPackard, 5890A) equipped with a
amounts of Ni(NO3 )2 6H2 O, Fe(NO3 )3 9H2 O, (NH4 )6 Mo7 O24 4H2 O, 0.32 mm i.d. 50 m fused silica capillary column and a ame ioniza-
Co(NO3 )2 6H2 O, (NH4 )6 W12 O39 xH2 O, with ammonium phosphate tion detector. The reactants and products were identied by their
in distilled water, and these solutions were used to impregnate retention time in comparison with commercially available stan-
H.Y. Zhao et al. / Applied Catalysis A: General 391 (2011) 305310 307
Turnover frequency [s1 ] Co2 P/SiO2 < Fe2 P/SiO2 < WP/SiO2 < Ni2 P/SiO2 < MoP/SiO2 assuming
that each active site adsorbs one CO molecule. The particle size
Reactant owrate [mol/s] conversion (d) was then calculated using equation d 0.9/D. It was found that
=
Quantity of sites [mol/g] Catalyst weight [g] nickel and molybdenum formed much smaller particles and were
better dispersed than the other transition metal phosphides. Except
The turnover frequency was calculated to compare the intrinsic for WP/SiO2 , all other transition metal phosphides show fairly high
activity of different catalysts. BET surface area.
3.1. CO chemisorption and BET areas X-ray diffraction (XRD) was used to ascertain the phase and
phase composition of the synthesized transition metal phos-
Table 1 reports uptakes of CO at room temperature for the metal phides by comparing with the standard powder diffraction patterns
phosphide catalysts and the noble metal and uptakes of O2 at dry- (Fig. 1). The diffraction pattern for silica supported nickel phos-
ice acetone temperature for CoMoS/Al2 O3 . Table 1 also provides BET phide shows three major peaks at 40.5 , 44.8 and 47.5 , which
characterization results. Earlier studies have shown that uptakes line up well with the standard pattern for Ni2 P. The peaks are
of the SiO2 and Al2 O3 were negligible [3436]. The CO chemisorp- signicantly broadened indicating that small Ni2 P crystals were
tion uptakes of the different samples varied in a wide range from formed. The three major peaks for cobalt phosphide line up well
42 to 200 mol/g. The dispersion (D) of metal sites was estimated with the standard Co2 P pattern suggesting that the major phase is
from the CO uptakes and the known loading of the samples (in all Co2 P in our synthesis, which is consistent with result reported by
cases 1.16 mmol g1 of total metal). The order of dispersion was Bussell that Co2 P is obtained by using a Co/P ratio of 1 [37]. The
Table 2
Activation energy for guaiacol reaction on transition metal phosphide catalysts.
Ni2 P/SiO2 31 52 65 85 93 40
Co2 P/SiO2 21 39 61 77 82 52
WP/SiO2 9 12 22 59 23
a
Fe2 P/SiO2 15 70
MoP/SiO2 10 14 19 50 63
a
Not calculated because of deactivation.
Table 3
Products distribution for HDO of guaiacol with a concentration of 0.024 mol% at 300 C, atmosphere pressure, at contact time 20.2 min and space velocity 1.4 h1 .
Ni2 P/SiO2 80 30 60 10 0 0
Co2 P/SiO2 70 32 52 1 0 15
Fe2 P/SiO2 64 94 0 6 0 0
WP/SiO2 60 100 0 0 0 0
MoP/SiO2 54 28 53 0 4 15
H.Y. Zhao et al. / Applied Catalysis A: General 391 (2011) 305310 309
Table 4
Effect of contact time on conversion of guaiacol and products distribution at 300 C.
Catalyst Contact time (min) Space velocity (h1 ) Conversion (%) Product distribution (%)
carbons [4144]. This reaction sequence suggests that catechol is methoxy group by hydrogenolysis of the aromatic carbonoxygen
the primary reaction product, which is transformed to phenol. Our bond [17].
results did not show catechol as a product for HDO of guaiacol in In the case of Co2 P/SiO2 , the products were 99% catechol and
all cases. Thus reactivity tests with lower contact time were carried only 1% phenol at lower contact time compared with 94% phe-
out to identify the reaction intermediates and the possible reac- nol and 6% methoxybenzene at higher contact time. With WP/SiO2 ,
tion pathway (Table 4). The contact time dened in the following at lower contact time 88% catechol was observed instead of 100%
equation, was decreased from 20.2 to 0.339 min phenol. Thus, the intermediate catechol was observed for HDO of
guaiacol at lower contact time. The results indicate that the rst
Contact time [min] bond to be broken is the bond between the oxygen and the methyl
Quantity of sites [mol/g] Catalyst weight [g] carbon, which is depicted in the reaction scheme illustrated in Fig. 3
= which shows the possible reaction pathway on transition metal
Reactant owrate [mol/min]
phosphides. The scheme was adapted from results of this study as
well as work from others. Cyclohexanol was proposed as an inter-
Three catalysts Ni2 P/SiO2 , Co2 P/SiO2 , WP/SiO2 were chosen for
mediate in the HDO of phenol [45], while cresol was reported in
the lower contact time reactivity tests because they had the high-
several studies [11,40].
est activity and showed minimal deactivation. As the contact time
decreased from 20.2 to 0.339 min, the conversion of HDO guaiacol
decreased signicantly for all the catalysts, as expected. However, 3.3.3. HDO activity comparison
the decrease of the contact time from 20.2 to 0.339 min was not The commercial catalysts Pd/Al2 O3 and CoMo/Al2 O3 were also
accompanied by a linear decrease of the conversion. Instead, the tested for the HDO of guaiacol at the lower contact time 0.339 min
conversion of guaiacol at the contact time of 0.339 min was higher at 300 C to compare with the transition metal phosphides. The
than expected, and this could be because the reactor operated in results are summarized in Table 5. The catalyst Pd/Al2 O3 is more
integral manner (at high conversion) and there may have been active in terms of guaiacol conversion at 70% than the most active
product inhibition by water. transition metal phosphide Co2 P/SiO2 with 35% conversion. How-
In the case of Ni2 P/SiO2 a new product, cresol, was observed ever, catechol was the only product for conversion of guaiacol with
and more methoxybenzene was formed while less benzene Pd/Al2 O3 . Catechol easily leads to coking, and this may explain the
was produced. Selectivity towards phenol was 28%, which was lower performance of the Pd catalyst. With CoMoS/Al2 O3 the con-
almost the same as at higher contact time, but no catechol was version rate of guaiacol decreased quickly and almost no conversion
observed. This result might be due to a direct elimination of the was observed for guaiacol. The deactivation may have two origins
Table 5
Activity comparison between transition metal phosphides and commercial catalysts at contact time 0.339 min and space velocity 59 h1 at 300 C.
Ni2 P/SiO2 19 28 4 38 0 30
Co2 P/SiO2 35 1 0 0 99 0
WP/SiO2 12 12 0 0 88 0
5% Pd/Al2 O3 70 0 0 0 100 0
CoMo/Al2 O3 1 0 0 100 0 0
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